WO2016061712A1 - 一种阴离子-阳离子-非离子型表面活性剂、其制造方法及其应用 - Google Patents

一种阴离子-阳离子-非离子型表面活性剂、其制造方法及其应用 Download PDF

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WO2016061712A1
WO2016061712A1 PCT/CN2014/000939 CN2014000939W WO2016061712A1 WO 2016061712 A1 WO2016061712 A1 WO 2016061712A1 CN 2014000939 W CN2014000939 W CN 2014000939W WO 2016061712 A1 WO2016061712 A1 WO 2016061712A1
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group
optionally substituted
straight
branched
linear
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PCT/CN2014/000939
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English (en)
French (fr)
Inventor
李应成
顾松园
张卫东
鲍新宁
沙鸥
沈之芹
杨一青
翟晓东
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CA2958914A priority Critical patent/CA2958914C/en
Priority to RU2017108635A priority patent/RU2668104C1/ru
Priority to PCT/CN2014/000939 priority patent/WO2016061712A1/zh
Priority to MYPI2017701401A priority patent/MY173019A/en
Priority to US15/520,377 priority patent/US10400156B2/en
Priority to MX2017005272A priority patent/MX2017005272A/es
Publication of WO2016061712A1 publication Critical patent/WO2016061712A1/zh
Priority to NO20170531A priority patent/NO20170531A1/en
Priority to US16/509,057 priority patent/US11186764B2/en
Priority to US17/451,086 priority patent/US20220033705A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C237/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
    • C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/20—Displacing by water

Definitions

  • This invention relates to an anionic-cationic-nonionic surfactant.
  • the present invention relates to an anionic-cationic-nonionic surfactant useful for tertiary oil recovery, a process for its manufacture and its use in tertiary oil recovery.
  • the tertiary oil recovery technology is an effective method to increase the oil recovery rate.
  • chemical flooding technology is a very important and large-scale implementation technology in tertiary oil recovery, including polymer flooding technology, surfactant flooding technology, alkaline water flooding technology, etc., as well as polymers, alkalis and surfactants.
  • Chemical flooding is the result of both physical and chemical interactions. The physical action utilizes the sweeping effect of the displacement fluid, while the chemical action utilizes the microscopic oil displacement of the displacement fluid. The core of the chemical action is to reduce the interfacial tension between the displacement fluid and the crude oil.
  • Surfactants have both oleophilic (hydrophobic) and hydrophilic (oleophobic) properties.
  • the molecules When the surfactant is dissolved in water, the molecules are mainly distributed at the oil-water interface, which can significantly reduce the oil-water interfacial tension.
  • the decrease in oil-water interfacial tension means that the surfactant system can overcome the cohesive force between crude oils and disperse large oil droplets into small oil droplets, thereby increasing the passage rate of crude oil flowing through the pore throat.
  • the oil displacement effect of the surfactant is also manifested in the reversal of the wettability of the oleophilic rock surface, the emulsification of the crude oil, the increase of the surface charge density and the oil droplets, etc., which is the role of the surfactant in the displacement fluid. The cause of the component of action.
  • the prior art tertiary oil displacement fluid has many problems, mainly due to the poor interfacial activity of the surfactant component, resulting in low displacement efficiency of the displacement fluid produced therefrom, and at the same time due to the displacement fluid system. It is too complicated, so it is difficult to break the milk, and the sewage treatment is difficult. Because the displacement fluid contains inorganic alkali, it will cause damage to the formation and the oil well, causing problems such as corrosion equipment and pipelines, and the inorganic base will seriously reduce the polymer.
  • Viscosity in order to achieve the desired viscosity, only greatly increase the concentration of the polymer used, so that the overall cost of oil recovery is increased; the surfactant component has limited ability to resist high temperature, high salt resistance and high salinity; surfactant component It has poor stability during compounding and is prone to precipitation.
  • the present inventors have diligently studied on the basis of the prior art, and discovered a novel anionic-cationic-nonionic surfactant, and further found that the use of the surfactant to manufacture the oil recovery combination for tertiary oil recovery
  • the object (displacement fluid) can solve the aforementioned problems existing in the prior art, and thus the present invention has been completed.
  • the present invention relates to the following aspects.
  • An anionic-cationic-nonionic surfactant characterized by being at least one selected from the group consisting of compounds substantially represented by the following formula (I),
  • the group N + is a quaternary nitrogen cation;
  • the groups R 1 to R 3 are the same or different from each other, and are each independently selected from an optionally substituted C 1-50 (preferably C 1-20 ) straight chain or Branched alkyl, optionally substituted C 5-50 (preferably C 5-10 or C 5-8 ) monocyclic or polycyclic cycloalkyl (preferably C 5-7 monocyclic cycloalkyl such as cyclohexyl), Substituted substituted C 2-50 (preferably C 2-20 ) straight or branched alkenyl, optionally substituted C 6-50 (preferably C 6-20 ) aryl and a representative group, provided that at least one of the groups R 1 to R 3 is a formula
  • the group represented, by "optionally substituted” herein, is meant to be optionally selected from one or more selected from the group consisting of oxo, hydroxy, and Representative group, C 1-20 (preferably C 1-10 ) straight or branched alkyl, C 1
  • the term "optionally substituted” means optionally one or more selected from the group consisting of oxo, hydroxy, C 1-20 (preferably C 1-10 ) straight or branched Alkyl, C 5-10 (preferably C 5-8 or C 5-7 ) monocyclic or polycyclic cycloalkyl (such as cyclohexyl), C 2-20 (preferably C 2-10 ) straight or branched olefin a substituent substituted with a C 6-20 (preferably C 6-10 ) aryl group, and the linear or branched heteroalkyl group is selected from one or more groups internal to the linear or branched alkyl molecular structure
  • the group -CH 2 - is selected from -O-, -S-, -NR'- (wherein the group R' is selected from an optionally substituted C 1-20 (preferably C 1-10 ) straight or branched alkane a optionally substituted C 5-10 (preferably C 5-8 or C 5-7 ) monocyclic
  • At least one of the group R 1 , the group R 2 , the group R 3 and the group Rh contains a C 8 linear portion in its structure.
  • each group Poly is independently selected from the group consisting of Representative ether segments; between each group Poly, the values m are identical or different from each other, each independently selected from any value between 0 and 100, preferably any value between 0 and 50; Between Poly, each value n is the same or different from each other, and each is independently selected from any value between 0 and 100, preferably any value between 0 and 50, provided that the sum of all values m and all values n is greater than 0; Preferably, the sum of all values m is greater than 0 and no more than 100 (preferably no more than 50) and/or the sum of all values n is greater than 0 and no more than 100 (preferably no more than 50).
  • the anion-cation-nonionic surfactant according to any one of the preceding aspects, which is selected from the group consisting of a compound represented by the following formula (I-1), a compound substantially represented by the following formula (I-2), Basically at least one of the compound represented by the following formula (I-3) and a compound substantially as shown in the following formula (I-4), and with the proviso that at least one N atom in the molecular structure of these compounds is additionally
  • the group Rh and the group X are bonded to each other (wherein the group N + is in the form of a quaternary nitrogen cation of the at least one N atom; the group Rh is selected from an optionally substituted C 1-50 (preferably C 1-20 ) straight or branched alkyl group, optionally Substituted C 5-50 (preferably C 5-10 or C 5-8 ) monocyclic or polycyclic cycloalkyl (such as cyclohexyl), optionally substituted C 2-50 (preferably C 2-20 ) straight or A
  • each group Ra is the same or different from each other, and each is independently selected from hydrogen, an optionally substituted C 1-20 linear or branched alkyl group, and an optionally substituted C 2-20 linear chain. Or a branched alkenyl group and an optionally substituted C 6-10 aryl group; each group Ra' being the same or different from each other, each independently selected from a single bond, an optionally substituted C 1-10 straight chain or branched alkylene group a optionally substituted C 2-10 straight or branched alkenylene group, a carbonyl group, an optionally substituted C 1-10 straight or branched alkylene carbonyl group, and an optionally substituted C 2-10 straight chain or Branched alkenylenecarbonyl, preferably each independently selected from a single bond and an optionally substituted C 1-6 straight or branched alkylene; b is any integer between 1 and 3, preferably 1; each group Y is the same or different from each other, and each is independently selected from N and
  • At least one of the group Ra and the group Rh comprises a C 8 linear portion in its structure
  • the group Rb is selected from an optionally substituted C 1-49 linear or branched alkyl group, an optionally substituted C 5 -49 monocyclic or polycyclic cycloalkyl group and optionally substituted C 2-49 linear or branched alkenyl (preferably selected from optionally substituted C 1-29 straight or branched alkyl, optionally substituted C 5-10 monocyclic or polycyclic cycloalkyl and optionally a substituted C 2-29 straight or branched alkenyl group, or an optionally substituted C 8-29 straight or branched alkyl group, an optionally substituted C 5-8 monocyclic or polycyclic cycloalkyl group, and An optionally substituted C 8-29 linear or branched alkenyl group, or an optionally substituted C 8-19 straight or branched alkyl group, optionally substituted C 5-7 monocyclic cycloalkyl group (such as a cyclohexyl) group and an optionally substituted C
  • At least one of the group Rb and the group Rh comprises a C 8 linear portion in its structure
  • each group Rc is the same or different from each other, and each is independently selected from an optionally substituted C 1-20 linear or branched alkyl group, an optionally substituted C 2-20 straight chain or a branch.
  • Alkenyl, optionally substituted C 1-20 straight or branched alkylcarbonyl and optionally substituted C 2-20 straight or branched alkenylcarbonyl (or each independently selected from optionally substituted C 1 a -10 linear or branched alkyl group, an optionally substituted C 2-10 straight or branched alkenyl group, an optionally substituted C 1-10 straight or branched alkylcarbonyl group, and an optionally substituted C 2 - 10 linear or branched alkenylcarbonyl, or each independently selected from optionally substituted C 8-20 straight or branched alkyl, optionally substituted C 8-20 straight or branched alkenyl, optionally a substituted C 8-20 linear or branched alkylcarbonyl group and an optionally
  • At least one of the group Rc and the group Rh comprises a C 8 linear portion in its structure
  • the group Rc is selected from an optionally substituted C 1-20 straight or branched alkyl group, an optionally substituted C 2-20 straight or branched alkenyl group, optionally substituted C a linear or branched alkylcarbonyl group and an optionally substituted C 2-20 linear or branched alkenylcarbonyl group (or each independently selected from an optionally substituted C 1-10 linear or branched alkyl group) , optionally substituted C 2-10 straight or branched alkenyl, optionally substituted C 1-10 straight or branched alkylcarbonyl, and optionally substituted C 2-10 straight or branched alkenylcarbonyl Or each independently selected from an optionally substituted C 8-20 straight or branched alkyl group, an optionally substituted C 8-20 straight or branched alkenyl group, an optionally substituted C 8-20 straight chain or a branched alkylcarbonyl group and an optionally substituted C 8-20 linear or branched alkenyl group (or each
  • At least one of the group Rc and the group Rh comprises a C 8 linear portion in its structure
  • said optional substitution refers to optionally being selected from one or more selected from the group consisting of hydroxyl, C 1-20 (preferably C 1-10 ) straight or branched alkyl, C 5-10 (preferably C 5-8) Or C 5-7 ) a monocyclic or polycyclic cycloalkyl group (such as cyclohexyl), a C 2-20 (preferably C 2-10 ) straight or branched alkenyl group and a C 6-20 (preferably C 6-10 ) The substituent of the aryl group is substituted.
  • a method of producing an anionic-cationic-nonionic surfactant comprising the steps of:
  • Step (1) one or more polyfunctional compounds containing nitrogen and having one or more functional groups selected from the group consisting of -OH, -NH 2 and -NH-, and one or more of the following formula (Y)
  • a basic catalyst preferably an alkali metal hydroxide
  • the group Ru' is selected from a C 2-6 straight or branched alkylene group (preferably selected from the group consisting of -CH 2 -CH 2 - and -CH 2 -CH(CH 3 )-),
  • Step (2) reacting the etherified product with a quaternizing agent represented by the following formula (A), thereby obtaining a cationic-nonionic surfactant, wherein the amount of the quaternizing agent is such that At least one N atom in the molecular structure of the etherification product forms a quaternary ammonium salt group,
  • the group Rh is selected from an optionally substituted C 1-50 (preferably C 1-20 ) straight or branched alkyl group, optionally substituted C 5-50 (preferably C 5-10 or C) 5-8 ) monocyclic or polycyclic cycloalkyl (such as cyclohexyl), optionally substituted C 2-50 (preferably C 2-20 ) straight or branched alkenyl and optionally substituted C 6-50 ( Preferred is a C 6-20 )aryl group; the group X' is selected from halogen (preferably fluorine, chlorine, bromine and iodine, more preferably chlorine),
  • At least one of the polyfunctional compound and the quaternizing agent comprises a C 8 linear portion in its molecular structure
  • Step (3) reacting the cationic-nonionic surfactant with one or more compounds represented by the following formula (Z) in the presence of a basic catalyst (preferably an alkali metal hydroxide), thereby Obtaining an anionic-cationic-nonionic surfactant,
  • a basic catalyst preferably an alkali metal hydroxide
  • the group G is selected from the group consisting of halogen (preferably fluorine, chlorine, bromine and iodine, more preferably chlorine) and a hydroxyl group; and the group L is selected from an optionally substituted C 1-10 linear or branched alkylene group.
  • halogen preferably fluorine, chlorine, bromine and iodine, more preferably chlorine
  • step (4) converting at least a portion of the quaternary ammonium salt groups of the anion-cationic-nonionic surfactant obtained in any step of the manufacturing process to the corresponding quaternary ammonium base group, and/ Or converting at least a portion of the quaternary ammonium base groups of the anion-cationic-nonionic surfactant to the corresponding quaternary ammonium salt groups,
  • step (5) separating at least a portion (preferably all) of the compound (M') r X in free form from the anion-cationic-nonionic surfactant obtained in any step of the manufacturing process ',
  • said optional substitution refers to optionally being selected from one or more selected from the group consisting of hydroxyl, C 1-20 (preferably C 1-10 ) straight or branched alkyl, C 5-10 (preferably C 5-8) Or C 5-7 ) a monocyclic or polycyclic cycloalkyl group (such as cyclohexyl), a C 2-20 (preferably C 2-10 ) straight or branched alkenyl group and a C 6-20 (preferably C 6-10 ) The substituent of the aryl group is substituted.
  • polyfunctional compound is at least one selected from the group consisting of compounds represented by the following formula (X),
  • the groups R' 1 to R' 3 are the same or different from each other, and are each independently selected from hydrogen, an optionally substituted C 1-50 (preferably C 1-20 ) straight or branched alkyl group, Optionally substituted C 5-50 (preferably C 5-10 or C 5-8 ) monocyclic or polycyclic cycloalkyl (preferably C 5-7 monocyclic cycloalkyl such as cyclohexyl), optionally substituted C 2 -50 (preferably C 2-20 ) a straight or branched alkenyl group, an optionally substituted C 6-50 (preferably C 6-20 ) aryl group and a group represented by the premise that at least one of the groups R' 1 to R' 3 is hydrogen or
  • the group represented, by "optionally substituted” herein, is meant to be optionally selected from one or more selected from the group consisting of oxo, hydroxy, and Representative group, C 1-20 (preferably C 1-10 ) straight or branched alkyl, C 5-10 (preferably C preferably C 5
  • the polyfunctional compound is preferably selected from the group consisting of a compound represented by the following formula (X-1), a compound represented by the following formula (X-2), a compound represented by the following formula (X-3), and the following formula (X-4). At least one of the compounds shown,
  • each group Ra is the same or different from each other, and each is independently selected from hydrogen, an optionally substituted C 1-20 straight or branched alkyl group, and an optionally substituted C 2-20 linear chain. Or a branched alkenyl group and an optionally substituted C 6-20 aryl group; each group Ra' being the same or different from each other, each independently selected from a single bond, an optionally substituted C 1-10 straight chain or branched alkylene group a optionally substituted C 2-10 straight or branched alkenylene group, a carbonyl group, an optionally substituted C 1-10 straight or branched alkylene carbonyl group, and an optionally substituted C 2-10 straight chain or Branched alkenylenecarbonyl, preferably each independently selected from a single bond and an optionally substituted C 1-6 straight or branched alkylene; b is any integer between 1 and 3, preferably 1; each group Y is the same or different from each other, and each is independently selected from N and
  • the group Rb is selected from an optionally substituted C 1-49 linear or branched alkyl group, an optionally substituted C 5 -49 monocyclic or polycyclic cycloalkyl group and optionally substituted C 2-49 linear or branched alkenyl (preferably selected from optionally substituted C 1-29 straight or branched alkyl, optionally substituted C 5-10 monocyclic or polycyclic cycloalkyl and optionally a substituted C 2-29 straight or branched alkenyl group, or an optionally substituted C 8-29 straight or branched alkyl group, an optionally substituted C 5-8 monocyclic or polycyclic cycloalkyl group, and An optionally substituted C 8-29 linear or branched alkenyl group, or an optionally substituted C 8-19 straight or branched alkyl group, optionally substituted C 5-7 monocyclic cycloalkyl group (such as a cyclohexyl) group and an optionally substituted C
  • each group Rc is the same or different from each other, and each is independently selected from an optionally substituted C 1-20 linear or branched alkyl group, an optionally substituted C 2-20 straight chain or a branch.
  • Alkenyl, optionally substituted C 1-20 straight or branched alkylcarbonyl and optionally substituted C 2-20 straight or branched alkenylcarbonyl (or each independently selected from optionally substituted C 1 a -10 linear or branched alkyl group, an optionally substituted C 2-10 straight or branched alkenyl group, an optionally substituted C 1-10 straight or branched alkylcarbonyl group, and an optionally substituted C 2 - 10 linear or branched alkenylcarbonyl, or each independently selected from optionally substituted C 8-20 straight or branched alkyl, optionally substituted C 8-20 straight or branched alkenyl, optionally a substituted C 8-20 linear or branched alkylcarbonyl group and an optionally
  • the group Rc is selected from an optionally substituted C 1-20 straight or branched alkyl group, an optionally substituted C 2-20 straight or branched alkenyl group, optionally substituted C a linear or branched alkylcarbonyl group and an optionally substituted C 2-20 linear or branched alkenylcarbonyl group (or each independently selected from an optionally substituted C 1-10 linear or branched alkyl group) , optionally substituted C 2-10 straight or branched alkenyl, optionally substituted C 1-10 straight or branched alkylcarbonyl, and optionally substituted C 2-10 straight or branched alkenylcarbonyl Or each independently selected from an optionally substituted C 8-20 straight or branched alkyl group, an optionally substituted C 8-20 straight or branched alkenyl group, an optionally substituted C 8-20 straight chain or a branched alkylcarbonyl group and an optionally substituted C 8-20 linear or branched alkenyl group (or each
  • the term "optionally substituted” means optionally one or more selected from the group consisting of oxo, hydroxy, C 1-20 (preferably C 1-10 ) straight or branched Alkyl, C 5-10 (preferably C 5-8 or C 5-7 ) monocyclic or polycyclic cycloalkyl (such as cyclohexyl), C 2-20 (preferably C 2-10 ) straight or branched olefin
  • the substituent is substituted with a substituent of a C 6-20 (preferably C 6-10 ) aryl group.
  • a molar ratio of the polyfunctional compound to the alkylene oxide is from 1:0 to 200 (preferably from 1:0 to 100), but does not include 0;
  • the molar ratio of the functional compound to the compound represented by the formula (Z) is from 1:1 to 10 (preferably from 1:1 to 3);
  • the reaction conditions of the step (1) include: the reaction temperature is from room temperature to 300 ° C ( Preferably, 100-200 ° C), the reaction time is 1-20 hours (preferably 1-10 hours);
  • the reaction conditions of the step (2) include: the reaction temperature is 0-300 ° C (preferably 50-150 ° C), the reaction time It is 1-20 hours (preferably 4-15 hours);
  • the reaction conditions of the step (3) include: the reaction temperature is 0-300 ° C (preferably 50-200 ° C), and the reaction time is 1-20 hours (preferably 4 10 hours).
  • An oil recovery composition for tertiary recovery comprising the anion-cation-nonionic surfactant according to any one of the preceding aspects, or an anion-cation produced by the production method according to any of the preceding aspects. a nonionic surfactant, and water, wherein the anionic-cationic-nonionic surfactant is present in an amount of 0.001 by weight based on 100% by weight based on the total weight of the tertiary oil recovery composition 10% by weight, preferably 0.005 to 5% by weight, more preferably 0.02 to 1% by weight.
  • a method for producing an oil-repellent composition for tertiary oil recovery which comprises the anionic-cationic-nonionic surfactant according to any one of the above aspects, or the production method according to any one of the preceding aspects.
  • the anionic-cationic-nonionic surfactant is at least mixed with water, wherein the anionic-cationic-nonionic surfactant is 100% by weight based on the total weight of the tertiary oil recovery flooding composition
  • the content is from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably from 0.02 to 1% by weight.
  • a tertiary oil recovery method comprising the anion-cation-nonionic surfactant produced by using the anion-cation-nonionic surfactant according to any of the preceding aspects, and the production method according to any of the preceding aspects.
  • the type of surfactant, the oil recovery composition for tertiary recovery according to any one of the above aspects, or the oil recovery composition for tertiary recovery produced by the production method according to any of the above aspects is used as a displacement liquid for the third oil recovery step.
  • anionic-cationic-nonionic surfactants according to the present invention exhibit significantly improved interfacial activity compared to the prior art.
  • an ultra-low interfacial tension of 10 -3 -10 -4 mN/m can be formed with the underground crude oil under the condition that the amount of the surfactant is as low as 0.01 to 0.05 wt%.
  • a stable and transparent aqueous solution can be formed in water even at a high temperature, and in a preferred case, even after a long period of time (especially at high temperatures) storage, its chemical composition and interfacial activity also maintain excellent stability.
  • anionic-cationic-nonionic surfactant or the tertiary oil recovery oil-displacing composition of the present invention chromatographic separation does not occur during use, and the use stability is excellent.
  • the oil recovery composition for tertiary recovery according to the present invention exhibits improved oil displacement efficiency and washing as compared with the prior art since the anionic-cationic-nonionic surfactant of the present invention is used as a surfactant component. Oil capacity (such as oil washing rate of crude oil can exceed 40%), can significantly improve oil recovery.
  • the oil recovery composition for tertiary oil recovery according to the present invention has a simple system, does not contain inorganic alkali, does not harm the formation and the oil well, avoids corrosion of equipment and pipelines, and does not cause difficulty in breaking milk.
  • halogen refers to fluorine, chlorine, bromine or iodine.
  • the term "straight or branched heteroalkyl” refers to the internal structure of a linear or branched alkyl molecule (excluding the end of the main chain or any side chain in the alkyl molecular structure)
  • One or more (such as 1 to 4, 1 to 3, 1 to 2 or 1) groups -CH 2 - are selected from -O-, -S-, -NR'- and One or more of the groups obtained by direct replacement of one of the alternative groups, or the inside of the linear or branched alkyl molecular structure (excluding the end of the main chain or any side chain in the alkyl molecular structure)
  • 1 to 3, 1 to 2 or 1) groups Substituted group or A group obtained by direct substitution.
  • the substitute group -NR'- or More preferably -NR'-.
  • the group R' is selected from an optionally substituted C 1-20 straight or branched alkyl group, an optionally substituted C 5-10 monocyclic or polycyclic cycloalkyl group, an optionally substituted C 2-20 A linear or branched alkenyl group and an optionally substituted C 6-20 aryl group.
  • a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group such as a methyl group or an ethyl group may be mentioned. Wait.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • -7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • a C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • a C 1-20 linear or branched alkyl group or a C 5-7 monocyclic cycloalkyl group is preferred, such as, for example, a methyl group, an ethyl group or a cyclohexyl group.
  • the group N + is a quaternary nitrogen cation.
  • the group Rh is selected from an optionally substituted C 1-50 straight or branched alkyl group, an optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl group, an optionally substituted C 2-50 straight chain or branch Alkenyl and optionally substituted C 6-50 aryl.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned.
  • C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group X - is selected from the group consisting of a halide ion (including a fluoride ion, a chloride ion, a bromide ion, and an iodide ion) and a hydroxide ion (OH - ), of which a halogen ion is preferred, and a chloride ion is more preferred.
  • a halide ion including a fluoride ion, a chloride ion, a bromide ion, and an iodide ion
  • OH ion hydroxide ion
  • the term “optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain.
  • a branched alkyl group a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • a C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned. .
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • -7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • the C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified. It is apparent that, from the viewpoint of structural stability, when there are a plurality of these, the substitution groups are not directly bonded.
  • the number of carbon atoms of the linear or branched alkyl group is due to the group -CH 2 - or a group
  • the substitution is correspondingly reduced, but for the sake of simplicity, the number of carbon atoms of the linear or branched alkyl group before the substitution is still used to refer to the number of carbon atoms of the linear or branched heteroalkyl group.
  • a C 4 linear alkyl group such as (where the group indicated by the arrow is not inside the molecular structure, but at the end of the main chain) is directly replaced by an alternative group -O- to obtain -CH 2 -O-CH 2 -CH 3 or -CH 2- CH 2 -O-CH 3 is referred to as a C 4 linear heteroalkyl group.
  • a C 4 branched alkyl group such as (where the group indicated by the arrow is not inside the molecular structure, but at the end of the main chain and the side chain) is replaced by an alternative group Direct substitution will be obtained It is called a C 4 branched heteroalkyl group.
  • a C 3-50 linear or branched heteroalkyl group for example, a C 3-50 linear or branched heteroalkyl group may be mentioned, specifically, for example, a C 8-50 linear or branched heteroalkyl group, C 8 -30 linear or branched heteroalkyl or C 8-20 linear or branched heteroalkyl, or C 3-20 linear or branched heteroalkyl, C 3-10 linear or branched heteroalkyl Or a C 3-6 linear or branched heteroalkyl group.
  • the expression "number + valence + group” or the like refers to the removal of the number represented by the base structure (such as a chain, a ring or a combination thereof, etc.) corresponding to the group.
  • the group obtained after the number of hydrogen atoms is preferably obtained by removing the number of hydrogen atoms represented by the number from the carbon atoms (preferably saturated carbon atoms and/or non-identical carbon atoms) contained in the structure. Group.
  • trivalent linear or branched alkyl refers to a group obtained by removing three hydrogen atoms from the linear or branched alkane (ie, the basic chain corresponding to the linear or branched alkyl group), and "a divalent linear or branched heteroalkane”
  • Base refers to a group obtained by removing two hydrogen atoms from the linear or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane or, further, from a non-identical carbon atom).
  • 0 valence + group represents the basic structure, such as a 0 valent alkyl group means an alkane.
  • the phrase "comprising a C 8 linear moiety in a structure” means that the compound or group involved comprises (eg one or more) 8 carbon atoms in its overall chemical structure. A structural segment that is successively bonded in a linear fashion. Depending on the specific definition or substitution of the chemical structure, the eight carbon atoms may each independently assume a substituted state or an unsubstituted state. Moreover, the C 8 linear portion may be internal to the chemical structure (such as the backbone constituting the chemical structure), or may be at the end of the chemical structure (such as an end group or a side chain constituting the chemical structure). ), there are no special restrictions.
  • the group R 1 (as described below) comprises a C 8 linear moiety in its structure
  • the group R 1 is an optionally substituted C 10 straight or branched alkyl group
  • the group R 1 may be -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -C H 2 -CH 3 ,
  • the group R 1 contains a C 8 linear portion as a part (fragment) of its structure in its structure, the position of the C 8 linear portion is not limited, It is possible that it is a main chain, a terminal group or a side chain, and it is obviously not limited that the group R 1 consists of only 8 carbon atoms or the C 8 linear moiety is only present as -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - .
  • an anionic-cationic-nonionic surfactant which is a compound substantially as shown in the following formula (I).
  • the compound represented by the formula (I) may be used singly or in combination of two or more kinds.
  • the group N + is a quaternary nitrogen cation, whereby the compound represented by the formula (I) is a quaternary ammonium type compound.
  • the groups R 1 to R 3 are the same or different from each other, each independently selected from an optionally substituted C 1-50 linear or branched alkyl group, optionally substituted C 5 -50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight or branched alkenyl, optionally substituted C 6-50 aryl and by formula Representative group.
  • the term "optionally substituted” means that one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) is selected from oxo (ie, ), hydroxyl, by Representative of a group, a C 1-20 straight or branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group, and a C 6-20 aryl group Substituted.
  • oxo ie, 1, 2, 3, 1 to 2 or 1 to 2 or 1
  • hydroxyl by Representative of a group, a C 1-20 straight or branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group, and a C 6-20 aryl group Substituted.
  • the C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • -7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • At least one of the groups R 1 to R 3 (for example, at most two) is required to be Representative group.
  • the group Rh is selected from an optionally substituted C 1-50 straight or branched alkyl group, an optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl group, A substituted C 2-50 straight or branched alkenyl group and an optionally substituted C 6-50 aryl group are selected.
  • the C 1-50 linear or branched alkyl group for example, C 1-20 may be mentioned.
  • a linear or branched alkyl group or a C 8-20 linear or branched alkyl group such as octadecyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl, and the like.
  • C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group X - is selected from the group consisting of halide ions (including fluoride ions, chloride ions, bromide ions and iodide ions) and hydroxide ions (OH - ), of which halogen ions are preferred, more preferably Chloride.
  • the group Link is selected from an optionally substituted x+1 valent C 1-50 linear or branched alkyl group, an optionally substituted x+1 valent C 5-50 monocyclic or polycyclic naphthenic a optionally substituted x+1 valent C 2-50 straight or branched alkenyl group, an optionally substituted x+1 valent C 6-50 aryl group, and an optionally substituted x +1 C 3-50 straight Chain or branched heteroalkyl.
  • an optionally substituted x+1 valent C 1-50 linear or branched alkyl group an optionally substituted x+1 valent C 1-20 linear or branched alkyl group is preferred.
  • an optionally substituted x+1 valent C 5-10 monocyclic or polycyclic cycloalkyl group may be mentioned.
  • an optionally substituted x+1 valent C 2-50 linear or branched alkenyl group an optionally substituted x+1 valent C 2-20 straight or branched alkenyl group is preferred.
  • an optionally substituted x+1 valent C 6-50 aryl group an optionally substituted x+1 valent C 6-20 aryl group such as a phenyl group or a naphthyl group is preferred.
  • an optionally substituted x+1 valent C 3-50 linear or branched heteroalkyl group an optionally substituted x+1 valent C 3-20 linear or branched heteroalkyl group is preferred.
  • each group Poly in the formula Among the groups represented, each group Poly is identical or different from each other, and each is independently Representative group.
  • the respective values y are the same or different from each other between the respective groups Poly, and are each independently selected from any value between 0 and 200, preferably any value between 0 and 100.
  • the value y represents the unit -O-Ru- in the formula The average number of groups represented, and thus may be non-integer.
  • the numerical value y may be, for example, 0, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5, 50.5, 55.2, 60.0, 75.5, 80.5, 85.0, 90.5 or 95.7.
  • the sum of the x values y is required (i.e., in the formula)
  • the overall average number of the units -O-Ru- is more than 0, but generally does not exceed 200, preferably does not exceed 100.
  • the compound or formula represented by formula (I) In the overall molecular structure of the represented group, it is necessary to contain (a certain number of) units -O-Ru-, thereby rendering the compound represented by the formula (I) nonionic.
  • the overall average number of the units -O-Ru- may be, for example, 0.1, 0.5, 1.5, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5, 50.5, 55.2, 60.0, 75.5, 80.5, 85.0, 90.5 or 95.7.
  • the respective groups Ru are identical or different from each other, and are each independently selected from a C 2-6 linear or branched alkylene group, preferably -CH 2 -CH 2 -, -CH 2 -CH(CH 3 )- or a combination thereof, especially -CH 2 -CH(CH 3 )- or -CH 2 -CH(CH 3 )- and other C 2-6 straight chains Or a combination of branched alkylene groups.
  • each (different) unit -O-Ru- may be as follows
  • the rules, (two or more) blocks or alternating means are bonded to each other at any ratio determined according to needs, but the overall average number of these units is y.
  • any ratio determined according to need for example, the molar ratio between the two may be 1:99 to 99:1) may be bonded to each other, but The overall average number of these two units is 2.2.
  • one or more groups Poly are present, preferably at least one (at least a certain number) of the groups Ru is selected from C 3-6 in at least one group Poly (preferably all groups Poly) a linear or branched alkylene group (corresponding to a non-O-CH 2 -CH 2 - unit), wherein -CH 2 -CH(CH 3 )- is preferred (corresponding to the unit ), thereby making the group Poly preferably contain (a certain number, upper limit of y) non-O-CH 2 -CH 2 - units (such as units) ) as a constituent unit.
  • each group Poly is independently or at least one of the groups Poly is selected from the (diblock) ether segment represented by the following formula (IA).
  • the ether segment and the group Link are bonded in the following manner.
  • the respective values m are identical or different from each other, each independently selected from any value between 0 and 100, preferably 0 to Any value between 50.
  • the value m represents the unit
  • the average number in formula (IA) can therefore be a non-integer.
  • the numerical value m may be, for example, 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n are identical or different from each other, each independently selected from any value between 0 and 100, preferably 0 to Any value between 50.
  • the value n represents the average number of units -O-CH 2 -CH 2 - in the formula (IA), and thus may be a non-integer.
  • the numerical value n for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • x groups Poly are each independently selected from the (diblock) ether segment represented by formula (IA), the sum of x values m (ie, in formula (I) Compound or formula The unit's overall molecular structure, the unit The overall average number) is greater than zero, but generally does not exceed 100, preferably does not exceed 50.
  • the overall molecular structure of the representative group preferably contains (a certain number of) units
  • the compound represented by the formula (I) or the formula In the overall molecular structure of the representative group as the unit
  • the overall average number can be, for example, 0.1, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • x groups of Poly are each independently selected from the (diblock) ether segment represented by formula (IA), the sum of x values n (ie, in formula (I) Compound or formula
  • the overall average number of units -O-CH 2 -CH 2 - does not exceed 100, preferably does not exceed 50.
  • the compound or formula represented by formula (I) The overall molecular structure of the represented group optionally contains (a certain number of) units -O-CH 2 -CH 2 -.
  • the compound represented by the formula (I) or the formula In the overall molecular structure of the group represented the overall average number of the units -O-CH 2 -CH 2 - may be, for example, 0, 0.1, 0.5, 1.2, 2.0, 2.5 , 3.0, 3.5, 5.4, 7.5. , 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 49.5.
  • the compound represented by the formula (I) or the formula In the overall molecular structure of the group represented the overall average number of the units -O-CH 2 -CH 2 - may be, for example, 0.1, 0.5, 1.2, 2.0, 2.5 , 3.0, 3.5, 5.4, 7.5, 10.0. , 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the overall molecular structure of the represented group preferably contains (a certain number of) units -O-CH 2 -CH 2 - and/or At this time, the compound represented by the formula (I) or the formula In the overall molecular structure of the represented group, as the overall average number of these units, for example, it may be 0.1, 0.5, 1.5, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5, 50.5. , 55.2, 60.0, 75.5, 80.5, 85.0, 90.5 or 95.7, etc.
  • each group L is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group and an optionally substituted C 2-10 straight chain or branched chain.
  • the alkenylene groups are preferably each independently selected from an optionally substituted C 1-5 linear or branched alkylene group.
  • alkali metals preferably Li, Na and K
  • alkaline earth metals preferably Mg and Ca
  • NH 4 ammonium
  • the group A - in the formula (I), in the formula Among the groups represented, depending on the number of groups Salt, the group A - may be one or x, preferably at least one of the groups A - is a carboxylate (COO - ). In view of this, in the overall molecular structure of the compound represented by the formula (I), at least one carboxylate (COO - ) is preferably present.
  • x+1 represents the valence state value of the group Link.
  • x is an arbitrary integer between 1 and 10, preferably any integer between 1 and 4, such as 1, 2 or 3.
  • the group R 1 , the group R 2 , the group R 3 and the group Rh must be included in its structure (one Or a plurality of C 8 linear moieties, thereby rendering the anionic-cationic-nonionic surfactants of the invention exhibit the desired surface active properties.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 5, 1 to 4, 1 to 3). , 1 to 2 or 1) selected from oxo (ie a substituent of a hydroxyl group, a C 1-20 linear or branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 linear or branched alkenyl group and a C 6-20 aryl group; Replace.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • oxo in the presence of oxo as a substituent, preferably at least one oxo substituent is located in combination with an N atom (if any, such as a linear or branched heteroalkyl group) N atoms) directly bonded to a carbon atom such that the carbon atom appears as a carbonyl group (ie In the form of a structure in which a carbonyl group is directly bonded to an N atom (such as an imido group) in the molecular structure of the compound represented by the formula (I).
  • N atom if any, such as a linear or branched heteroalkyl group
  • At least a part (preferably all) is not present on the carbon atom to which the O or S atom, if any, is directly bonded. And/or at least a portion (preferably all) of the oxo substituent is absent from a carbon atom at the position of the chain end (referring to the free end of the molecular chain and/or the end to be bonded to other atoms), And/or, the two directly bonded carbon atoms are not replaced by oxo at the same time. By doing so, it is possible to avoid introduction of a chemically active or unstable group such as an ester group or an aldehyde group into the molecular structure of the compound represented by the formula (I).
  • the group Link is a divalent linear alkyl group substituted with one oxo substituent. (when it includes two carbon atoms at the chain end position, as indicated by the arrow in the formula), according to the foregoing principle, the group Link is preferably, for example, or Wait.
  • the group Link is a divalent branched heteroalkyl group substituted by one oxo substituent (When it includes three carbon atoms at the chain end position, as indicated by the arrow in the formula, and also includes three carbon atoms directly bonded to the N atom), according to the foregoing principle, the group Link is preferably, for example, or Wait.
  • anion-cation-nonionic surfactant or the compound represented by the formula (I) for example, a compound substantially represented by the following formula (I-1) can be specifically mentioned, basically The compound represented by the following formula (I-2) is substantially as shown in the following formula (I-3) The compound shown is basically a compound represented by the following formula (I-4). These compounds may be used singly or in combination of two or more kinds.
  • N atoms contained in the molecular structure of these compounds are required with the additional groups Rh and groups X (these groups) It is represented by a bond in the following formula (I-1), formula (I-2), formula (I-3) or formula (I-4) The form of the quaternary ammonium salt (base) shown.
  • the group Rh is selected from an optionally substituted C 1-50 straight or branched alkyl group, an optionally substituted C 5-50 single ring Or a polycyclic cycloalkyl group, an optionally substituted C 2-50 straight or branched alkenyl group, and an optionally substituted C 6-50 aryl group.
  • the group Rh as the C 1-50 linear or branched alkyl group, for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned.
  • octadecyl lauryl, octyl, hexadecyl, hexyl, methyl or ethyl.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group X - is selected from the group consisting of a halide ion (including a fluoride ion, a chloride ion, a bromide ion, and an iodide ion) and a hydroxide ion (OH - ), of which a halogen ion is preferred, and a chloride ion is more preferred.
  • a halide ion including a fluoride ion, a chloride ion, a bromide ion, and an iodide ion
  • OH ion hydroxide ion
  • the term “optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain.
  • a branched alkyl group a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • a C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned. .
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • -7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the respective groups Ra are the same or different from each other, each independently selected from hydrogen, an optionally substituted C 1-20 straight or branched alkyl group, optionally substituted C 2-20 straight or branched alkenyl and optionally substituted C 6-10 aryl, preferably hydrogen, optionally substituted C 8-20 straight or branched alkyl and optionally substituted C 6-10 aryl base.
  • each group Ra' is the same or different from each other, and each is independently selected from a single bond, an optionally substituted C 1-10 linear or branched alkylene group, optionally Substituted C 2-10 linear or branched alkenylene, carbonyl, optionally substituted C 1-10 straight or branched alkylene carbonyl, and optionally substituted C 2-10 straight or branched alkylene
  • the carbonyl groups are preferably each independently selected from the group consisting of a single bond and an optionally substituted C 1-6 straight or branched alkylene group.
  • b is an arbitrary integer between 1 and 3, preferably 1.
  • x' represents a group The number is any integer between 1 and 5, preferably any integer between 1 and 4, such as 1, 2 or 3. Obviously, b+x' ⁇ 6.
  • each (i.e., x') groups Rp 1 are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group, provided that at least one (such as one or two) groups Rp 1 is a formula Representative group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • each (i.e., x' x a) groups Rp 2 are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the respective values m' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m' represents the unit The average number, so it can be a non-integer.
  • the numerical value m' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value n' represents the average number of units -CH 2 -CH 2 -O- and thus may be a non-integer.
  • the numerical value n' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values m" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m′′ represents the unit The average number, so it can be a non-integer.
  • the numerical value m for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the stated value n" represents the average number of units -CH 2 -CH 2 -O- and thus may be non-integer.
  • the numerical value n" for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x') values m' and all (i.e., x' x a) values m" i.e., in the formula (I-1)
  • the overall average number is greater than zero, but generally does not exceed 100, preferably does not exceed 50.
  • the overall average number can be, for example, 0.1, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x') values n' and all (i.e., x' x a) values n" i.e., in the formula (I-1)
  • the overall average number of units -CH 2 -CH 2 -O- is not more than 100, preferably not more than 50.
  • the average number may be, for example, 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x') values n' and all (i.e., x' x a) values n" i.e., in the formula
  • the overall average number of units -CH 2 -CH 2 -O- is more than 0.
  • the overall molecular structure of the compound represented by the formula (I - 1) as the unit -CH 2 -CH
  • the overall average number of 2 -O- may be, for example, 0.1, 0.5, 1.2, 2.0, 2.5 , 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x') numerical values n' and all (i.e., x' x a) numerical values n" i.e., as shown in the formula (I-1)
  • the overall molecular structure of the compound, the overall average number of units -CH 2 -CH 2 -O-) and the sum of all (ie x') values m' and all (ie x' x a) values m" ie
  • the unit The sum of the overall average numbers is greater than zero, but generally does not exceed 200, preferably does not exceed 100.
  • the overall molecular structure of the compound represented by the formula (I-1) it is necessary to contain (a certain number of) units -O-CH 2 -CH 2 - and/or At this time, in the overall molecular structure of the compound represented by the formula (I-1), as the overall average number of these units, for example, it may be 0.1, 0.5, 1.5, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0. , 30.2, 35.0, 40.0, 45.5, 50.5, 55.2, 60.0, 75.5, 80.5, 85.0, 90.5 or 95.7.
  • each group L is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group and an optionally substituted C 2 .
  • the -10 linear or branched alkenylene group is preferably each independently selected from an optionally substituted C 1-5 linear or branched alkylene group.
  • each group Salt is identical or different from each other, and each is independently selected from a group represented by -A - (M) r + wherein the group A - is selected from a carboxylate group ( COO - ) and sulfonate (SO 3 - ), the group M is selected from the group consisting of alkali metals (preferably Li, Na and K), alkaline earth metals (preferably Mg and Ca) and ammonium (NH 4 ).
  • alkali metals preferably Li, Na and K
  • alkaline earth metals preferably Mg and Ca
  • NH 4 ammonium
  • the group Ra and the group Rh (including all the groups Ra and the group Rh contained in the compound represented by the formula (I-1), obviously include the aforementioned quaternary ammonium salt groups Rh (base) included) at least one (such as one, two, or three, etc.) must contain (s) in their structure a straight-chain C 8 fraction consisting of This allows the compound represented by the formula (I-1) to exhibit the desired surface activity properties.
  • the group A - may be one or plural, and at least one of the groups A - is a carboxylate ( COO - ).
  • at least one carboxylate (COO - ) is preferably present.
  • the group Rb is selected from an optionally substituted C 1-49 linear or branched alkyl group, an optionally substituted C 5-49 monocyclic or polycyclic cycloalkyl group.
  • optionally substituted C 2 - 49 linear or branched alkenyl preferably selected from optionally substituted C 1-29 straight or branched alkyl, optionally substituted C 5-10 monocyclic or polycyclic ring
  • An alkyl group and an optionally substituted C 2-29 straight or branched alkenyl group, or an optionally substituted C 8-29 straight or branched alkyl group, optionally substituted C 5-8 monocyclic or poly Cyclocycloalkyl and optionally substituted C 8-29 straight or branched alkenyl preferably selected from optionally substituted C 8-19 straight or branched alkyl, optionally substituted C 5-7 monocyclic
  • a cycloalkyl group such as a cyclohexyl group and an optionally substituted
  • each of the groups Rb' is the same or different from each other, and each is independently selected from a single bond and a carbonyl group.
  • x represents a group The number is any integer between 1 and 10, preferably any integer between 1 and 4, such as 1, 2 or 3.
  • each (i.e., x") groups Rp 1 are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group, provided that at least one (such as one or two) groups Rp 1 is a formula Representative group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • each (i.e., x"xa) groups Rp 2 are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the respective values m' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m' represents the unit The average number, so it can be a non-integer.
  • the numerical value m' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value n' represents the average number of units -CH 2 -CH 2 -O- and thus may be a non-integer.
  • the numerical value n' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values m" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m′′ represents the unit The average number, so it can be a non-integer.
  • the numerical value m for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the stated value n" represents the average number of units -CH 2 -CH 2 -O- and thus may be non-integer.
  • the numerical value n" for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x") values m' and all (i.e., x" x a) values m" i.e., in the formula (I-2)
  • the overall average number is greater than zero, but generally does not exceed 100, preferably does not exceed 50.
  • the overall average number can be, for example, 0.1, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x") values n' and all (i.e., x" x a) numerical values n" i.e., in the formula (I-2)
  • the overall average number of units -CH 2 -CH 2 -O- does not exceed 100, preferably does not exceed 50.
  • the average number may be, for example, 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x") values n' and all (i.e., x" x a) values n" i.e., in the formula
  • the overall average number of units -CH 2 -CH 2 -O- is more than 0.
  • the overall average number of 2 -O- may be, for example, 0.1, 0.5, 1.2, 2.0, 2.5 , 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x") values n' and all (i.e., x" x a) numerical values n" i.e., as shown in the formula (I-2)
  • the overall molecular structure of the compound, the overall average number of units -CH 2 -CH 2 -O-) and the sum of all (ie x") values m' and all (ie x" x a) values m" ie
  • the unit The sum of the overall average numbers is greater than zero, but generally does not exceed 200, preferably does not exceed 100.
  • the overall molecular structure of the compound represented by the formula (I-2) it is necessary to contain (a certain number of) units -O-CH 2 -CH 2 - and/or At this time, in the overall molecular structure of the compound represented by the formula (I-2), as the overall average number of these units, for example, it may be 0.1, 0.5, 1.5, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0. , 30.2, 35.0, 40.0, 45.5, 50.5, 55.2, 60.0, 75.5, 80.5, 85.0, 90.5. or 95.7.
  • each group L is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group and an optionally substituted C 2 .
  • the -10 linear or branched alkenylene group is preferably each independently selected from an optionally substituted C 1-5 linear or branched alkylene group.
  • each group Salt is identical or different from each other, and each is independently selected from a group represented by -A - (M) r + wherein the group A - is selected from a carboxylate group ( COO - ) and sulfonate (SO 3 - ), the group M is selected from the group consisting of alkali metals (preferably Li, Na and K), alkaline earth metals (preferably Mg and Ca) and ammonium (NH 4 ).
  • alkali metals preferably Li, Na and K
  • alkaline earth metals preferably Mg and Ca
  • NH 4 ammonium
  • the group A - may be one or plural, and at least one of the groups A - is a carboxylate ( COO - ).
  • at least one carboxylate (COO - ) is preferably present.
  • the group Rb and the group Rh (including all the groups Rb and Rh contained in the compound represented by the formula (I-2), obviously include the aforementioned quaternary ammonium salt groups Rh (base) included) at least one (such as one, two, or three, etc.) must contain (s) in their structure a straight-chain C 8 fraction consisting of This allows the compound represented by the formula (I-2) to exhibit the desired surface activity properties.
  • each group Rc is the same or different from each other, and each is independently selected from an optionally substituted C 1-20 straight or branched alkyl group, optionally substituted C 2 - a 20- or branched-chain alkenyl group, an optionally substituted C 1-20 straight or branched alkylcarbonyl group, and an optionally substituted C 2-20 straight or branched alkenylcarbonyl group, or each independently selected from any Substituted substituted C 1-10 linear or branched alkyl, optionally substituted C 2-10 straight or branched alkenyl, optionally substituted C 1-10 straight or branched alkyl carbonyl, and optionally Substituted C 2-10 straight or branched alkenylcarbonyl, or each independently selected from optionally substituted C 8-20 straight or branched alkyl, optionally substituted C 8-20 straight or branched Alkenyl, optionally substituted C 8-20 straight or branched alky
  • each group Rd is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group, optionally substituted C 2 a linear or branched alkenylene group, an optionally substituted C 1-10 linear or branched alkylenecarbonyl group, an optionally substituted C 2-10 linear or branched alkenylenecarbonyl group, optionally substituted
  • the carbonyl C 1-10 linear or branched alkylenecarbonyl group and the optionally substituted carbonyl C 2-10 linear or branched alkenylenecarbonyl group are preferably each independently selected from optionally substituted C 1-5 straight A chain or branched alkylene group and an optionally substituted C 1-5 linear or branched alkylene carbonyl group.
  • x'" represents a unit The number is any integer between 1 and 10, preferably any integer between 1 and 4, such as 1, 2 or 3.
  • each (i.e., x'') groups Rp are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group, provided that at least one (such as one or two) groups Rp is a formula Representative group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the respective values m' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m' represents the unit The average number, so it can be a non-integer.
  • the numerical value m' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value n' represents the average number of units -CH 2 -CH 2 -O- and thus may be a non-integer.
  • the numerical value n' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x"" values m' i.e., in the overall molecular structure of the compound represented by the formula (I-3), a unit The overall average number) is greater than zero, but generally does not exceed 100, preferably does not exceed 50. In view of this, it is preferred to contain (a certain number of) units in the overall molecular structure of the compound represented by the formula (I-3).
  • the overall average number can be, for example, 0.1, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the unit The overall average number of -CH 2 -CH 2 -O- is not more than 100, preferably not more than 50.
  • the overall average number of the units -CH 2 -CH 2 -O- may be, for example, 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x'') numerical values n' i.e., the overall molecule of the compound represented by the formula (I-3)
  • the overall average number of the units -CH 2 -CH 2 -O- is more than 0.
  • the overall average number of the units -CH 2 -CH 2 -O- may be, for example, 0.1, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (i.e., x''') values n' i.e., in the overall molecular structure of the compound represented by the formula (I-3)
  • the unit -CH 2 - The sum of the total number of CH 2 -O-) and the total (i.e., x''') values m' (i.e., in the overall molecular structure of the compound represented by the formula (I-3)
  • the unit The sum of the overall average numbers is greater than zero, but generally does not exceed 200, preferably does not exceed 100.
  • the overall molecular structure of the compound represented by the formula (I-3) it is necessary to contain (a certain number of) units -O-CH 2 -CH 2 - and/or At this time, in the overall molecular structure of the compound represented by the formula (I-3), as the overall average number of these units, for example, it may be 0.1, 0.5, 1.5, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0. , 30.2, 35.0, 40.0, 45.5, 50.5, 55.2, 60.0, 75.5, 80.5, 85.0, 90.5. or 95.7.
  • each group L is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group and an optionally substituted C 2 .
  • the -10 linear or branched alkenylene group is preferably each independently selected from an optionally substituted C 1-5 linear or branched alkylene group.
  • each of the groups Salt is the same or different from each other, and each is independently selected from a group represented by -A - (M) r + wherein the group A - is selected from a carboxylate group ( COO - ) and sulfonate (SO 3 - ), the group M is selected from the group consisting of alkali metals (preferably Li, Na and K), alkaline earth metals (preferably Mg and Ca) and ammonium (NH 4 ).
  • alkali metals preferably Li, Na and K
  • alkaline earth metals preferably Mg and Ca
  • NH 4 ammonium
  • the group A - may be one or plural, and at least one group A - is a carboxylate ( COO - ).
  • at least one carboxylate (COO - ) is preferably present.
  • the group Rc and the group Rh (including all the groups Rc and Rh contained in the compound represented by the formula (I-3), obviously include the aforementioned quaternary ammonium salt groups Rh (base) included) at least one (such as one, two, or three, etc.) must contain (s) in their structure a straight-chain C 8 fraction consisting of This allows the compound represented by the formula (I-3) to exhibit the desired surface activity properties.
  • the group Rc is selected from an optionally substituted C 1-20 straight or branched alkyl group, an optionally substituted C 2-20 straight or branched alkenyl group, An optionally substituted C 1-20 linear or branched alkylcarbonyl group and an optionally substituted C 2-20 straight or branched alkenylcarbonyl group, or each independently selected from optionally substituted C 1-10 straight chain Or a branched alkyl group, an optionally substituted C 2-10 straight or branched alkenyl group, an optionally substituted C 1-10 straight or branched alkylcarbonyl group, and an optionally substituted C 2-10 straight chain or A branched alkenylcarbonyl group, or each independently selected from an optionally substituted C 8-20 straight or branched alkyl group, an optionally substituted C 8-20 straight or branched alkenyl group, optionally substituted C 8 a -20 linear or branched alkylcarbonyl group and
  • each group Rd is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group, optionally substituted C 2 a linear or branched alkenylene group, an optionally substituted C 1-10 linear or branched alkylenecarbonyl group, an optionally substituted C 2-10 linear or branched alkenylenecarbonyl group, optionally substituted
  • the carbonyl C 1-10 linear or branched alkylenecarbonyl group and the optionally substituted carbonyl C 2-10 linear or branched alkenylenecarbonyl group are preferably each independently selected from optionally substituted C 1-5 straight A chain or branched alkylene group and an optionally substituted C 1-5 linear or branched alkylene carbonyl group.
  • x"" represents a unit The number is an arbitrary integer between 1 and 9, preferably any integer between 1 and 3, more preferably 1 or 2.
  • each (i.e., x"") groups Rp 1 are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group, provided that at least one (such as one or two) groups Rp 1 is a formula Representative group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 may be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group Rp 2 is selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • each (i.e., a) groups Rp 3 are the same or different from each other, and are each independently selected from the formula Representative group, hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight chain Or a branched alkenyl group and an optionally substituted C 6-50 aryl group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the respective values m' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m' represents the unit The average number, so it can be a non-integer.
  • the numerical value m' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n' are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value n' represents the average number of units -CH 2 -CH 2 -O- and thus may be a non-integer.
  • the numerical value n' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values m" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m′′ represents the unit The average number, so it can be a non-integer.
  • the numerical value m for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the stated value n" represents the average number of units -CH 2 -CH 2 -O- and thus may be non-integer.
  • the numerical value n" for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values m'" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • the value m'" represents the unit The average number, so it can be a non-integer.
  • the numerical value m'" for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the respective values n'" are the same or different from each other, and are each independently selected from any value between 0 and 100, preferably any value between 0 and 50.
  • said value n "' represents the average number of units -CH 2 -CH 2 -O-, and thus may be non-integers.
  • the numerical value n' for example, it may be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the unit The overall average number is greater than 0, but generally does not exceed 100, preferably does not exceed 50. In view of this, it is preferred to contain (a certain number of) units in the overall molecular structure of the compound represented by the formula (I-4).
  • the overall average number can be, for example, 0.1, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the overall average number of the units -CH 2 -CH 2 -O- is not more than 100, preferably not more than 50.
  • the overall average number of the units -CH 2 -CH 2 -O- may be, for example, 0, 0.5, 1.2, 2.0, 2.5 , 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0. , 45.5 or 50.5, etc.
  • all (x"" numerical values n', all (one) numerical values n" and all (a) numerical values n'" The sum (i.e., the overall average number of units -CH 2 -CH 2 -O- in the overall molecular structure of the compound represented by the formula (I-4)) is more than 0. In view of this, in the overall molecular structure of the compound represented by the formula (I-4), it is preferred to contain (a certain number of) units -CH 2 -CH 2 -O-.
  • the overall average number of the units -CH 2 -CH 2 -O- may be, for example, 0.1, 0.5, 1.2, 2.0, 2.5 . , 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5 or 50.5.
  • the sum of all (x"" numerical values n', all (one) numerical values n" and all (a) numerical values n'" i.e., in the formula (I) -4) the overall molecular structure of the compound shown, the overall average number of units -CH 2 -CH 2 -O-) and all (x"" values m', all (1) values m" and all (a) the sum of the values m′′′ (ie, in the overall molecular structure of the compound represented by the formula (I-4), the unit
  • the sum of the overall average numbers is greater than zero, but generally does not exceed 200, preferably does not exceed 100.
  • the overall molecular structure of the compound represented by the formula (I-4) it is preferred to contain (a certain number of) units -O-CH 2 -CH 2 - and/or At this time, in the overall molecular structure of the compound represented by the formula (I-4), as the overall average number of these units, for example, it may be 0.1, 0.5, 1.5, 2.0, 3.0, 3.5, 7.5, 10.0, 15.0, 25.0. , 30.2, 35.0, 40.0, 45.5, 50.5, 55.2, 60.0, 75.5, 80.5, 85.0, 90.5 or 95.7.
  • each group L is the same or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group and an optionally substituted C 2 .
  • the -10 linear or branched alkenylene group is preferably each independently selected from an optionally substituted C 1-5 linear or branched alkylene group.
  • each of the groups Salt is identical or different from each other, and each is independently selected from a group represented by -A - (M) r + wherein the group A - is selected from a carboxylate group ( COO - ) and sulfonate (SO 3 - ), the group M is selected from the group consisting of alkali metals (preferably Li, Na and K), alkaline earth metals (preferably Mg and Ca) and ammonium (NH 4 ).
  • alkali metals preferably Li, Na and K
  • alkaline earth metals preferably Mg and Ca
  • NH 4 ammonium
  • the group A - may be one or plural, and at least one of the groups A - is a carboxylate ( COO - ).
  • at least one carboxylate (COO - ) is preferably present in the entire molecular structure of the compound represented by the formula (I-4).
  • the group Rc and the group Rh (including all the groups Rc and Rh contained in the compound represented by the formula (I-4), obviously include the aforementioned quaternary ammonium salt groups Rh (base) included) at least one (such as one, two, or three, etc.) must contain (s) in their structure a straight-chain C 8 fraction consisting of This allows the compound represented by the formula (I-4) to exhibit the desired surface activity properties.
  • the so-called optional substitution it is meant that one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) are optionally selected from a hydroxyl group, a C 1-20 linear or branched alkyl group. Substituted with a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the anionic-cationic-nonionic surfactants of the present invention represented by the above respective formulas, as shown by their respective structural formulae, clarify that their respective molecular structures must simultaneously contain an ionic group (M) r + and the group X - (sometimes it is also possible to write (M) r and X separately).
  • M ionic group
  • X group X
  • these two ionic groups show high reactivity to each other, so if they coexist in the same system, such as coexisting in the same molecular structure, they tend to occur with each other.
  • the reaction produces an inorganic compound of the formula (M) r + X - (sometimes may also be written as (M) r X).
  • the inorganic compound is sometimes present in free form (even such as precipitation or formation of a separate phase) independently of the anionic-cationic-nonionic surfactant of the invention, resulting in these groups (ie group (M) r + At least a part (and sometimes all) of the group X - ) cannot be a constituent of the molecular structure of the anion-cation-nonionic surfactant of the present invention as is clear from these structural formulae.
  • the anionic-cationic-nonionic surfactant of the present invention substantially (such as losing all of the group (M) r + or the group X - ) or at least partially (such as losing a portion of the group) (M) The form of r + or the group X - ) betaine is present.
  • the group A - and the group N + contained in the molecular structure of the anion-cation-nonionic surfactant become new counter ions to each other.
  • the total number of the groups X - is e1
  • the total number of the groups N + is e2
  • the anionic-cationic-nonionic surfactant of the present invention sometimes contains the group (M) r + and the group X in its molecular structure.
  • the anionic-cationic-nonionic surfactant of the present invention are not produced due to the formation of the inorganic compound, or the amount thereof, or the form thereof. Substantial influence, therefore the invention is not intended to give any special provisions for the inorganic compound.
  • the anionic-cationic-nonionic surfactant of the present invention in order to more precisely describe or define the anionic-cationic-nonionic surfactant of the present invention, "substantially as shown in Formula ##" or the like is used.
  • the phrase "substantially as shown in the formula ##" (such as the foregoing is substantially as shown in the formula (I), substantially as shown in the formula (I-1), and substantially as in the formula (I-2). Shown, substantially as shown in formula (I-3) or substantially as shown in formula (I-4), or the like, refers to the anionic-cationic-nonionic surfactant of the present invention.
  • the group (M) r + and the group X ⁇ are simultaneously contained, and as explained above, at least a part (or even all) of the groups (M) r + and/or groups are lost.
  • X - does not even contain (or does not exist) a group (M) r + and / or a group X - .
  • the anionic-cationic-nonionic surfactants of the above formulas can be produced, for example, according to the following production method, wherein the production method includes, for example, the following steps (1) to (5).
  • Step (1) contacting one or more nitrogen and having one or more substituents selected from -OH, -NH 2 and - NH - shown polyfunctional compound with one or more functional group of formula (Y)
  • the alkylene oxide is reacted in the presence of a basic catalyst to obtain an etherified product.
  • any one or more for example, 1 to 10, preferably 1 to 4, such as 2, 3 or 4) may be used.
  • the compound of the functional group of -OH, -NH 2 and -NH- is not particularly limited. Since these functional groups contain an active hydrogen, a ring-opening (polymerization) reaction can be caused by an alkylene oxide such as ethylene oxide, whereby a (poly)ether segment is introduced into the molecular structure of the polyfunctional compound.
  • These polyfunctional compounds may be used singly or in combination of two or more kinds. Further, these polyfunctional compounds may be used as they are, or may be produced by any known method.
  • the polyfunctional compound in step (1), must contain a nitrogen atom.
  • the nitrogen atom may be derived from a primary amine group, a tertiary amine group or a secondary amine group which the polyfunctional compound may contain.
  • an amine compound represented by the following formula (X) can be mentioned. These compounds may be used singly or in combination of two or more kinds.
  • the groups R' 1 to R' 3 are the same or different from each other, each independently selected from hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally Substituted C 5-50 monocyclic or polycyclic cycloalkyl, optionally substituted C 2-50 straight or branched alkenyl, optionally substituted C 6-50 aryl and Representative group.
  • the term "optionally substituted” means that one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) is selected from oxo (ie, ), hydroxyl, by Representative of a group, a C 1-20 straight or branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group, and a C 6-20 aryl group Substituted.
  • oxo ie, 1, 2, 3, 1 to 2 or 1 to 2 or 1
  • hydroxyl by Representative of a group, a C 1-20 straight or branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group, and a C 6-20 aryl group Substituted.
  • the C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 can be mentioned.
  • -7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • At least one of the groups R' 1 to R' 3 (for example, at most two) is required to be hydrogen or Representative group.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear chain may be mentioned.
  • a branched alkyl group or a C 8-20 linear or branched alkyl group such as octadecyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl, and the like.
  • C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group L A is selected from an optionally substituted x0+1 valent C 1-50 straight or branched alkyl group, an optionally substituted x0 +1 C 5-50 monocyclic or polycyclic ring Alkyl, optionally substituted x0+1 valent C 2-50 straight or branched alkenyl, optionally substituted x0+1 valent C 6-50 aryl, and optionally substituted x0 +1 C 3-50 Linear or branched heteroalkyl.
  • an optionally substituted x0+1 valent C 1-20 linear or branched alkyl group is preferred.
  • an optionally substituted x0+1-valent C 5-50 monocyclic or polycyclic cycloalkyl group for example, an optionally substituted x0+1 valent C 5-10 monocyclic or polycyclic cycloalkyl group may be mentioned.
  • an optionally substituted x0+1-valent C 2-50 straight-chain or branched alkenyl group an optionally substituted x0+1-valent C 2-20 straight-chain or branched alkenyl group is preferred.
  • an optionally substituted x0+1 valent C 6-50 aryl group an optionally substituted x0+1 valent C 6-20 aryl group such as a phenyl group or a naphthyl group is preferred.
  • an optionally substituted x0+1 valent C 3-50 linear or branched heteroalkyl group an optionally substituted x0+1 valent C 3-20 linear or branched heteroalkyl group is preferred.
  • the respective groups Func are identical or different from each other, each independently selected from -OH, -NH- and -NH 2 , preferably each independently selected from -OH and -NH 2 .
  • x0+1 generally represents a valence state value of the group L A , wherein x0 is an arbitrary integer between 1 and 10, preferably any integer between 1 and 4, such as 1. 2 or 3.
  • x0 is an arbitrary integer between 1 and 10, preferably any integer between 1 and 4, such as 1. 2 or 3.
  • x0 represents the number of interruptions, and does not necessarily represent the valence state of the group L A (the lowest value of the valence may be 1, such as x0 When the group Func is both -NH-).
  • the group L A is interrupted multiple times by these -NH- at any (acceptable) position.
  • the term "interruption” as used herein refers to the internal insertion of the -NH- to the molecular structure of the group L A without being at the end of the main chain or any side chain in its molecular structure.
  • each -NH- is not directly bonded.
  • the group Func is -NH-
  • x0 is 1 (the number of interruptions is 1)
  • the group L A is 1 valence (no longer a divalent) C 8 linear alkyl group (where the position indicated by the arrow is the end of the main chain in the molecular structure)
  • the group L A may be or Wait.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 5, 1 to 4, 1 to 3). , 1 to 2 or 1) selected from oxo, hydroxy, C 1-20 straight or branched alkyl, C 5-10 monocyclic or polycyclic cycloalkyl, C 2-20 straight or branched Substituents of alkenyl and C 6-20 aryl groups are substituted.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • embodiment A in formula (X), in the presence of oxo as a substituent for a group such as group L A , preferably at least one oxo substitution
  • the group is located on a carbon atom directly bonded to an N atom (if any, such as a N atom which may be contained in a linear or branched heteroalkyl group), such that the carbon atom appears as a carbonyl group (ie, a form whereby a structure in which a carbonyl group is directly bonded to an N atom (such as an imido group) is introduced into the group.
  • At least a part (preferably all) is not present on the carbon atom to which the O or S atom, if any, is directly bonded.
  • a base, and/or at least a portion (preferably all) of carbon atoms at the position of the chain end (referring to the free end of the molecular chain and/or the end to be bonded to other atoms) (if the group Func is -NH- Or -NH 2 , such as a chain terminal carbon atom in the group L A directly bonded to the group Func, see the absence of the oxo substituent on the embodiment B) below, and/or two The directly bonded carbon atoms are not replaced by oxo at the same time.
  • the group L A is a divalent linear alkyl group substituted with one oxo substituent. (which includes two carbon atoms at the position of the chain end, as indicated by the arrow in the formula), according to the foregoing principle, the group is preferably, for example, or Wait.
  • the group L A is a divalent branched heteroalkyl group substituted by one oxo substituent (which includes three carbon atoms at the chain end position, as indicated by the arrow in the formula, and also includes three carbon atoms directly bonded to the N atom), according to the foregoing principle, the group is preferably, for example, or Wait.
  • Embodiment B when the group Func is -NH- or -NH 2 , in the formula (X), in the presence of oxo as a substituent, preferably at least one oxygen
  • the substituent is located on a carbon atom directly bonded to the group Func, or an oxo substituent is present on at least one of the carbon atoms directly bonded to the group Func, thereby being in the group L A
  • a structure in which a carbonyl group is directly bonded to an N atom (such as an acylamino group) is introduced.
  • the group L A is a divalent linear alkyl group substituted with one oxo substituent.
  • Representative groups are preferred in addition to embodiment A In addition, it can be
  • At least one of the polyfunctional compound and the quaternizing agent represented by the formula (A) described below must contain a C 8 linear portion (in one or more) in its molecular structure ( Hereinafter, it is sometimes referred to as regulation (1)).
  • the amine compound of the formula (X) with the quaternizing agent must contain at least one (one or more) in the molecular structure thereof C 8 linear Chain part.
  • the groups R' 1 to R' 3 (from the amine compound represented by the formula (X)) and the group Rh (see below, from the quaternization) At least one of the agents (such as 1, 2, or 3, etc.) must contain a C 8 linear portion in one or more of its structures.
  • the amine compound represented by the formula (X) is more specifically, for example, a compound represented by the following formula (X-1) and a compound of the following formula (X-2).
  • the respective groups Ra are the same or different from each other, and are each independently selected from hydrogen, an optionally substituted C 1-20 straight or branched alkyl group, and an optionally substituted C. 2-20 linear or branched alkenyl group and optionally substituted C 6-20 aryl group, preferably an optionally substituted C 8-20 linear or branched alkyl group and an optionally substituted C 6-10 aryl group.
  • each group Ra' is the same or different from each other, and each is independently selected from a single bond, an optionally substituted C 1-10 linear or branched alkylene group, optionally Substituted C 2-10 linear or branched alkenylene, carbonyl, optionally substituted C 1-10 straight or branched alkylene carbonyl, and optionally substituted C 2-10 straight or branched alkylene
  • the carbonyl groups are preferably each independently selected from the group consisting of a single bond and an optionally substituted C 1-6 straight or branched alkylene group.
  • b is an arbitrary integer between 1 and 3, preferably 1.
  • x1 represents a group The number is an arbitrary integer between 1 and 5, preferably any integer between 1 and 4, such as 1, 2 or 3. Obviously, b+x1 ⁇ 6.
  • each (i.e., x1) groups Rp' 1 are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 linear or branched alkane. a optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl group, an optionally substituted C 2-50 straight or branched alkenyl group, and an optionally substituted C 6-50 aryl group, provided that at least one The group Rp' 1 is hydrogen.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • each (i.e., x1 ⁇ a1) groups Rp' 2 are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 straight chain or branch.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group Ra and the group Rh (including all the groups Ra contained in the compound represented by the formula (X-1) are desired. At least one (such as 1, 2, 3, etc.) of all the groups Rh) contained in the quaternizing agent represented by the formula (A) described below must contain (one or more) in its structure The C 8 linear portion.
  • the group Rb is selected from an optionally substituted C 1-49 linear or branched alkyl group, an optionally substituted C 5-49 monocyclic or polycyclic cycloalkyl group.
  • optionally substituted C 2 - 49 linear or branched alkenyl preferably selected from optionally substituted C 1-29 straight or branched alkyl, optionally substituted C 5-10 monocyclic or polycyclic ring
  • a cycloalkyl group such as a cyclohexyl group and an optionally substituted
  • each of the groups Rb' is the same or different from each other, and each is independently selected from a single bond and a carbonyl group.
  • x2 represents a group The number is any integer between 1 and 10, preferably any integer between 1 and 4, such as 1, 2 or 3.
  • each (i.e., x2) groups Rp' 1 are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 linear or branched alkane. a optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl group, an optionally substituted C 2-50 straight or branched alkenyl group, and an optionally substituted C 6-50 aryl group, provided that at least one The group Rp' 1 is hydrogen.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • each (i.e., x2 ⁇ a2) groups Rp' 2 are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 straight chain or branch.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group Rb and the group Rh (including all the groups Rb contained in the compound represented by the formula (X-2) are desired. At least one (such as 1, 2, 3, etc.) of all the groups Rh) contained in the quaternizing agent represented by the formula (A) described below must contain (one or more) in its structure The C 8 linear portion.
  • each group Rc is the same or different from each other, and each is independently selected from an optionally substituted C 1-20 linear or branched alkyl group, optionally substituted C 2 - a 20- or branched-chain alkenyl group, an optionally substituted C 1-20 straight or branched alkylcarbonyl group, and an optionally substituted C 2-20 straight or branched alkenylcarbonyl group, or each independently selected from any Substituted substituted C 1-10 linear or branched alkyl, optionally substituted C 2-10 straight or branched alkenyl, optionally substituted C 1-10 straight or branched alkyl carbonyl, and optionally Substituted C 2-10 straight or branched alkenylcarbonyl, or each independently selected from optionally substituted C 8-20 straight or branched alkyl, optionally substituted C 8-20 straight or branched Alkenyl, optionally substituted C 8-20 straight or branched alky
  • each group Rd is identical or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group, optionally substituted C 2 a linear or branched alkenylene group, an optionally substituted C 1-10 linear or branched alkylenecarbonyl group, an optionally substituted C 2-10 linear or branched alkenylenecarbonyl group, optionally substituted
  • the carbonyl C 1-10 linear or branched alkylenecarbonyl group and the optionally substituted carbonyl C 2-10 linear or branched alkenylenecarbonyl group are preferably each independently selected from optionally substituted C 1-5 straight A chain or branched alkylene group and an optionally substituted C 1-5 linear or branched alkylene carbonyl group.
  • x3 represents a unit The number is any integer between 1 and 10, preferably any integer between 1 and 4, such as 1, 2 or 3.
  • each (i.e., x3) groups Rp' are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 linear or branched alkyl group.
  • the group Rp' is hydrogen.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group Rc and the group Rh (including all the groups Rc contained in the compound represented by the formula (X-3) are desired.
  • At least one (such as 1, 2, 3, etc.) of all the groups Rh) contained in the quaternizing agent represented by the formula (A) described below must contain (one or more) in its structure The C 8 linear portion.
  • the group Rc is selected from an optionally substituted C 1-20 straight or branched alkyl group, an optionally substituted C 2-20 straight or branched alkenyl group, An optionally substituted C 1-20 linear or branched alkylcarbonyl group and an optionally substituted C 2-20 straight or branched alkenylcarbonyl group, or each independently selected from optionally substituted C 1-10 straight chain Or a branched alkyl group, an optionally substituted C 2-10 straight or branched alkenyl group, an optionally substituted C 1-10 straight or branched alkylcarbonyl group, and an optionally substituted C 2-10 straight chain or A branched alkenylcarbonyl group, or each independently selected from an optionally substituted C 8-20 straight or branched alkyl group, an optionally substituted C 8-20 straight or branched alkenyl group, optionally substituted C 8 a -20 linear or branched alkylcarbonyl group and
  • each group Rd is identical or different from each other, and each is independently selected from an optionally substituted C 1-10 linear or branched alkylene group, optionally substituted C 2 a linear or branched alkenylene group, an optionally substituted C 1-10 linear or branched alkylenecarbonyl group, an optionally substituted C 2-10 linear or branched alkenylenecarbonyl group, optionally substituted
  • the carbonyl C 1-10 linear or branched alkylenecarbonyl group and the optionally substituted carbonyl C 2-10 linear or branched alkenylenecarbonyl group are preferably each independently selected from optionally substituted C 1-5 straight A chain or branched alkylene group and an optionally substituted C 1-5 linear or branched alkylene carbonyl group.
  • x4 represents a unit The number is an arbitrary integer between 1 and 9, preferably any integer between 1 and 3, more preferably 1 or 2.
  • each (i.e., x4) groups Rp' 1 are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 linear or branched alkane. a optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl group, an optionally substituted C 2-50 straight or branched alkenyl group, and an optionally substituted C 6-50 aryl group, provided that at least one The group Rp' 1 is hydrogen.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group Rp' 2 is selected from hydrogen, optionally substituted C 1-50 straight or branched alkyl, optionally substituted C 5-50 monocyclic or poly Cyclocycloalkyl , optionally substituted C 2-50 straight or branched alkenyl and optionally substituted C 6-50 aryl.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 linear or branched alkenyl group and a C 6-20 aryl substituent.
  • a C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned. .
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • -7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • each (i.e., a4) groups Rp' 3 are the same or different from each other, and are each independently selected from hydrogen, optionally substituted C 1-50 linear or branched alkane.
  • the C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, specifically, for example, eighteen Alkyl, lauryl, octyl, hexadecyl, hexyl, methyl or ethyl and the like.
  • the C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group Rc and the group Rh (including all the groups Rc contained in the compound represented by the formula (X-4) are desired. At least one (such as 1, 2, 3, etc.) of all the groups Rh) contained in the quaternizing agent represented by the formula (A) described below must contain (one or more) in its structure The C 8 linear portion.
  • the term "optionally substituted” means Optionally selected from one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) selected from oxo, hydroxy, C 1-20 straight or branched alkane Substituent, C 5-10 monocyclic or polycyclic cycloalkyl, C 2-20 straight or branched alkenyl and C 6-20 aryl substituent.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the polyfunctional compound, the amine compound represented by the formula (X), the compound represented by the formula (X-1), the compound represented by the formula (X-2), and the formula (X-3) can be directly used as a commercially available product, or can be produced by any method known in the art.
  • an amidating agent such as diisopropanolamine
  • the group Rb and the value x2 are the same as defined in the formula (X-2), and the group R ac is H or a C 1-4 straight or branched alkyl group.
  • the amidation step can be carried out in any manner known in the art, but the reaction temperature is usually from 100 to 200 ° C, the reaction time is usually from 1 to 10 hours, and the reaction pressure can be normal pressure or any suitable reaction. pressure.
  • any basic catalyst conventionally used in the prior art for this purpose can be directly used, and among them, an alkali metal hydroxide, particularly sodium hydroxide, is preferable. Or potassium hydroxide.
  • these basic catalysts may be used singly or in combination of two or more kinds.
  • the amount of the basic catalyst the usual amount in the art can be directly applied, but generally the basic catalyst is made to reach the total weight of the compound represented by the formula (X-2-1) and the amidating agent. 0.2-20% by weight, preferably 0.5-15% by weight.
  • the molar ratio of the compound represented by the formula (X-2-1) to the amidating agent is generally 1:1 to 15, 1-10, 1 1-8, 1:1-5 or 1:2-4, but sometimes it is not limited thereto, and may be any molar ratio capable of converting all of the x2 groups -COOR ac into an amide group.
  • the unreacted amidating agent is removed from the reaction product mixture by a conventionally known separation means such as vacuum suction to obtain the formula (X-2).
  • the group Ru' is selected from a C 2-6 straight or branched alkylene group, of which -CH 2 -CH 2 - and/or -CH 2 -CH (CH 3 is preferred) -, more preferably, a combination of -CH 2 -CH 2 - and -CH 2 -CH(CH 3 )-.
  • examples of the alkylene oxide represented by the formula (Y) include ethylene oxide, propylene oxide, butylene oxide, and hexylene oxide. These alkylene oxides may be used singly or in combination of two or more kinds, such as a combination of ethylene oxide and propylene oxide.
  • one or more alkylene oxides of the formula (Y) are used, preferably wherein at least one alkylene oxide is propylene oxide.
  • the propylene oxide can be used in combination with other alkylene oxides (especially ethylene oxide) represented by the formula (Y) as needed.
  • the molar ratio of propylene oxide to other alkylene oxide (especially ethylene oxide) represented by the formula (Y) may be, for example, 1:0.1-10, but is not limited thereto.
  • any basic catalyst conventionally used in the prior art for this purpose can be directly used, and among them, an alkali metal hydroxide, particularly potassium hydroxide, is preferable.
  • These basic catalysts may be used singly or in combination of two or more kinds.
  • the amount of the basic catalyst in the step (1), the usual amount in the art can be directly applied, but generally the polyfunctional compound (such as the amine compound represented by the formula (X)) is The molar ratio of the basic catalyst is from 1:1-10, preferably from 1:1-5.
  • the molar ratio of the polyfunctional compound (such as the amine compound represented by the formula (X)) to the alkylene oxide is generally from 1:0 to 200, preferably 1:0. 100, but not including 0, more preferably 1:0.1-50.
  • the reaction temperature is usually from room temperature to 300 ° C, preferably from 100 to 200 ° C
  • the reaction time is usually from 1 to 20 hours, preferably from 1 to 10 hours
  • the reaction pressure may be any suitable for the reaction.
  • the pressure that is being carried out such as atmospheric pressure.
  • the alkylene oxide represented by the formula (Y) if two or more (preferably including at least propylene oxide) are used in combination, the A polyfunctional compound (such as an amine compound of formula (X)) is first reacted with (at least a portion or all of the amount) of propylene oxide, and then (preferably after at least partially or completely ending the reaction with said propylene oxide) And other alkylene oxides (such as rings Oxyethane) reaction.
  • the A polyfunctional compound such as an amine compound of formula (X)
  • the obtained reaction product mixture can be directly subjected to the subsequent step (2) as an etherification product without any separation or purification, or only needs to be separated (for example by
  • the aqueous catalyst may be washed with water.
  • Step (2) The etherified product is reacted with a quaternizing agent represented by the following formula (A), whereby the cationic-nonionic surfactant is obtained.
  • the group Rh is selected from an optionally substituted C 1-50 linear or branched alkyl group, an optionally substituted C 5-50 monocyclic or polycyclic cycloalkyl group, A substituted C 2-50 straight or branched alkenyl group and an optionally substituted C 6-50 aryl group are selected.
  • C 1-50 linear or branched alkyl group for example, a C 1-20 linear or branched alkyl group or a C 8-20 linear or branched alkyl group may be mentioned, and specifically, for example, octadecyl group, Lauryl, octyl, hexadecyl, hexyl, methyl or ethyl.
  • C 5-50 monocyclic or polycyclic cycloalkyl group for example, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 can be mentioned.
  • Monocyclic or polycyclic cycloalkyl especially C 5-7 monocyclic cycloalkyl, such as, for example, cyclopentyl or cyclohexyl.
  • C 2-50 linear or branched alkenyl group for example, a C 2-20 linear or branched alkenyl group or a C 8-20 linear or branched alkenyl group may be mentioned, and specifically, for example, octadecyl group , dodecenyl, linoleyl, vinyl, propenyl or allyl.
  • C 6-50 aryl group for example, a C 6-20 aryl group or a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the term "optionally substituted” means optionally one or more (for example, 1 to 4, 1 to 3, 1 to 2 or 1) selected from a hydroxyl group, a C 1-20 linear chain. Substituted by a branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 straight or branched alkenyl group and a C 6-20 aryl group.
  • C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned.
  • C 5-10 monocyclic or polycyclic cycloalkyl group for example, a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C 5 may be mentioned.
  • C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • C 6-20 aryl group for example, a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the group X' is selected from halogens, including fluorine, chlorine, bromine and iodine, with chlorine being preferred.
  • the molar ratio of the polyfunctional compound (such as the amine compound represented by the formula (X)) to the quaternizing agent represented by the formula (A) is generally 1: 0.1-200, preferably 1:0.1-50, but sometimes it is not limited thereto, as long as the quaternizing agent is used in an amount such that at least one N atom in the molecular structure of the etherified product forms a quaternary ammonium salt group.
  • the reaction temperature is usually from 0 to 300 ° C, preferably from 50 to 150 ° C
  • the reaction time is usually from 1 to 20 hours, preferably from 4 to 15 hours
  • the reaction pressure is It is any pressure suitable for the reaction, such as atmospheric pressure.
  • the step (2) may be carried out in the presence of a catalyst or may be omitted.
  • a catalyst conventionally used for this purpose in the art can be used as it is, and specific examples thereof include potassium iodide.
  • the amount of the catalyst a conventional amount in the art can be directly applied, and specific examples thereof include 0.5 to 3.0% by weight, particularly 1.0 to 2.0% by weight.
  • the reaction product mixture obtained in the step (2) can be treated by a conventional separation method, thereby separating the cationic-nonionic surfactant.
  • a separation method for example, extraction under alkaline conditions can be mentioned.
  • Step (3) reacting the cationic-nonionic surfactant with one or more compounds represented by the following formula (Z) in the presence of a basic catalyst, thereby obtaining an anion-cation-non of the present invention
  • An ionic surfactant including a compound substantially as shown in the above formula (I), a compound substantially as shown in the above formula (I-1), a compound substantially as shown in the above formula (I-2), A compound substantially as shown in the above formula (I-3) or a compound substantially as shown in the above formula (I-4).
  • any basic catalyst conventionally used in the prior art for this purpose can be directly used, and among them, an alkali metal hydroxide, particularly sodium hydroxide or Potassium hydroxide.
  • alkali metal hydroxide particularly sodium hydroxide or Potassium hydroxide.
  • These basic catalysts may be used singly or in combination of two or more kinds.
  • the amount of the basic catalyst in the step (3), the usual amount in the art can be directly applied, but generally the polyfunctional compound (such as the amine compound represented by the formula (X)) is
  • the polyfunctional compound such as the amine compound represented by the formula (X)
  • the molar ratio of the basic catalyst is from 1:1-10, preferably from 1:1-5.
  • the group G is selected from the group consisting of halogen and hydroxyl, preferably halogen.
  • halogen for example, fluorine, chlorine, bromine and iodine are mentioned, and chlorine is preferred.
  • the group L is selected from the group consisting of an optionally substituted C 1-10 straight or branched alkylene group and an optionally substituted C 2-10 straight or branched alkenylene group, It is preferably selected from an optionally substituted C 1-5 linear or branched alkylene group.
  • the group AS is selected from the group consisting of -A - (M') r + wherein the group A - is selected from the group consisting of carboxylate (COO - ) and sulfonate (SO 3 -
  • the group M' is selected from the group consisting of hydrogen, alkali metals (preferably Li, Na and K), alkaline earth metals (preferably Mg and Ca) and ammonium (NH 4 ), preferably alkali metals (preferably Li, Na and K) and alkaline earths. Metal (preferably Mg and Ca).
  • the group G when the group A - is a carboxylate (COO - ), the group G is a halogen, and when the group A - is a sulfonate (SO 3 - ) The group G is a halogen or a hydroxyl group.
  • one or more compounds of the formula (Z) are used, wherein in at least one compound of the formula (Z), the group A - is a carboxylate (COO - ).
  • the group A - is a carboxylate (COO - ).
  • the term "optionally substituted” means optionally one or more (for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1). a substituent selected from a hydroxyl group, a C 1-20 linear or branched alkyl group, a C 5-10 monocyclic or polycyclic cycloalkyl group, a C 2-20 linear or branched alkenyl group and a C 6-20 aryl group Substituted.
  • a C 1-20 linear or branched alkyl group for example, a C 1-10 linear or branched alkyl group or a C 1-6 linear or branched alkyl group, or a methyl group or an ethyl group may be mentioned. .
  • C 5-10 monocyclic or polycyclic cycloalkyl group
  • a C 5-8 monocyclic or polycyclic cycloalkyl group or a C 5-7 monocyclic or polycyclic cycloalkyl group, especially C may be mentioned.
  • 5-7 monocyclic cycloalkyl specifically such as cyclopentyl or cyclohexyl.
  • the C 2-20 linear or branched alkenyl group for example, a C 2-10 linear or branched alkenyl group may be mentioned, and specific examples thereof include a vinyl group, a propenyl group or an allyl group.
  • a C 6-10 aryl group such as a phenyl group or a naphthyl group can be exemplified.
  • the molar ratio of the polyfunctional compound (such as the amine compound represented by the formula (X)) to the compound represented by the formula (Z) is 1:1-10. , preferably 1:1.
  • the reaction temperature is usually from 0 to 300 ° C, preferably from 50 to 200 ° C
  • the reaction time is usually from 1 to 20 hours, preferably from 4 to 10 hours
  • the reaction pressure may be any suitable for the reaction.
  • the pressure that is being carried out such as atmospheric pressure.
  • the reaction product mixture obtained in the step (3) can be treated by a conventional separation method, thereby separating the surfactant.
  • a conventional separation method for example, an acidic aqueous solution (such as an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous phosphoric acid solution, an aqueous sodium hydrogen sulfate solution, an aqueous potassium hydrogen sulfate solution, or the like) may be added to the reaction product mixture obtained in the step (3).
  • the anionic-cationic-nonionic surfactant obtained as described above may be further contacted with a neutralizing agent as needed, whereby the surfactant may be contained therein.
  • the free acidic group (such as a free carboxyl group or a sulfonic acid group) is converted into a salt form (hereinafter referred to as a neutralization step).
  • a neutralizing agent for example, an alkali metal (preferably Li, Na, and K) hydroxide, an alkaline earth metal (preferably Mg and Ca) hydroxide, or ammonia water can be given.
  • alkali metal preferably Li, Na, and K
  • an alkaline earth metal preferably Mg and Ca
  • ammonia water preferably ammonia water
  • an aqueous solution or an aqueous suspension in which a certain amount of the neutralizing agent is added to the anion-cation-nonionic surfactant may be mentioned, and the mixture is neutralized to pH. Values are 7-9 or 8-10, then remove moisture (Methods such as heating evaporation, vacuum removal, etc.), but are not limited thereto.
  • Step (4) an anion-cation-non obtained by any step of the production method of the present invention (including the aforementioned step (3) and neutralization step, and the step (5) described below), as needed Converting at least a portion (or all) of the quaternary ammonium salt groups in the molecular structure of the ionic surfactant to the corresponding quaternary ammonium base group, and/or, the obtained anionic-cationic-nonionic surfactant molecule At least a portion (or all) of the quaternary ammonium groups in the structure are converted to the corresponding quaternary ammonium salt groups.
  • this step (4) is an optional step and not a necessary step.
  • the step (4) can be carried out in any manner conventionally known, and examples thereof include an electrolysis method or an ion exchange method, and are not particularly limited.
  • Step (5) separating at least a part of the anion-cation-nonionic surfactant obtained from any step of the production method of the present invention (including the aforementioned step (3), step (4), and neutralization step) (preferably all) the compound (M') r X' (corresponding to the inorganic compound represented by the formula (M) r + X - described above) in a free form.
  • the group (M') r is derived from the compound represented by the above formula (Z)
  • the group X' is derived from the quaternizing agent represented by the above formula (A).
  • the compound (M') r X' mainly serves as an ionic group (M') r + and an ionic group X' which are highly reactive with each other during the progress of the above step (3) or step (4). - Generated by encounter.
  • an anionic-cationic-nonionic surfactant of the invention substantially or at least partially in the form of a betaine salt, is obtained as previously described.
  • a component of a nonionic surfactant (mixed component or innocuous impurity).
  • anionic-cationic-nonionic surfactants of the present invention are collectively referred to as anionic-cationic-nonionic surfactants of the present invention without distinction and are included in the scope of protection of the present invention. within.
  • this step (5) is an optional step, not a necessary step, and is not considered as a purification step for the anionic-cationic-nonionic surfactant of the present invention.
  • any step including the aforementioned step (3), step (4), and neutralization step from the production method of the present invention can be exemplified.
  • the compound (M') r X' Since the compound (M') r X' has strong water solubility, at least a part thereof may already be in the production process of the anion-cation-nonionic surfactant of the present invention (for example, in the step (3)) It is separated and removed by dissolving in water. The presence or absence or content of the compound (M') r X' has no substantial effect on various properties (such as interfacial activity and stability) of the anion-cation-nonionic surfactant produced by the present invention. Therefore, the present invention is not intended to specifically specify the content or the form of the compound (M') r X' in the anion-cation-nonionic surfactant obtained by the production method, and of course, the compound (M' is not present. r X' is removed from any of the anionic-cationic-nonionic surfactants previously obtained in the present invention.
  • the anionic-cationic-nonionic surfactant including a compound substantially as shown in the above formula (I), a compound substantially as shown in the above formula (I-1), substantially as The compound represented by the above formula (I-2), a compound substantially as shown in the above formula (I-3) or a compound substantially as shown in the above formula (I-4), etc.
  • the compound may also be a mixture comprising a plurality of compounds, and may even further comprise the aforementioned compound (M') r X', which are contemplated by the present invention.
  • the anionic-cationic-nonionic surfactant there is no further purification of the anionic-cationic-nonionic surfactant, or further separation from the obtained anionic-cationic-nonionic surfactant (mixture)
  • the necessity of a compound of a specific structure for example, a column chromatography method or a preparative chromatography method can be mentioned.
  • anionic-cationic-nonionic surfactant of the present invention different anionic-cationic-nonionic surfactant molecules may be present separately or in combination with anions and cations because they attract each other.
  • the association or even the occurrence of a chemical reaction (for example, by eliminating the compound (M) r + X - or the compound (M') r X', etc.) to form a new compound is not particularly limited. These states of existence are within the scope of protection of the present invention and are not limited to this literal expression.
  • the anionic-cationic-nonionic surfactant of the present invention due to the strong electrostatic attraction between the oppositely charged polar groups of the anionic and cationic surfactants, the adsorption amount of the surfactant molecules at the interface is increased.
  • the critical micelle concentration is significantly reduced, so that it has a high surface activity unmatched by a single surfactant.
  • the aqueous solution can form an ultra-low interfacial tension with the crude oil, thereby effectively overcoming the crude oil. Cohesion is conducive to the outflow of crude oil, which in turn greatly increases the efficiency of oil displacement.
  • the surfactant can change the wettability of the surface of the oil layer, for example, the cationic portion thereof is desorbed by interacting with a negatively charged group adsorbed on the solid surface, so that the oil wets the surface to change. It is a neutral wetting or water wetting surface, which reduces the adhesion work of crude oil on the solid surface, which is beneficial to the peeling of crude oil.
  • the mixture of anion and cation has a solubilizing effect on the crude oil, and the crude oil adhered to the rock and sand can be further washed to improve the oil recovery.
  • the anionic-cationic-nonionic surfactant of the present invention is particularly suitable for use in the manufacture of oil recovery compositions (displacement fluids) for tertiary recovery.
  • a third oil recovery oil flooding composition comprising the anionic-cationic-nonionic surfactant of the present invention, and water.
  • the anionic-cationic-nonionic surfactant of the present invention accounts for the total weight (in 100% by weight) of the tertiary oil recovery composition. 0.001-10% by weight, preferably 0.005 to 5% by weight, more preferably 0.02-1wt%.
  • the tertiary oil recovery composition may further include various additives conventionally used in the art at the time of manufacture, including but not limited to cationic water-soluble polymers, anionic water-soluble polymers or fatty alcohol ethers. Solvents, etc. These additives may be used singly or in combination of two or more kinds, and the amounts thereof may also be directly referred to conventional amounts in the art.
  • polyacrylamide As the cationic water-soluble polymer, for example, polyacrylamide can be mentioned.
  • the polyacrylamide generally has a number average molecular weight of 10 to 40 million, preferably 10 to 30 million, and is generally used in an amount of 0.05 to 5.0% by weight, preferably 0.1 to 0.5% by weight based on the total weight of the tertiary oil recovery composition. %, but sometimes it is not limited to this.
  • the oil recovery composition for tertiary oil recovery can obtain high oil displacement efficiency and oil washing ability even if it does not contain an inorganic base as a component. Therefore, according to a preferred embodiment of the present invention, the tertiary oil recovery composition does not contain (or is not intentionally added) an inorganic base as a component.
  • an inorganic basic compound conventionally used in the oil recovery composition for tertiary oil recovery particularly an alkali metal carbonate such as sodium carbonate, sodium hydrogencarbonate or the like can be mentioned.
  • the tertiary oil recovery composition can be produced by the following production method.
  • the method for producing the oil recovery composition for tertiary oil recovery comprises the step of mixing (to uniformity) the anionic-cationic-nonionic surfactant of the present invention with water (and additives as needed). At this time, the amount of the anionic-cationic-nonionic surfactant and the additive is previously specified.
  • the anionic-cationic-nonionic surfactant or the tertiary oil recovery composition can be used in a tertiary oil recovery method, and exhibits improved oil displacement efficiency and washing oil as compared with the prior art. Capacity (such as oil washing rate of crude oil can exceed 40%), which can significantly improve oil recovery.
  • the present invention also relates to a tertiary oil recovery method comprising the steps of performing tertiary oil recovery using the anionic-cationic-nonionic surfactant of the present invention or the above-described tertiary oil recovery oil displacement composition of the present invention as a displacement fluid. .
  • the inorganic base is not used or intentionally added during the tertiary recovery process. Therefore, the tertiary oil recovery method of the present invention does not harm the formation and the oil well, avoids corrosion of equipment and pipelines, and does not cause difficulty in breaking milk.
  • the anion-cation-nonionic surfactant or the oil recovery composition for tertiary oil recovery is easily soluble in water, and even at a high temperature, a stable and clear transparent aqueous solution can be formed in water without precipitation. Produced, excellent in chemical composition and interfacial activity.
  • the clear and transparent state of the aqueous solution can be stably maintained for a long period of time (even at a high temperature), thereby exhibiting excellent long-term chemical composition stability.
  • the anionic-cationic-nonionic surfactant, the oil recovery composition for tertiary oil recovery or an aqueous solution thereof is substantially stable even after long-term storage (especially at a high temperature). This shows excellent long-term interfacial activity stability.
  • the anionic-cationic-nonionic surfactant does not (substantially) exhibit chromatographic separation during use (i.e., component separation does not occur), chemical composition and interfacial activity in use. Excellent stability.
  • the temperature of the reaction system was raised to 220 ° C, and 1 mol of propylene oxide was introduced into the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After the reaction for 5 hours, an etherified product was obtained. All the etherification products were dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel.
  • quaternization reagent methyl chloride 1.1 mol was added with a nitrogen pressure of 0.8 MPa, and the reaction system was heated to 80 ° C and then reacted 3 to After 10 hours, the excess quaternization reagent methyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product (i.e., a cationic-nonionic surfactant, the same hereinafter).
  • a quaternized product i.e., a cationic-nonionic surfactant, the same hereinafter.
  • 1 mole of quaternized product 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel and the temperature was raised to 80 ° C, stirring was continued, and the quaternized product was converted into the corresponding potassium salt by azeotropic removal of moisture in the reaction system.
  • the temperature of the reaction system was raised to 220 ° C, and 1 mole of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and the reaction was small.
  • the etherified product was obtained afterwards. All etherification products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternization reagent methyl chloride was added with a nitrogen pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternization reagent methyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure thereof is 1-2 in Table 1, The nuclear magnetic resonance spectrum is shown in Table 5.
  • the temperature of the reaction system was raised to 220 ° C, 49 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 37 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa.
  • the etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternizing agent allyl chloride was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternization reagent allyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, 39 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 41 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa.
  • the etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternizing agent, benzyl chloride, was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternizing agent benzyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, and 1 mole of propylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After reacting for 5 hours, 39 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. The etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and a quaternizing agent, 1.1 moles of 2-chloropropane, was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternizing agent 2-chloropropane and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 11 moles of the carboxylating agent sodium chloroacetate was added to the reaction vessel.
  • the reactant was adjusted to be acidic with hydrochloric acid, and the reaction product was washed twice with 15% NaBr brine, and the product was converted into the corresponding product with aqueous magnesium hydroxide solution.
  • Magnesium salt The reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure thereof is 1-5 in Table 1, The nuclear magnetic resonance spectrum is shown in Table 5.
  • the temperature of the reaction system was raised to 220 ° C, 21 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 17 moles of propylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa.
  • the etherified product was obtained in an hour. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternizing agent ethyl chloride was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternizing agent ethyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, 11 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 27 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa.
  • the etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternizing agent allyl chloride was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternization reagent allyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • reaction was acidified with hydrochloric acid, and the reaction product was washed twice with 15% NaBr brine, and the product was converted to the corresponding ammonium salt with aqueous ammonia.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure of the agent is shown in Table 1 in Table 1 and its nuclear magnetic resonance spectrum is shown in Table 5.
  • the temperature of the reaction system was raised to 220 ° C, and 2 moles of propylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After reacting for 5 hours, 48 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. The etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 2.2 moles of quaternizing agent, benzyl chloride, was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternizing agent benzyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 2.2 mol of sodium sulfonate sodium chloromethylsulfonate was added to the reaction vessel.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure thereof is 2-1 in Table 2, The nuclear magnetic resonance spectrum is shown in Table 6.
  • the temperature of the reaction system was raised to 220 ° C, and 1 mole of ethylene oxide was introduced into the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After the reaction for 5 hours, an etherified product was obtained. All etherification products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternization reagent methyl chloride was added with a nitrogen pressure of 0.8 MPa. The reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternization reagent methyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 2-2.
  • the nuclear magnetic resonance spectrum is shown in Table 6.
  • the temperature of the reaction system was raised to 220 ° C, 49 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 37 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa.
  • the etherified product was obtained after 5 hours. All the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 1 mol of the quaternizing agent 1-chlorooctane was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess solvent ethanol was removed under reduced pressure to obtain a quaternized product.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure thereof is 2-3 in Table 2, The nuclear magnetic resonance spectrum is shown in Table 6.
  • the temperature of the reaction system was raised to 220 ° C, 25 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 17 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa.
  • the etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternizing agent allyl chloride was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternization reagent allyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, 25 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 17 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa.
  • the etherified product was obtained after 5 hours. All etherified products were dissolved in absolute ethanol to make a 40% solution, which was added to the reaction vessel, and 1.1 moles of the quaternizing agent, benzyl chloride, was added with nitrogen at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess solvent ethanol was removed under reduced pressure to obtain a quaternized product.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 2, 2-6.
  • the nuclear magnetic resonance spectrum is shown in Table 6.
  • the reaction product is dissolved in a large amount of absolute ethanol, the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 2, 2-7.
  • the nuclear magnetic resonance spectrum is shown in Table 6.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 2, 2-8.
  • the nuclear magnetic resonance spectrum is shown in Table 6.
  • the temperature of the reaction system was raised to 220 ° C, 14 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 9 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After 5 hours To the etherification product, all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 1.1 mole of the quaternization reagent methyl chloride was added with a nitrogen pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternization reagent methyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, 4 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 22 moles of propylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After 5 hours, an etherified product was obtained, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 1 mol of the quaternizing agent 1-chloro 12 was added with a nitrogen gas at a pressure of 0.8 MPa. alkyl.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess solvent ethanol was removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 2.2 mol of sodium carboxylate sodium chloroacetate was added to the reaction kettle.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternizing agent chlorocyclohexane and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then add 1 mole of ammonium quaternized product, 10 liters of solvent benzene and 1.1 moles of potassium hydroxide to the reaction kettle, heat up to 80 ° C and stir constantly, use azeotropic to remove the water produced by the reaction until the quaternized product is converted into the corresponding Potassium alkoxide. 1.1 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, 16 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 49 moles of propylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After 5 hours, an etherified product was obtained, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 1 mol of the quaternizing agent 1-chloro 12 was added with a nitrogen gas at a pressure of 0.8 MPa. alkyl.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess solvent ethanol was removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 2.2 mol of sodium carboxylate sodium chloroacetate was added to the reaction kettle.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure thereof is 3-5 in Table 3, The nuclear magnetic resonance spectrum is shown in Table 7.
  • the reaction product is dissolved in a large amount of absolute ethanol, the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 3, 3-6.
  • the nuclear magnetic resonance spectrum is shown in Table 7.
  • the reaction product is dissolved in a large amount of absolute ethanol, the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 3, 3-7.
  • the nuclear magnetic resonance spectrum is shown in Table 7.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 3, 3-8.
  • the nuclear magnetic resonance spectrum is shown in Table 7.
  • the temperature of the reaction system was raised to 220 ° C, 23 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 19 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After an hour, an etherified product was obtained, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 3.3 moles of the quaternizing agent ethyl chloride was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternizing agent ethyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 3.3 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 3.3 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • reaction was adjusted to be acidic with hydrochloric acid, and the reaction product was washed twice with 15% NaCl brine, and the product was converted into the corresponding aqueous solution with sodium hydroxide. Sodium salt.
  • the reaction product is dissolved in a large amount of anhydrous ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • Table 4-1 The nuclear magnetic resonance spectrum is shown in Table 8.
  • the temperature of the reaction system was raised to 220 ° C, 11 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 9 moles of ethylene oxide was added to the reaction vessel for 5 hours.
  • the etherified product was obtained, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 2.2 moles of the quaternizing agent allyl chloride was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternization reagent allyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 4, 4-2.
  • the nuclear magnetic resonance spectrum is shown in Table 8.
  • the reaction product is dissolved in a large amount of absolute ethanol, the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 4, 4-3.
  • the nuclear magnetic resonance spectrum is shown in Table 8.
  • the temperature of the reaction system was raised to 220 ° C, 47 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 32 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa.
  • the etherification product was obtained in an hour, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 1.1 mole of the quaternizing agent chlorocyclohexane was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternizing agent chlorocyclohexane and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 2010 liters of solvent benzene and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 2.2 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • reaction was adjusted to be acidic with hydrochloric acid, and the reaction product was washed twice with 15% NaI brine, and the product was converted into the corresponding Sodium salt.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in 4-4 of Table 4, The nuclear magnetic resonance spectrum is shown in Table 8.
  • the temperature of the reaction system was raised to 220 ° C, 41 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 21 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa.
  • the etherification product was obtained in an hour, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 2.2 moles of the quaternizing agent allyl chloride was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and the excess quaternization reagent allyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 20 liters of solvent benzene and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 2.2 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the reaction was adjusted to be acidic with hydrochloric acid, and the reaction product was washed twice with 15% NaCl brine, and the product was converted into the corresponding product with aqueous magnesium hydroxide solution.
  • Magnesium salt The reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anion-cation.
  • the specific chemical structure of the ionic-nonionic surfactant is shown in Table 4, 4-5, and the nuclear magnetic resonance spectrum is shown in Table 8.
  • the temperature of the reaction system was raised to 220 ° C, 31 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 11 moles of ethylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa. After an hour, an etherified product was obtained, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 2.2 moles of the quaternizing agent chlorocyclohexane was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternizing agent chlorocyclohexane and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then 1 mole of quaternized product, 10 liters of solvent benzene and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the water produced by the reaction was removed by azeotropy until the quaternized product was converted into a corresponding one. Potassium alkoxide. 2.2 mol of sodium carboxylate sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, 42 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa, and after reacting for 5 hours, 17 moles of ethylene oxide was added to the reaction vessel with a nitrogen gas at a pressure of 0.8 MPa. After an hour, an etherified product was obtained, and all the etherified product was dissolved in absolute ethanol to prepare a 40% solution, which was added to the reaction vessel, and 2.2 moles of the quaternizing agent chlorocyclohexane was added with a nitrogen gas at a pressure of 0.8 MPa.
  • the reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternizing agent chlorocyclohexane and solvent ethanol were removed under reduced pressure to obtain a quaternized product. Then, 1 mole of the quaternized product, 20 liters of solvent benzene, and 2.2 moles of potassium hydroxide were added to the reaction vessel, and the mixture was heated to 80 ° C and continuously stirred, and the reaction was carried out by azeotropic removal. Moisture until the quaternized product is converted to the corresponding potassium alkoxide. 2.2 moles of carboxylating agent sodium chloroacetate was added to the reaction vessel.
  • the temperature of the reaction system was raised to 220 ° C, and 2 moles of propylene oxide was added to the reaction vessel with a nitrogen pressure of 0.8 MPa. After the reaction for 5 hours, an etherified product was obtained, and all the etherified products were dissolved in absolute ethanol to prepare 40. The % solution was added to the reaction vessel, and 2.2 moles of the quaternization reagent methyl chloride was added with a nitrogen pressure of 0.8 MPa. The reaction system was heated to 80 ° C and reacted for 3 to 10 hours, and excess quaternization reagent methyl chloride and solvent ethanol were removed under reduced pressure to obtain a quaternized product.
  • the reaction product is dissolved in a large amount of absolute ethanol, and the inorganic salt in the product is removed by filtration, and the solvent is distilled off under reduced pressure to obtain an anionic-cationic-nonionic surfactant.
  • the specific chemical structure is shown in Table 4, 4-8.
  • the nuclear magnetic resonance spectrum is shown in Table 8.
  • Example 19 0.30 wt% of the anionic-cationic-nonionic surfactant prepared in Example 19 was uniformly mixed with an aqueous solution of 0.15 wt% polyacrylamide (molecular weight: 26 million) to obtain a tertiary oil recovery composition.
  • the interfacial tension between the surfactant and the oil layer of the IV5-11 layer of Henan Shuanghe Oilfield was measured by TX-500C rotary drop interfacial tension meter.
  • the measurement temperature is 81 °C
  • the formation water is NaHCO 3 type
  • the salinity is 7947mg/L
  • the chloride ion content is 2002mg/L
  • the Ca 2+ content is 20mg/L
  • the Mg 2+ content is 12.2mg/L
  • the surfactant dosage is 0.3 wt%.
  • the surfactants other than the 1, 2, 27, and 32 examples have good interfacial activity for the Henan oil field.
  • Example 33 shows that the surfactant prepared by the present invention has good interfacial activity after compounding with the polymer.
  • the surfactant prepared in Example 33 was formulated into different concentrations and tested separately with Henan.
  • the oil-water interfacial tension of the IV5-11 layer in Shuanghe Oilfield is shown in Table 10.
  • the interfacial tension between the composite surfactant prepared in Example 1-4 and the oil production in the No. 3 Oil Production Plant of Zhongyuan Oilfield was again measured by a TX-500C rotary drop interface tension meter.
  • the measurement temperature was 80 ° C
  • the formation water salinity was 79439 mg / L
  • the Ca 2+ content was 592 mg / L
  • the Mg 2+ content was 2871 mg / L
  • the surfactant dosage was 0.3 wt%.
  • the oil-water interfacial tension is 0.003 mN/m, indicating that the surfactant of the present invention has good interfacial activity not only for low salinity reservoirs, but also for high temperature and high salinity reservoirs, and has the advantage of wide application range.
  • the oil displacement test was carried out on a core having a length of 30 cm, a diameter of 2.5 cm and a permeability of 1.5 ⁇ m 2 .
  • the water in the IV5-11 stratum of the Shuanghe Oilfield in Henan province was driven to oil-free production, and the 0.3PV (core pore volume) surfactant was transferred to the oil-free production.
  • the oil recovery results are shown in Table 7. .
  • the surfactant in the example was formulated into a 0.3% wt solution with Shuanghe IV5-11 layer formation water of Henan Oilfield, placed in a constant temperature oven, and aged at 81 ° C for 1 day, 1 month, 2 months, 3 respectively. After a month, the appearance of the observation solution was taken out from the incubator and the interfacial tension of the solution was tested.
  • the ability of surfactant to reduce the oil/water interfacial tension of the IV5-11 layer of Henan Shuanghe Oilfield was determined by TX-500C rotary drop interfacial tension meter.
  • the measurement temperature is 81 ° C
  • the formation water is NaHCO 3 type
  • the salinity is 7947 mg / L
  • the chloride ion content is 2002 mg / L
  • the Ca 2+ content is 20 mg / L
  • the Mg 2+ content is 122 mg / L.
  • Table 13 where the interface The unit of tension is mN/m.
  • the anionic-cationic-nonionic surfactant of the present invention has excellent solubility in water even at high temperatures, and preferably exhibits excellent long-term interfacial activity. stability.
  • the surfactant in the examples was formulated into a 0.3% wt solution using Shuanghe IV5-11 layer formation water of Henan Oilfield.
  • the thin tube model was filled with 30% Henan Shuanghe IV5-11 layer oil sand + 70% quartz sand.
  • the inner diameter of the thin tube was 0.4cm and the length was 4.5 meters.
  • the concentration of surfactant in the effluent was measured by high performance liquid chromatography (HPLC) and total organic carbon analyzer (TOC) as a function of volume of the infusate. If a separate surfactant component is present, the recovery of each surfactant component is calculated separately based on the amount of injection and the amount of output.
  • HPLC high performance liquid chromatography
  • TOC total organic carbon analyzer
  • anion-cation-nonionic surfactant of the present invention does not exhibit chromatographic separation.
  • CTAB cetyltrimethylammonium bromide
  • SDS sodium dodecyl sulfate

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Abstract

本发明涉及一种基本上如式（Ｉ）所示的阴离子-阳离子-非离子型表面活性剂、其制造方法及其在三次采油中的应用。本发明的阴离子-阳离子-非离子型表面活性剂显示出与现有技术相比显著改善的界面活性和稳定性。使用本发明的阴离子-阳离子-非离子型表面活性剂，可以制造出与现有技术相比驱油效率和洗油能力改善的三次采油用驱油组合物。式（Ｉ）中，各基团的定义同说明书。

Description

一种阴离子-阳离子-非离子型表面活性剂、其制造方法及其应用 技术领域
本发明涉及一种阴离子-阳离子-非离子型表面活性剂。具体而言，本发明涉及一种可用于三次采油的阴离子-阳离子-非离子型表面活性剂、其制造方法及其在三次采油中的应用。
背景技术
随着世界能源需求的增加，石油的合理开发利用已引起人们的极大重视，对石油的开采量及开采效率的要求也越来越高。常规的采油方法(一次和二次法)一般仅采出原油地质储量的1/3，还有约2/3的原油未能采出，因此在能源日趋紧张的情况下，提高采油率已成为石油开采研究的重大课题。
三次采油技术则是一种有效的提高采油率的方法。其中，化学驱油技术是三次采油中非常重要并大规模实施的技术，包括聚合物驱油技术、表面活性剂驱油技术、碱水驱油技术等以及聚合物、碱、表面活性剂的多种组合技术。化学驱油是物理作用和化学作用的共同结果，物理作用利用了驱替液的波及作用，而化学作用则利用了驱替液的微观驱油作用。化学作用的核心是降低驱替液与原油的界面张力。表面活性剂由于兼具亲油(疏水)和亲水(疏油)性质，当表面活性剂溶于水时，分子主要分布在油水界面上，可以显著降低油水界面张力。油水界面张力的降低意味着表面活性剂体系能够克服原油间的内聚力，将大油滴分散成小油滴，从而提高原油流经孔喉时的通过率。表面活性剂的驱油效果还表现在使亲油的岩石表面润湿性反转、原油乳化、提高表面电荷密度及油滴聚并等作用，这是表面活性剂能够成为驱替液中起举足轻重作用的组分的原因。
但是，现有技术的三次采油用驱替液存在较多问题，主要是表面活性剂组分的界面活性差，导致由其制造的驱替液的驱油效率低，同时由于驱替液的体系过于复杂，因而采出液破乳困难，污水处理难度大；由于驱替液含无机碱，对地层和油井带来伤害，引起腐蚀设备和管道等问题，而且由于无机碱会严重降低聚合物的粘度，为达到所需的粘度只得大大提高聚合物的使用浓度，使采油综合成本提高；表面活性剂组分的抗高温、抗高盐、抗高矿化度的能力有限；表面活性剂组分在复配时稳定性差，容易产生沉淀。
因此，目前的现状是，仍旧需要一种表面活性剂，其可以克服现有技术存在的前述问题，并显示出与现有技术相比改善的界面活性和稳定性。
发明内容
本发明人在现有技术的基础上经过刻苦的研究，发现了一种新型的阴离子-阳离子-非离子型表面活性剂，并进一步发现，通过使用该表面活性剂来制造三次采油用驱油组合物(驱替液)，就可以解决现有技术存在的前述问题，并由此完成了本发明。
具体而言，本发明涉及以下方面的内容。
1.一种阴离子-阳离子-非离子型表面活性剂，其特征在于，选自基本上如下式(I)所示的化合物中的至少一种，
Figure PCTCN2014000939-appb-000001
式(I)中，基团N+是季氮阳离子；基团R1至R3彼此相同或不同，各自独立地选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基、任选取代的C6-50(优选C6-20)芳基和由式
Figure PCTCN2014000939-appb-000002
代表的基团，前提是基团R1至R3中的至少一个是由式
Figure PCTCN2014000939-appb-000003
代表的基团，此处所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、由式
Figure PCTCN2014000939-appb-000004
代表的基团、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-)；基团Link选自任选取代的x+1价C1-50(优选C1-20)直链或支链烷基、任选取代的x+1价C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的x+1价C2-50(优选C2-20)直链或支链烯基、任选取代的x+1价C6-50(优选C6-20)芳基和任选取代的x+1价C3-50(优选C3-20)直链或支链杂烷基；各基团Poly彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000005
代表的基团；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10 直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；x是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；在各基团Poly之间，各数值y彼此相同或不同，各自独立地选自0至200之间的任意数值(优选0至100之间的任意数值)，前提是x个数值y之和大于0；在各基团Poly之间，各基团Ru彼此相同或不同，各自独立地选自C2-6直链或支链亚烷基(优选各自独立地选自-CH2-CH2-和-CH2-CH(CH3)-)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
其中，在没有特别明确的情况下，所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代，并且，所述直链或支链杂烷基选自直链或支链烷基分子结构内部的一个或多个基团-CH2-被选自-O-、-S-、-NR′-(其中，基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基)和
Figure PCTCN2014000939-appb-000006
(其中，基团N+是季氮阳离子；基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))之一的替代基团直接替代而获得的基团；以及直链或支链烷基分子结构内部的一个或多个基团
Figure PCTCN2014000939-appb-000007
被替代基团
Figure PCTCN2014000939-appb-000008
或
Figure PCTCN2014000939-appb-000009
(其中，基团N+是季氮阳离子；基团Rh选自任选取代的C1-50(优选C1-20)直链或 支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))直接替代而获得的基团，
前提是，所述基团R1、所述基团R2、所述基团R3和所述基团Rh中的至少一个在其结构中包含C8直链状部分。
2.前述任一方面所述的阴离子-阳离子-非离子型表面活性剂，其中各基团Poly各自独立地选自式
Figure PCTCN2014000939-appb-000010
代表的醚链段；在各基团Poly之间，各数值m彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值；在各基团Poly之间，各数值n彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m与全部数值n之和大于0；优选的是，全部数值m之和大于0且不超过100(优选不超过50)和/或全部数值n之和大于0且不超过100(优选不超过50)。
3.前述任一方面所述的阴离子-阳离子-非离子型表面活性剂，选自基本上如下式(I-1)所示的化合物、基本上如下式(I-2)所示的化合物、基本上如下式(I-3)所示的化合物和基本上如下式(I-4)所示的化合物中的至少一种，并且附加条件是：这些化合物分子结构中的至少一个N原子与另外的基团Rh和基团X键合而呈现为式
Figure PCTCN2014000939-appb-000011
(其中，基团N+是所述至少一个N原子的季氮阳离子形式；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))所示的季铵盐和/或季铵碱的形式，
Figure PCTCN2014000939-appb-000012
式(I-1)中，各基团Ra彼此相同或不同，各自独立地选自氢、任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-10芳基；各基团Ra′彼此相同或不同，各自独立地选自单键、任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、羰基、任选取代的C1-10直链或支链亚烷基羰基和任选取代的C2-10直链或支链亚烯基羰基，优选各自独立地选自单键和任选取代的C1-6直链或支链亚烷基；b是1至3之间的任意整数，优选1；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0，并且至少一个基团Y是N；x′是1至5之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp1彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000013
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp1是式
Figure PCTCN2014000939-appb-000014
代表的基团；各基团Rp2彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000015
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值 m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′、全部数值m″、全部数值n′与全部数值n″之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
前提是，所述基团Ra和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
Figure PCTCN2014000939-appb-000016
式(I-2)中，基团Rb选自任选取代的C1-49直链或支链烷基、任选取代的C5-49单环或多环环烷基和任选取代的C2-49直链或支链烯基(优选选自任选取代的C1-29直链或支链烷基、任选取代的C5-10单环或多环环烷基和任选取代的C2-29直链或支链烯基，或者选自任选取代的C8-29直链或支链烷基、任选取代的C5-8单环或多环环烷基和任选取代的C8-29直链或支链烯基，或者选自任选取代的C8-19直链或支链烷基、任选取代的C5-7单环环烷基(比如环己基)和任选取代的C8-19直链或支链烯基)；各基团Rb′彼此相同或不同，各自独立地选自单键和羰基；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0，并且至少一个基团Y是N；x″是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp1彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000017
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp1是式
Figure PCTCN2014000939-appb-000018
代表的基团；各基团Rp2彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000019
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′、全部数值m″、全部数值n′与全部数值n″之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
前提是，所述基团Rb和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
Figure PCTCN2014000939-appb-000020
式(I-3)中，各基团Rc彼此相同或不同，各自独立地选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基 (或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；x″′是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000021
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp是式
Figure PCTCN2014000939-appb-000022
代表的基团；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′与全部数值n′之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
前提是，所述基团Rc和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
Figure PCTCN2014000939-appb-000023
式(I-4)中，基团Rc选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；基团Y是N或O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0；x″″是1至9之间的任意整数(优选1至3之间的任意整数，更优选1或2)；各基团Rp1彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000024
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp1是式
Figure PCTCN2014000939-appb-000025
代表的基团；各基团Rp2彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000026
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各基团Rp3彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000027
代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′、全部数值m″、全部数值m″′、全部数值n′、全部数值n″与全部数值n″′之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
前提是，所述基团Rc和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
其中，所述任选取代指的是任选被一个或多个选自羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代。
4.前述任一方面所述的阴离子-阳离子-非离子型表面活性剂，其中所述基团X-与所述基团(M)r +中的至少一部分以(M)r +X-的形式独立于所述阴离子-阳离子-非离子型表面活性剂而存在，优选的是，在所述阴离子-阳离子-非离子型表面活性剂的整个分子结构中，设所述基团X-的总个数为e1，所述基团N+的总个数为e2，所述基团A-的总个数为e3，所述基团(M)r +的总个数为e4，当e2＝e3时，0≤e1≤e2，0≤e4≤e3，当e2＞e3时，0＜e1≤e2，0≤e4≤e3，当e2＜e3时，0≤e1≤e2，0＜e4≤e3，但前提是e1+e3＝e2+e4，或者，e2＝e3，e1＝0，e4＝0。
5.一种阴离子-阳离子-非离子型表面活性剂的制造方法，其特征在于，包括以下步骤：
步骤(1)：使一种或多种含氮且带有一个或多个选自-OH、-NH2和-NH-的官能团的多官能化合物与一种或多种下式(Y)所示的烯化氧在碱性催化剂(优选碱金属氢氧化物)的存在下反应，获得醚化产物，
Figure PCTCN2014000939-appb-000028
式(Y)中，基团Ru′选自C2-6直链或支链亚烷基(优选选自-CH2-CH2-和-CH2-CH(CH3)-)，
步骤(2)：使所述醚化产物与下式(A)所示的季铵化剂进行反应，由此获得阳离子-非离子型表面活性剂，其中所述季铵化剂的用量使得所述醚化产物分子结构中的至少一个N原子形成季铵盐基团，
Rh-X′         (A)
式(A)中，基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X′选自卤素(优选氟、氯、溴和碘，更优选氯)，
前提是，所述多官能化合物与所述季铵化剂中的至少一个在其分子结构中包含C8直链状部分，
步骤(3)：使所述阳离子-非离子型表面活性剂与一种或多种下式(Z)所示的化合物在碱性催化剂(优选碱金属氢氧化物)的存在下反应，由此获得阴离子-阳离子-非离子型表面活性剂，
G-L-AS     (Z)
式(Z)中，基团G选自卤素(优选氟、氯、溴和碘，更优选氯)和羟基；基团L选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选选自任选取代的C1-5直链或支链亚烷基)；基团AS选自由-A-(M′)r +代表的基团；基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M′选自氢、碱金属(优选Li、Na和K)、碱土金属 (优选Mg和Ca)和铵根(NH4)；当基团M′为氢、碱金属或铵根时，r＝1；当基团M′为碱土金属时，r＝0.5，
任选，步骤(4)：将所述制造方法的任意步骤所获得的阴离子-阳离子-非离子型表面活性剂中的至少一部分季铵盐基团转换为相应的季铵碱基团，和/或，将所述阴离子-阳离子-非离子型表面活性剂中的至少一部分季铵碱基团转换为相应的季铵盐基团，
任选，步骤(5)：从所述制造方法的任意步骤所获得的阴离子-阳离子-非离子型表面活性剂中分离出至少一部分(优选全部)以游离形式存在的化合物(M′)rX′，
其中，所述任选取代指的是任选被一个或多个选自羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代。
6.前述任一方面所述的制造方法，其中所述多官能化合物选自下式(X)所示的化合物中的至少一种，
Figure PCTCN2014000939-appb-000029
式(X)中，基团R′1至R′3彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基、任选取代的C6-50(优选C6-20)芳基和由式
Figure PCTCN2014000939-appb-000030
代表的基团，前提是基团R′1至R′3中的至少一个是氢或由式
Figure PCTCN2014000939-appb-000031
代表的基团，此处所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、由式
Figure PCTCN2014000939-appb-000032
代表的基团、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代；基团LA选自任选取代的x0+1价C1-50(优选C1-20)直链或支链烷基、任选取代的x0+1价C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的x0+1价C2-50(优选C2-20)直链或支链烯基、任选取代的x0+1价C6-50(优选C6-20)芳基和任选取代的x0+1价C3-50(优选C3-20)直链或支链杂烷基；x0是1至10之间 的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Func彼此相同或不同，各自独立地选自-OH、＞NH和-NH2，并且，所述直链或支链杂烷基选自直链或支链烷基分子结构内部的一个或多个基团-CH2-被选自-O-、-S-、-NR′-(其中，基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基)和
Figure PCTCN2014000939-appb-000033
(其中，基团N+是季氮阳离子；基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))之一的替代基团直接替代而获得的基团；以及直链或支链烷基分子结构内部的一个或多个基团
Figure PCTCN2014000939-appb-000034
被替代基团
Figure PCTCN2014000939-appb-000035
或
Figure PCTCN2014000939-appb-000036
(其中，基团N+是季氮阳离子；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))直接替代而获得的基团，
所述多官能化合物优选选自下式(X-1)所示的化合物、下式(X-2)所示的化合物、下式(X-3)所示的化合物和下式(X-4)所示的化合物中的至少一种，
Figure PCTCN2014000939-appb-000037
式(X-1)中，各基团Ra彼此相同或不同，各自独立地选自氢、任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-20芳基；各基团Ra′彼此相同或不同，各自独立地选自单键、任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、羰基、任选取代的C1-10直链或支链亚烷基羰基和任选取代的C2-10直链或支链亚烯基羰基，优选各自独立地选自单键和任选取代的C1-6直链或支链亚烷基；b是1至3之间的任意整数，优选1；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a1＝1，当基团Y是O时，a1＝0，并且至少一个基团Y是N；x1是1至5之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′1是氢；各基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，
Figure PCTCN2014000939-appb-000038
式(X-2)中，基团Rb选自任选取代的C1-49直链或支链烷基、任选取代的C5-49单环或多环环烷基和任选取代的C2-49直链或支链烯基(优选选自任选取代的C1-29直链或支链烷基、任选取代的C5-10单环或多环环烷基和任选取代的C2-29直链或支链烯基，或者选自任选取代的C8-29直链或支链烷基、任选取代的C5-8单环或多环环烷基和任选取代的C8-29直链或支链烯基，或者选自任选取代的C8-19直链或支链烷基、任选取代的C5-7单环环烷基(比如环己基)和任选取代的C8-19直链或支链烯基)；各基团Rb′彼此相同或不同，各自独立地选自单键和羰基；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a2＝1，当基团Y是O时，a2＝0，并且至少一个基团Y是N； x2是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′1是氢；各基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，
Figure PCTCN2014000939-appb-000039
式(X-3)中，各基团Rc彼此相同或不同，各自独立地选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；x3是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp′彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′是氢，
Figure PCTCN2014000939-appb-000040
式(X-4)中，基团Rc选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；基团Y是N或O，前提是当基团Y是N时，a4＝1，当基团Y是O时，a4＝0；x4是1至9之间的任意整数(优选1至3之间的任意整数，更优选1或2)；各基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′1是氢；各基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各基团Rp′3彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，
其中，在没有特别明确的情况下，所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、C1-20(优选C1-10)直链或支链烷基、 C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代。
7.前述任一方面所述的制造方法，其中所述多官能化合物与所述烯化氧的摩尔比为1∶0-200(优选1∶0-100)，但不包括0；所述多官能化合物与所述式(Z)所示的化合物的摩尔比为1∶1-10(优选1∶1-3)；所述步骤(1)的反应条件包括：反应温度为室温至300℃(优选100-200℃)，反应时间为1-20小时(优选1-10小时)；所述步骤(2)的反应条件包括：反应温度为0-300℃(优选50-150℃)，反应时间为1-20小时(优选4-15小时)；所述步骤(3)的反应条件包括：反应温度为0-300℃(优选50-200℃)，反应时间为1-20小时(优选4-10小时)。
8.前述任一方面所述的制造方法，其中所述烯化氧至少包括环氧丙烷，并且使所述多官能化合物先与所述环氧丙烷反应。
9.一种三次采油用驱油组合物，其特征在于，包含前述任一方面所述的阴离子-阳离子-非离子型表面活性剂或者按照前述任一方面所述的制造方法制造的阴离子-阳离子-非离子型表面活性剂，以及水，其中以所述三次采油用驱油组合物的总重量为100wt％计，所述阴离子-阳离子-非离子型表面活性剂的重量百分含量为0.001-10wt％，优选0.005-5wt％，更优选0.02-1wt％。
10.前述任一方面所述的三次采油用驱油组合物，其中不包含无机碱。
11.一种三次采油用驱油组合物的制造方法，其特征在于，使前述任一方面所述的阴离子-阳离子-非离子型表面活性剂或者按照前述任一方面所述的制造方法制造的阴离子-阳离子-非离子型表面活性剂至少与水混合，其中以所述三次采油用驱油组合物的总重量为100wt％计，所述阴离子-阳离子-非离子型表面活性剂的重量百分含量为0.001-10wt％，优选0.005-5wt％，更优选0.02-1wt％。
12.一种三次采油方法，其特征在于，包括使用前述任一方面所述的阴离子-阳离子-非离子型表面活性剂、按照前述任一方面所述的制造方法制造的阴离子-阳离子-非离子型表面活性剂、前述任一方面所述的三次采油用驱油组合物或者按照前述任一方面所述的制造方法制造的三次采油用驱油组合物作为驱替液进行三次采油的步骤。
13.前述任一方面所述的三次采油方法，其中不使用无机碱。
技术效果
根据本发明的阴离子-阳离子-非离子型表面活性剂，显示出与现有技术相比显著改善的界面活性。比如，在该表面活性剂的用量低至0.01～0.05wt％的条件下仍能与地下原油形成10-3-10-4毫牛/米的超低界面张力。
根据本发明的阴离子-阳离子-非离子型表面活性剂或三次采油用驱油组合物，即使是在高温下，在水中也能够形成稳定而透明的水溶液，并且在优选的情况下，即使经过长期(特别是在高温下)贮存，其化学组成和界面活性也保持优异的稳定性。
根据本发明的阴离子-阳离子-非离子型表面活性剂或三次采油用驱油组合物，在使用过程中不会出现色谱分离现象，使用稳定性优异。
根据本发明的三次采油用驱油组合物，由于使用了本发明的阴离子-阳离子-非离子型表面活性剂作为表面活性剂组分，显示出与现有技术相比改善的驱油效率和洗油能力(比如对原油的洗油率可以超过40％)，可以显著提高原油采收率。
根据本发明的三次采油用驱油组合物，体系简单，不含有无机碱，对地层和油井没有伤害，避免了设备和管道的腐蚀，并且不会造成破乳困难。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此而形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合是明显不合理的。
在本发明的上下文中，表述“卤素”指的是氟、氯、溴或碘。
在本发明的上下文中，所谓“直链或支链杂烷基”，指的是直链或支链烷基分子结构内部(不包括该烷基分子结构中主链或任何侧链的端部)的一个或多个(比如1至4个、1至3个、1至2个或者1个)基 团-CH2-被选自-O-、-S-、-NR′-和
Figure PCTCN2014000939-appb-000041
之一的替代基团直接替代而获得的基团、或者直链或支链烷基分子结构内部(不包括该烷基分子结构中主链或任何侧链的端部)的一个或多个(比如1至3个、1至2个或者1个)基团
Figure PCTCN2014000939-appb-000042
被替代基团
Figure PCTCN2014000939-appb-000043
或
Figure PCTCN2014000939-appb-000044
直接替代而获得的基团。作为所述替代基团，优选-NR′-或
Figure PCTCN2014000939-appb-000045
更优选-NR′-。在此，基团R′选自任选取代的C1-20直链或支链烷基、任选取代的C5-10单环或多环环烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-20芳基。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，具体比如甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。作为所述基团R′，优选C1-20直链或支链烷基或者C5-7单环环烷基，具体比如甲基、乙基或者环己基。基团N+是季氮阳离子。基团Rh选自任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在基团Rh的定义中，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。基团X-选自卤素离子(包括氟离子、氯离子、溴离子和碘离子)和氢氧根离子(OH-)，其中优选卤素离子，更优选氯离子。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、 C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。显然的是，从结构稳定性的角度而言，在存在多个时，这些替代基团之间并不直接键合。另外，虽然该直链或支链烷基的碳原子数因为基团-CH2-或基团
Figure PCTCN2014000939-appb-000046
被替代而相应减少，但为了表述简便，依然用该替代之前所述直链或支链烷基的碳原子数指代所述直链或支链杂烷基的碳原子数。作为所述直链或支链杂烷基，具体举例而言，C4直链烷基比如
Figure PCTCN2014000939-appb-000047
(式中箭头所指示的基团未处于分子结构内部，而是处于主链的端部)被一个替代基团-O-直接替代将获得-CH2-O-CH2-CH3或-CH2-CH2-O-CH3，称之为C4直链杂烷基。或者，C4支链烷基比如
Figure PCTCN2014000939-appb-000048
(式中箭头所指示的基团未处于分子结构内部，而是处于主链和侧链的端部)被一个替代基团
Figure PCTCN2014000939-appb-000049
直接替代将获得
Figure PCTCN2014000939-appb-000050
称之为C4支链杂烷基。根据本发明，作为所述直链或支链杂烷基，比如可以举出C3-50直链或支链杂烷基，具体比如C8-50直链或支链杂烷基、C8-30直链或支链杂烷基或者C8-20直链或支链杂烷基，或者C3-20直链或支链杂烷基、C3-10直链或支链杂烷基或者C3-6直链或支链杂烷基。
在本说明书的上下文中，表达方式“数字+价+基团”或其类似用语指的是从该基团所对应的基础结构(比如链、环或其组合等)上除去该数字所代表的数量的氢原子后获得的基团，优选指的是从该结构所含的碳原子(优选饱和碳原子和/或非同一个碳原子)上除去该数字所代表的数量的氢原子后获得的基团。举例而言，“3价直链或支链烷基” 指的是从该直链或支链烷烃(即该直链或支链烷基所对应的基础链)上除去3个氢原子而获得的基团，而“2价直链或支链杂烷基”则指的是从该直链或支链杂烷烃(优选从该杂烷烃所含的碳原子，或者更进一步，从非同一个碳原子)上除去2个氢原子而获得的基团。显然，表达方式“0价+基团”代表所述基础结构，比如0价烷基指的是烷烃。
在本说明书的上下文中，所谓“结构中包含C8直链状部分”，指的是所涉及的化合物或基团在其整体的化学结构中包含(比如一个或多个)由8个碳原子按直链方式相继键合而成的结构片段。取决于所述化学结构的具体定义或取代情况，这8个碳原子可以各自独立地呈现为取代状态或未取代状态。而且，该C8直链状部分可以处于所述化学结构的内部(比如构成该化学结构的主链)，也可以处于所述化学结构的端部(比如构成该化学结构的端基或侧链)，并没有特别的限定。具体举例而言，如果基团R1(如下文所述)在其结构中包含C8直链状部分，如果设该基团R1是任选取代的C10直链或支链烷基，则该基团R1可能是-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3、
-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH(CH3)-CH3、
-CH2-CH2-CH2-CH2-CH2-CH(CH3)-CH(CH3)-CH3、
-CH2-CH(OH)-CH2-CH2-CH2-CH(CH3)-CH(CH3)-CH3、
-CH2-CH2-CH2-CH2-CH2-C(OH)(CH3)-CH(CH3)-CH3、
-CH2-CH2-C(＝O)-CH2-CH2-CH(CH3)-CH(CH3)-CH3或者
-CH2-CH(CH3)-CH2-C(＝O)-CH2-CH2-CH(CH3)-CH3(在这些烷基中，各下划线所示的由8个碳原子按直链方式相继键合而成的结构片段即为所述的C8直链状部分)等，但不可以是
-CH(CH3)-CH2-CH2-CH2-CH(CH3)-CH(CH3)-CH3或
-CH(CH2CH2CH2CH3)-CH(CH3)-CH(CH3)-CH3等(不存在由8个碳原子按直链方式相继键合而成的结构片段)。如该例子所示，只要该基团R1在其结构中包含C8直链状部分作为其结构的一部分(片段)即可，而对该C8直链状部分所处的位置没有限定，有可能是主链、端基或侧链，而且显然也不限定所述基团R1仅由8个碳原子构成或者该C8直链状部分仅呈现为-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，除非以重量为基准时不符合本领域技术人员的常规认识。
根据本发明，涉及一种阴离子-阳离子-非离子型表面活性剂，该阴离子-阳离子-非离子型表面活性剂是基本上如下式(I)所示的化合物。该式(I)所示的化合物可以仅使用一种，也可以两种或多种组合使用。
Figure PCTCN2014000939-appb-000051
根据本发明，在式(I)中，基团N+是季氮阳离子，由此使得该(I)所示的化合物成为季铵型化合物。
根据本发明，在式(I)中，基团R1至R3彼此相同或不同，各自独立地选自任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基、任选取代的C6-50芳基和由式
Figure PCTCN2014000939-appb-000052
代表的基团。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自氧代(即
Figure PCTCN2014000939-appb-000053
)、羟基、由式
Figure PCTCN2014000939-appb-000054
代表的基团、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I)中，要求基团R1至R3中的至少一个(比如至多两个)是由式
Figure PCTCN2014000939-appb-000055
代表的基团。
根据本发明，在式(I)中，基团Rh选自任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。
根据本发明，在式(I)中，在基团Rh和基团R1至R3的定义中，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20 芳基或者C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I)中，基团X-选自卤素离子(包括氟离子、氯离子、溴离子和碘离子)和氢氧根离子(OH-)，其中优选卤素离子，更优选氯离子。
根据本发明，在式(I)中，在由式
Figure PCTCN2014000939-appb-000056
代表的基团中，基团Link选自任选取代的x+1价C1-50直链或支链烷基、任选取代的x+1价C5-50单环或多环环烷基、任选取代的x+1价C2-50直链或支链烯基、任选取代的x+1价C6-50芳基和任选取代的x+1价C3-50直链或支链杂烷基。作为所述任选取代的x+1价C1-50直链或支链烷基，优选任选取代的x+1价C1-20直链或支链烷基。作为所述任选取代的x十1价C5-50单环或多环环烷基，比如可以举出任选取代的x+1价C5-10单环或多环环烷基、任选取代的x+1价C5-8单环或多环环烷基或者任选取代的x+1价C5-7单环或多环环烷基，尤其是任选取代的x+1价C5-7单环环烷基，比如环己基。作为所述任选取代的x+1价C2-50直链或支链烯基，优选任选取代的x+1价C2-20直链或支链烯基。作为所述任选取代的x+1价C6-50芳基，优选任选取代的x+1价C6-20芳基，比如苯基或者萘基。作为任选取代的x+1价C3-50直链或支链杂烷基，优选任选取代的x+1价C3-20直链或支链杂烷基。
根据本发明，在式(I)中，在由式
Figure PCTCN2014000939-appb-000057
代表的基团中，各基团Poly彼此相同或不同，各自独立地是式
Figure PCTCN2014000939-appb-000058
代表的基团。
根据本发明，在式(I)中，在由式
Figure PCTCN2014000939-appb-000059
代表的基团中，在各基团Poly之间，各数值y彼此相同或不同，各自独立地选自0至200之间的任意数值，优选0至100之间的任意数值。此时，所述数值y代表了单元-O-Ru-在式
Figure PCTCN2014000939-appb-000060
代表的基团中的平均数目，因此可以是非整数。作为所述数值y，比如可以是0、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5或者95.7等。
根据本发明，在式(I)中，要求x个数值y之和(即在由式
Figure PCTCN2014000939-appb-000061
代表的基团或式(I)所示的化合物的整体分子结构中，单元-O-Ru-的总体平均数目)大于0，但一般不超过200，优选不超过100。鉴于此，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000062
代表的基团的整体分子结构中，必须含有(一定数量的)单元-O-Ru-，由此使得式(I)所示的化合物呈现为非离子性质。此时，在由式
Figure PCTCN2014000939-appb-000063
代表的基团的整体分子结构中或者在式(I)所示的化合物的整体分子结构中，作为所述单元-O-Ru-的总体平均数目，比如可以是0.1、0.5、1.5、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5或者95.7等。
根据本发明，在式(I)中，在各基团Poly之间，各基团Ru彼此相同或不同，各自独立地选自C2-6直链或支链亚烷基，优选-CH2-CH2-、-CH2-CH(CH3)-或其组合，尤其是-CH2-CH(CH3)-或者-CH2-CH(CH3)-与其他C2-6直链或支链亚烷基的组合。
根据本发明，在式(I)中，在式
Figure PCTCN2014000939-appb-000064
代表的基团中，当基团Ru为选自C2-6直链或支链亚烷基中的两种或多种时，各(不同的)单元-O-Ru-之间可以按照无规、(两或多)嵌段或者交替等方式以任意根据需要确定的比例相互键合，但这些单元的总体平均数目为y。举例而言，当基团Ru是-CH2-CH2-与-CH2-CH(CH3)-的组合，并且y为2.2时，单元-O-CH2-CH2-与单元
Figure PCTCN2014000939-appb-000065
之间可以按照(两或多)嵌段、交替或者无规等任意方式以任意根据需要确定的比例(比如二者之间的摩尔比可以为1∶99至99∶1)相互键合，但这两种单元的总体平均数目为2.2。
根据本发明，存在一个或多个基团Poly，优选的是，在至少一个基团Poly(优选全部的基团Poly)中，至少一部分(至少一定数量)的基团Ru选自C3-6直链或支链亚烷基(相应于非-O-CH2-CH2-单元)，其中优选-CH2-CH(CH3)-(相应于单元
Figure PCTCN2014000939-appb-000066
)，由此使得该基团Poly优选包含(一定数量，其上限为y)非-O-CH2-CH2-单元(比如单元
Figure PCTCN2014000939-appb-000067
)作为构成单元。
根据本发明的一个实施方式，在式(I)中，各基团Poly各自独立地或者其中至少一个基团Poly选自下式(I-A)代表的(两嵌段)醚链 段。此时，如式(I-A)所示，单元-O-CH2-CH2-与单元
Figure PCTCN2014000939-appb-000068
之间按照(两)嵌段的方式键合。
Figure PCTCN2014000939-appb-000069
根据本发明的该实施方式，优选的是，所述醚链段与基团Link按照以下方式键合。
Figure PCTCN2014000939-appb-000070
根据本发明的该实施方式，在各基团Poly之间(或者在该基团Poly中)，各数值m彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m代表了单元
Figure PCTCN2014000939-appb-000071
在式(I-A)中的平均数目，因此可以是非整数。作为所述数值m，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的该实施方式，在各基团Poly之间(或者在该基团Poly中)，各数值n彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n代表了单元-O-CH2-CH2-在式(I-A)中的平均数目，因此可以是非整数。作为所述数值n，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的该实施方式，在式(I)或由式
Figure PCTCN2014000939-appb-000072
代表的基团中，优选的是，当x个基团Poly均各自独立地选自式(I-A)代表的(两嵌段)醚链段时，x个数值m之和(即在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000073
代表的基团的整体分子结构中，单元
Figure PCTCN2014000939-appb-000074
的总体平均数目)大于0，但一般不超过100，优选不超过50。鉴于此，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000075
代表的基团的整体分子结构中，优选含有(一定数量的)单元
Figure PCTCN2014000939-appb-000076
此时，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000077
代表的基团的整体分子结构中，作为所述单元
Figure PCTCN2014000939-appb-000078
的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的该实施方式，在式(I)或由式
Figure PCTCN2014000939-appb-000079
代表的基团中，优选的是，当x个基团Poly均各自独立地选自式(I-A)代表的(两嵌段)醚链段时，x个数值n之和(即在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000080
代表的基团的整体分子结构中，单元-O-CH2-CH2-的总体平均数目)不超过100，优选不超过50。鉴于此，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000081
代表的基团的整体分子结构中，任选含有(一定数量的)单元-O-CH2-CH2-。此时，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000082
代表的基团的整体分子结构中，作为所述单元-O-CH2-CH2-的总体平均数目，比如可以是0、0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者49.5等。
根据本发明的该实施方式，优选的是，在式(I)或由式
Figure PCTCN2014000939-appb-000083
代表的基团中，当x个基团Poly均各自独立地选自式(I-A)代表的(两嵌段)醚链段时，x个数值n之和(即在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000084
代表的基团的整体分子结构中，单元-O-CH2-CH2-的总体平均数目)大于0。鉴于此，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000085
代表的基团的整体分子结构中，优选含有(一定数量的)单元 -O-CH2-CH2-。此时，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000086
代表的基团的整体分子结构中，作为所述单元-O-CH2-CH2-的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的该实施方式，优选的是，在式(I)或由式
Figure PCTCN2014000939-appb-000087
代表的基团中，当x个基团Poly均各自独立地选自式(I-A)代表的(两嵌段)醚链段时，x个数值n之和(即在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000088
代表的基团的整体分子结构中，单元-O-CH2-CH2-的总体平均数目)与x个数值m之和(即在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000089
代表的基团的整体分子结构中，单元
Figure PCTCN2014000939-appb-000090
的总体平均数目)的总和大于0，但一般不超过200，优选不超过100。鉴于此，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000091
代表的基团的整体分子结构中，优选含有(一定数量的)单元-O-CH2-CH2-和/或
Figure PCTCN2014000939-appb-000092
此时，在式(I)所示的化合物或由式
Figure PCTCN2014000939-appb-000093
代表的基团的整体分子结构中，作为这些单元的总体平均数目，比如可以是0.1、0.5、1.5、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5或者95.7等。
根据本发明，在式(I)中，在由式
Figure PCTCN2014000939-appb-000094
代表的基团中，各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基。
根据本发明，在式(I)中，在由式
Figure PCTCN2014000939-appb-000095
代表的基团中，各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表 的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)，基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5。
根据本发明的一个实施方式，在式(I)中，在由式
Figure PCTCN2014000939-appb-000096
代表的基团中，取决于基团Salt的数目，基团A-可以是一个，也可以是x个，优选其中至少一个基团A-是羧酸根(COO-)。鉴于此，在式(I)所示的化合物的整体分子结构中，优选存在至少一个羧酸根(COO-)。
根据本发明，在式(I)中，在由式
Figure PCTCN2014000939-appb-000097
代表的基团中，x+1代表基团Link的价态值。此时，x是1至10之间的任意整数，优选1至4之间的任意整数，比如1、2或3。
根据本发明，在式(I)中，要求所述基团R1、所述基团R2、所述基团R3和所述基团Rh中的至少一个在其结构中必须包含(一个或多个)C8直链状部分，由此使得本发明的阴离子-阳离子-非离子型表面活性剂表现出预期的表面活性性质。
根据本发明，在式(I)中，在没有其他明确定义的情况下，所谓任选取代，指的是任选被一个或多个(比如1至5个、1至4个、1至3个、1至2个或者1个)选自氧代(即
Figure PCTCN2014000939-appb-000098
)、羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I)中，在存在氧代作为取代基时，优选至少有一个氧代取代基位于与N原子(如果有的话，比如直链或支链杂烷基所可能包含的N原子)直接键合的碳原子上，使所述碳原子呈现为羰基(即
Figure PCTCN2014000939-appb-000099
)的形式，由此在式(I)所示的化合物的分子结构中引入羰基与N原子直接键合的结构(比如酰亚氨基)。另外，为了获得更好的耐水解稳定性或者化学稳定性，优选的是，至少一部分(优 选全部)与O或S原子(如果有的话)直接键合的碳原子上不存在该氧代取代基，和/或，至少一部分(优选全部)处于链端(指的是分子链的自由端和/或待与其他原子键合的端部)位置的碳原子上不存在该氧代取代基，和/或，两个直接键合的碳原子不同时被氧代取代。通过如此，可以避免在式(I)所示的化合物的分子结构中引入酯基或者醛基等化学活泼性或不稳定基团。具体举例而言，基团Link为被1个氧代取代基取代的2价直链烷基
Figure PCTCN2014000939-appb-000100
(其包括两个处于链端位置的碳原子，如式中箭头所示)时，则按照前述原则，该基团Link比如优选是
Figure PCTCN2014000939-appb-000101
或者
Figure PCTCN2014000939-appb-000102
等。或者，基团Link为被1个氧代取代基取代的2价支链杂烷基
Figure PCTCN2014000939-appb-000103
(其包括三个处于链端位置的碳原子，如式中箭头所示，还包括三个与N原子直接键合的碳原子)时，则按照前述原则，该基团Link比如优选是
Figure PCTCN2014000939-appb-000104
或者
Figure PCTCN2014000939-appb-000105
等。
根据本发明，作为所述阴离子-阳离子-非离子型表面活性剂或者所述式(I)所示的化合物，比如具体可以举出基本上如下式(I-1)所示的化合物、基本上如下式(I-2)所示的化合物、基本上如下式(I-3) 所示的化合物或者基本上如下式(I-4)所示的化合物。这些化合物可以仅使用一种，也可以两种或多种组合使用。
根据本发明的该实施方式，要求这些化合物分子结构中所含的至少一个(比如1个、2个、3个或者4个等)N原子与另外的基团Rh和基团X(这些基团在以下的式(I-1)、式(I-2)、式(I-3)或式(I-4)中未示出)键合而呈现为式
Figure PCTCN2014000939-appb-000106
所示的季铵盐(碱)的形式。在式
Figure PCTCN2014000939-appb-000107
中，基团N+是所述至少一个N原子的季氮阳离子形式，基团Rh选自任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在基团Rh的定义中，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。基团X-选自卤素离子(包括氟离子、氯离子、溴离子和碘离子)和氢氧根离子(OH-)，其中优选卤素离子，更优选氯离子。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
Figure PCTCN2014000939-appb-000108
根据本发明，在式(I-1)中，各基团Ra彼此相同或不同，各自独立地选自氢、任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-10芳基，优选氢、任选取代的C8-20直链或支链烷基和任选取代的C6-10芳基。
根据本发明，在式(I-1)中，各基团Ra′彼此相同或不同，各自独立地选自单键、任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、羰基、任选取代的C1-10直链或支链亚烷基羰基和任选取代的C2-10直链或支链亚烯基羰基，优选各自独立地选自单键和任选取代的C1-6直链或支链亚烷基。
根据本发明，在式(I-1)中，b是1至3之间的任意整数，优选1。
根据本发明，在式(I-1)中，x′代表基团
Figure PCTCN2014000939-appb-000109
的数目，是1至5之间的任意整数，优选1至4之间的任意整数，比如1、2或3。显然的是，b+x′≤6。
根据本发明，在式(I-1)中，各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0。并且，至少一个基团Y是N。
根据本发明，在式(I-1)中，各(即x′个)基团Rp1彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000110
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个(比如一个或两个)基团Rp1是式
Figure PCTCN2014000939-appb-000111
代表的基团。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者 C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-1)中，各(即x′×a个)基团Rp2彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000112
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链 烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-1)中，各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m′代表了单元
Figure PCTCN2014000939-appb-000113
的平均数目，因此可以是非整数。作为所述数值m′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-1)中，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n′代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-1)中，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m″代表了单元
Figure PCTCN2014000939-appb-000114
的平均数目，因此可以是非整数。作为所述数值m″，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-1)中，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n″代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n″，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-1)中，优选的是，全部(即x′个)数值m′与全部(即x′×a个)数值m″之和(即在式(I-1)所示的化合物的整体 分子结构中，单元
Figure PCTCN2014000939-appb-000115
的总体平均数目)大于0，但一般不超过100，优选不超过50。鉴于此，在式(I-1)所示的化合物的整体分子结构中，优选含有(一定数量的)单元
Figure PCTCN2014000939-appb-000116
此时，在式(I-1)所示的化合物的整体分子结构中，作为所述单元
Figure PCTCN2014000939-appb-000117
的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-1)中，优选的是，全部(即x′个)数值n′与全部(即x′×a个)数值n″之和(即在式(I-1)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)不超过100，优选不超过50。作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的一个实施方式，优选的是，在式(I-1)中，全部(即x′个)数值n′与全部(即x′×a个)数值n″之和(即在式(I-1)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)大于0。鉴于此，在式(I-1)所示的化合物的整体分子结构中，优选含有(一定数量的)单元-CH2-CH2-O-。此时，在式(I-1)所示的化合物的整体分子结构中，作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-1)中，全部(即x′个)数值n′与全部(即x′×a个)数值n″之和(即在式(I-1)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)与全部(即x′个)数值m′与全部(即x′×a个)数值m″之和(即在式(I-1)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000118
的总体平均数目)的总和大于0，但一般不超过200，优选不超过100。鉴于此，在式(I-1)所示的化合物的整体分子结构中，必须含有(一定数量的)单元 -O-CH2-CH2-和/或
Figure PCTCN2014000939-appb-000119
此时，在式(I-1)所示的化合物的整体分子结构中，作为这些单元的总体平均数目，比如可以是0.1、0.5、1.5、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5或者95.7等。
根据本发明，在式(I-1)中，各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基。
根据本发明，在式(I-1)中，各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)，基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)。当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5。
根据本发明，在式(I-1)中，基团Ra和基团Rh(涵盖所述式(I-1)所示的化合物所包含的全部基团Ra和基团Rh，显然还包括前述的季铵盐(碱)所包含的基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)C8直链状部分，由此使得该式(I-1)所示的化合物表现出预期的表面活性性能。
根据本发明的一个实施方式，在式(I-1)中，取决于基团Salt的数目，基团A-可以是一个，也可以是多个，其中至少一个基团A-是羧酸根(COO-)。鉴于此，在式(I-1)所示的化合物的整体分子结构中，优选存在至少一个羧酸根(COO-)。
Figure PCTCN2014000939-appb-000120
根据本发明，在式(I-2)中，基团Rb选自任选取代的C1-49直链或支链烷基、任选取代的C5-49单环或多环环烷基和任选取代的C2-49直链或支链烯基，优选选自任选取代的C1-29直链或支链烷基、任选取代的C5-10单环或多环环烷基和任选取代的C2-29直链或支链烯基，或者选自任选取代的C8-29直链或支链烷基、任选取代的C5-8单环或多环环烷基和任选取代的C8-29直链或支链烯基，优选选自任选取代的C8-19直链或支链烷基、任选取代的C5-7单环环烷基(比如环己基)和任选取代的C8-19直链或支链烯基。
根据本发明，在式(I-2)中，各基团Rb′彼此相同或不同，各自独立地选自单键和羰基。
根据本发明，在式(I-2)中，各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0。并且，至少一个基团Y是N。
根据本发明，在式(I-2)中，x″代表基团的数目，是1至10之间的任意整数，优选1至4之间的任意整数，比如1、2或者3。
根据本发明，在式(I-2)中，各(即x″个)基团Rp1彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000122
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个(比如一个或两个)基团Rp1是式
Figure PCTCN2014000939-appb-000123
代表的基团。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单 环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-2)中，各(即x″×a个)基团Rp2彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000124
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-2)中，各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m′代表了单元
Figure PCTCN2014000939-appb-000125
的平均数目，因此可以是非整数。作为所述数值m′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5 等。
根据本发明，在式(I-2)中，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n′代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-2)中，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m″代表了单元
Figure PCTCN2014000939-appb-000126
的平均数目，因此可以是非整数。作为所述数值m″，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-2)中，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n″代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n″，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-2)中，优选的是，全部(即x″个)数值m′与全部(即x″×a个)数值m″之和(即在式(I-2)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000127
的总体平均数目)大于0，但一般不超过100，优选不超过50。鉴于此，在式(I-2)所示的化合物的整体分子结构中，优选含有(一定数量的)单元
Figure PCTCN2014000939-appb-000128
此时，在式(I-2)所示的化合物的整体分子结构中，作为所述单元
Figure PCTCN2014000939-appb-000129
的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-2)中，优选的是，全部(即x″个)数值n′与全部(即x″×a个)数值n″之和(即在式(I-2)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)不超过100， 优选不超过50。作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的一个实施方式，优选的是，在式(I-2)中，全部(即x″个)数值n′与全部(即x″×a个)数值n″之和(即在式(I-2)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)大于0。鉴于此，在式(I-2)所示的化合物的整体分子结构中，优选含有(一定数量的)单元-CH2-CH2-O-。此时，在式(I-2)所示的化合物的整体分子结构中，作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-2)中，全部(即x″个)数值n′与全部(即x″×a个)数值n″之和(即在式(I-2)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)与全部(即x″个)数值m′与全部(即x″×a个)数值m″之和(即在式(I-2)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000130
的总体平均数目)的总和大于0，但一般不超过200，优选不超过100。鉴于此，在式(I-2)所示的化合物的整体分子结构中，必须含有(一定数量的)单元-O-CH2-CH2-和/或
Figure PCTCN2014000939-appb-000131
此时，在式(I-2)所示的化合物的整体分子结构中，作为这些单元的总体平均数目，比如可以是0.1、0.5、1.5、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5.或者95.7等。
根据本发明，在式(I-2)中，各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基。
根据本发明，在式(I-2)中，各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)，基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)。当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5。
根据本发明的一个实施方式，在式(I-2)中，取决于基团Salt的 数目，基团A-可以是一个，也可以是多个，其中至少一个基团A-是羧酸根(COO-)。鉴于此，在式(I-2)所示的化合物的整体分子结构中，优选存在至少一个羧酸根(COO-)。
根据本发明，在式(I-2)中，基团Rb和基团Rh(涵盖所述式(I-2)所示的化合物所包含的全部基团Rb和基团Rh，显然还包括前述的季铵盐(碱)所包含的基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)C8直链状部分，由此使得该式(I-2)所示的化合物表现出预期的表面活性性能。
Figure PCTCN2014000939-appb-000132
根据本发明，在式(I-3)中，各基团Rc彼此相同或不同，各自独立地选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基，或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基。
根据本发明，在式(I-3)中，各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基。
根据本发明，在式(I-3)中，x″′代表单元
Figure PCTCN2014000939-appb-000133
的数目，是1至10之间的任意整数，优选1至4之间的任意整数，比如1、2或者3。
根据本发明，在式(I-3)中，各(即x″′个)基团Rp彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000134
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个(比如一个或两个)基团Rp是式
Figure PCTCN2014000939-appb-000135
代表的基团。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-3)中，各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m′代表了单元
Figure PCTCN2014000939-appb-000136
的平均数目，因此可以是非整数。作为所述数值m′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5 等。
根据本发明，在式(I-3)中，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n′代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-3)中，优选的是，全部(即x″′个)数值m′之和(即在式(I-3)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000137
的总体平均数目)大于0，但一般不超过100，优选不超过50。鉴于此，在式(I-3)所示的化合物的整体分子结构中，优选含有(一定数量的)单元
Figure PCTCN2014000939-appb-000138
此时，在式(I-3)所示的化合物的整体分子结构中，作为所述单元
Figure PCTCN2014000939-appb-000139
的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-3)中，优选的是，全部(即x″′个)数值n′之和(即在式(I-3)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)不超过100，优选不超过50。作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的一个实施方式，优选的是，在式(I-3)中，全部(即x″′个)数值n′之和(即在式(I-3)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)大于0。鉴于此，在式(I-3)所示的化合物的整体分子结构中，优选含有(一定数量的)单元-CH2-CH2-O-。此时，在式(I-3)所示的化合物的整体分子结构中，作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-3)中，全部(即x″′个)数值n′之和(即在式(I-3)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的 总体平均数目)与全部(即x″′个)数值m′之和(即在式(I-3)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000140
的总体平均数目)的总和大于0，但一般不超过200，优选不超过100。鉴于此，在式(I-3)所示的化合物的整体分子结构中，必须含有(一定数量的)单元-O-CH2-CH2-和/或
Figure PCTCN2014000939-appb-000141
此时，在式(I-3)所示的化合物的整体分子结构中，作为这些单元的总体平均数目，比如可以是0.1、0.5、1.5、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5.或者95.7等。
根据本发明，在式(I-3)中，各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基。
根据本发明，在式(I-3)中，各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)，基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)。当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5。
根据本发明的一个实施方式，在式(I-3)中，取决于基团Salt的数目，基团A-可以是一个，也可以是多个，其中至少一个基团A-是羧酸根(COO-)。鉴于此，在式(I-3)所示的化合物的整体分子结构中，优选存在至少一个羧酸根(COO-)。
根据本发明，在式(I-3)中，基团Rc和基团Rh(涵盖所述式(I-3)所示的化合物所包含的全部基团Rc和基团Rh，显然还包括前述的季铵盐(碱)所包含的基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)C8直链状部分，由此使得该式(I-3)所示的化合物表现出预期的表面活性性能。
Figure PCTCN2014000939-appb-000142
Figure PCTCN2014000939-appb-000143
根据本发明，在式(I-4)中，基团Rc选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基，或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基。
根据本发明，在式(I-4)中，各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基。
根据本发明，在式(I-4)中，基团Y是N或O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0。
根据本发明，在式(I-4)中，x″″代表单元
Figure PCTCN2014000939-appb-000144
的数目，是1至9之间的任意整数，优选1至3之间的任意整数，更优选1或2。
根据本发明，在式(I-4)中，各(即x″″个)基团Rp1彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000145
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个(比如一个或两个)基团Rp1是式
Figure PCTCN2014000939-appb-000146
代表的基团。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以 举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-4)中，基团Rp2选自式
Figure PCTCN2014000939-appb-000147
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单 环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-4)中，各(即a个)基团Rp3彼此相同或不同，各自独立地选自式
Figure PCTCN2014000939-appb-000148
代表的基团、氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(I-4)中，各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m′代表了单元
Figure PCTCN2014000939-appb-000149
的平均数目，因此可以是非整数。作为所述数值m′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5 等。
根据本发明，在式(I-4)中，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n′代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m″代表了单元
Figure PCTCN2014000939-appb-000150
的平均数目，因此可以是非整数。作为所述数值m″，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n″代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n″，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，各数值m″′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值m″′代表了单元
Figure PCTCN2014000939-appb-000151
的平均数目，因此可以是非整数。作为所述数值m″′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，各数值n″′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值。此时，所述数值n″′代表了单元-CH2-CH2-O-的平均数目，因此可以是非整数。作为所述数值n″′，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，优选的是，全部(x″″个)数值m′、全部(1个)数值m″与全部(a个)数值m″′之和(即在式(I-4)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000152
的总体平均数 目)大于0，但一般不超过100，优选不超过50。鉴于此，在式(I-4)所示的化合物的整体分子结构中，优选含有(一定数量的)单元
Figure PCTCN2014000939-appb-000153
此时，在式(I-4)所示的化合物的整体分子结构中，作为所述单元
Figure PCTCN2014000939-appb-000154
的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，优选的是，全部(x″″个)数值n′、全部(1个)数值n″与全部(a个)数值n″′之和(即在式(I-4)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)不超过100，优选不超过50。作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明的一个实施方式，优选的是，在式(I-4)中，全部(x″″个)数值n′、全部(1个)数值n″与全部(a个)数值n″′之和(即在式(I-4)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)大于0。鉴于此，在式(I-4)所示的化合物的整体分子结构中，优选含有(一定数量的)单元-CH2-CH2-O-。此时，在式(I-4)所示的化合物的整体分子结构中，作为所述单元-CH2-CH2-O-的总体平均数目，比如可以是0.1、0.5、1.2、2.0、2.5、3.0、3.5、5.4、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5或者50.5等。
根据本发明，在式(I-4)中，全部(x″″个)数值n′、全部(1个)数值n″与全部(a个)数值n″′之和(即在式(I-4)所示的化合物的整体分子结构中，单元-CH2-CH2-O-的总体平均数目)与全部(x″″个)数值m′、全部(1个)数值m″与全部(a个)数值m″′之和(即在式(I-4)所示的化合物的整体分子结构中，单元
Figure PCTCN2014000939-appb-000155
的总体平均数目)的总和大于0，但一般不超过200，优选不超过100。鉴于此，在式(I-4)所示的化合物的整体分子结构中，优选含有(一 定数量的)单元-O-CH2-CH2-和/或
Figure PCTCN2014000939-appb-000156
此时，在式(I-4)所示的化合物的整体分子结构中，作为这些单元的总体平均数目，比如可以是0.1、0.5、1.5、2.0、3.0、3.5、7.5、10.0、15.0、25.0、30.2、35.0、40.0、45.5、50.5、55.2、60.0、75.5、80.5、85.0、90.5或者95.7等。
根据本发明，在式(I-4)中，各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基。
根据本发明，在式(I-4)中，各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)，基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)。当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5。
根据本发明的一个实施方式，在式(I-4)中，取决于基团Salt的数目，基团A-可以是一个，也可以是多个，其中至少一个基团A-是羧酸根(COO-)。鉴于此，在式(I-4)所示的化合物的整体分子结构中，优选存在至少一个羧酸根(COO-)。
根据本发明，在式(I-4)中，基团Rc和基团Rh(涵盖所述式(I-4)所示的化合物所包含的全部基团Rc和基团Rh，显然还包括前述的季铵盐(碱)所包含的基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)C8直链状部分，由此使得该式(I-4)所示的化合物表现出预期的表面活性性能。
根据本发明，在前述的式(I-1)、式(I-2)、式(I-3)和式(I-4)中，在没有其他明确定义的情况下，所谓任选取代，指的是任选被一个或多个(比如1至5个、1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，前述各式所示的本发明的阴离子-阳离子-非离子型表面活性剂如其各自的结构式所示，明确了其各自的分子结构中必须同 时含有离子性的基团(M)r +和基团X-(有时也可能分别写作(M)r和X)。但已知的是，这两种离子性基团对彼此显示出较高的反应活性，因此二者如果共存于同一个体系中的话，比如共存于同一个分子结构中，就会倾向于彼此发生反应而生成式(M)r +X-(有时也可能写作(M)rX)所示的无机化合物。该无机化合物有时以游离形式(甚至比如析出或者形成独立的物相)独立于本发明的阴离子-阳离子-非离子型表面活性剂而存在，从而导致这些基团(即基团(M)r +和基团X-)中的至少一部分(有时是全部)无法象这些结构式所明确的那样，成为本发明的阴离子-阳离子-非离子型表面活性剂的分子结构的组成部分。在这种情况下，本发明的阴离子-阳离子-非离子型表面活性剂实质上以(比如失去全部的基团(M)r +或基团X-)或者至少部分以(比如失去一部分基团(M)r +或基团X-)内铵盐的形式存在。此时，该阴离子-阳离子-非离子型表面活性剂的分子结构中所含的基团A-和基团N+成为彼此的新抗衡离子。鉴于此，在本发明的阴离子-阳离子-非离子型表面活性剂的整个分子结构中，设所述基团X-的总个数为e1，所述基团N+的总个数为e2，所述基团A-的总个数为e3，所述基团(M)r +的总个数为e4，当e2＝e3时，0≤e1≤e2，0≤e4≤e3。或者，当e2＞e3时，0＜e1≤e2，0≤e4≤e3。或者，当e2＜e3时，0≤e1≤e2，0＜e4≤e3。前提是，e1+e3＝e2+e4。或者，优选的是，e2＝e3，e1＝0，e4＝0。因此，取决于所述无机化合物的生成程度，尤其是本发明的阴离子-阳离子-非离子型表面活性剂在其整个分子结构中的基团(M)r +和基团X-的个数比例，或者是否存在有利于该无机化合物生成的反应条件，本发明的阴离子-阳离子-非离子型表面活性剂在其分子结构中有时不同时含有所述的基团(M)r +和基团X-，有时甚至同时不含有所述的基团(M)r +和基团X-。由于该无机化合物的生成与否，或者其含量的多少，或者其存在形式是怎样，对本发明的阴离子-阳离子-非离子型表面活性剂的各种性能(比如界面活性和稳定性)并不产生实质性影响，因此本发明无意针对该无机化合物给出任何特殊的规定。鉴于此，在本说明书的上下文中，为了更为精确地描述或定义本发明的阴离子-阳离子-非离子型表面活性剂，使用了“基本上如式##所示”或其类似表述。在此，所谓“基本上如式##所示”(比如前述的基本上如式(I)所示、基本上如式(I-1)所示、基本上如式(I-2)所示、基本上如式(I-3)所示或者基本上如式(I-4)所示等)或其类似表述，指的是本发明的阴离子-阳离子-非离子型表面活性剂，既如该式所明确的那样，同时含有基团(M)r +和基团X-，也如前文所解释的那样，失去至少一部分(甚至全部)基团(M)r +和/或基团X-，甚至不含有(或不存在)基团(M)r +和/或基团X-。对于本领域技术人员而言，这些代表的是着本发明阴离子-阳离子-非离子型表面活性剂的不同存在形式，都必然 涵盖在本发明的保护范围之内。
根据本发明，前述各式所示的阴离子-阳离子-非离子型表面活性剂比如可以按照如下的制造方法进行制造，其中该制造方法比如包括如下的步骤(1)至(5)。
步骤(1)：使一种或多种含氮且带有一个或多个选自-OH、-NH2和-NH-的官能团的多官能化合物与一种或多种式(Y)所示的烯化氧在碱性催化剂的存在下反应，获得醚化产物。
根据本发明，在步骤(1)中，作为所述多官能化合物，可以使用任何带有一个或多个(比如1至10个，优选1至4个，比如2、3或者4个)选自-OH、-NH2和-NH-的官能团的化合物，并没有特别的限定。这些官能团由于含有活泼氢，因此可以使环氧乙烷等烯化氧发生开环(聚合)反应，由此在该多官能化合物的分子结构中引入(聚)醚链段。这些多官能化合物可以仅使用一种，也可以两种或多种组合使用。另外，这些多官能化合物可以直接使用市售产品，也可以按照任何已知的方法进行制造。
根据本发明，在步骤(1)中，所述多官能化合物必须含氮原子。该氮原子可来自于该多官能化合物可能含有的伯胺基团、叔胺基团或者仲胺基团。
根据本发明，在步骤(1)中，作为所述多官能化合物，具体比如可以举出下式(X)所示的胺化合物。这些化合物可以仅使用一种，也可以两种或多种组合使用。
Figure PCTCN2014000939-appb-000157
根据本发明，在式(X)中，基团R′1至R′3彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基、任选取代的C6-50芳基和由式
Figure PCTCN2014000939-appb-000158
代表的基团。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自氧代(即
Figure PCTCN2014000939-appb-000159
)、羟基、由式
Figure PCTCN2014000939-appb-000160
代表的基团、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基 或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X)中，要求基团R′1至R′3中至少有一个(比如至多两个)是氢或者由式
Figure PCTCN2014000939-appb-000161
代表的基团。
根据本发明，在式(X)中，在基团R′1至R′3的定义中，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X)中，在由式
Figure PCTCN2014000939-appb-000162
代表的基团中，基团LA选自任选取代的x0+1价C1-50直链或支链烷基、任选取代的x0+1价C5-50单环或多环环烷基、任选取代的x0+1价C2-50直链或支链烯基、任选取代的x0+1价C6-50芳基和任选取代的x0+1价C3-50直链或支链杂烷基。作为所述任选取代的x0+1价C1-50直链或支链烷基，优选任选取代的x0+1价C1-20直链或支链烷基。作为所述任选取代的x0+1价C5-50单环或多环环烷基，比如可以举出任选取代的x0+1价C5-10单环或多环环烷基、任选取代的x0+1价C5-8单环或多环环烷基或者任选取代的x0+1价C5-7单环或多环环烷基，尤其是任选取代的x0+1价C5-7单环环烷基，比如环己基。作为所述任选取代的x0+1价C2-50直链或支链烯基，优选任选取代的x0+1价C2-20直链或支链烯基。作为所述任选取代的x0+1价C6-50芳基，优选任选取代的x0+1价C6-20芳基，比如苯基或者萘基。作为任选取代的x0+1价C3-50直链或支链杂烷基，优选任选取代的x0+1价C3-20直链或支链杂烷基。
根据本发明，在式(X)中，各基团Func彼此相同或不同，各自独立地选自-OH、-NH-和-NH2，优选各自独立地选自-OH和-NH2。
根据本发明，在式(X)中，x0+1一般代表基团LA的价态值，其中x0是1至10之间的任意整数，优选1至4之间的任意整数，比如1、2或3。但是，技术人员可以理解的是，当基团Func为-NH-时，基团LA被该-NH-在任意(可以接受的)位置处中断。此时，x0(或其至少 一部分，这取决于-NH-的数目)代表该中断的次数，而不必然代表基团LA的价态值(其价态值最低可能为1，比如x0个基团Func均为-NH-时)。当存在多个-NH-时，基团LA被这些-NH-在任意(可以接受的)位置处相应多次中断。这里所谓的中断，指的是该-NH-向基团LA的分子结构内部***，而不处于其分子结构中主链或任何侧链的端部。优选的是，各-NH-之间不直接键合。具体举例而言，当基团Func为-NH-，x0为1(中断次数为1)，而基团LA为1价(不再是2价)C8直链烷基即
Figure PCTCN2014000939-appb-000163
(式中箭头所指示的位置是分子结构中主链的端部)时，基团LA可能是
Figure PCTCN2014000939-appb-000164
或
Figure PCTCN2014000939-appb-000165
等。
根据本发明，在式(X)中，在没有其他明确定义的情况下，所谓任选取代，指的是任选被一个或多个(比如1至5个、1至4个、1至3个、1至2个或者1个)选自氧代、羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明的一个实施方式(称为实施方式A)，在式(X)中，在存在氧代作为某一基团(比如基团LA)的取代基时，优选至少有一个氧代取代基位于与N原子(如果有的话，比如直链或支链杂烷基所可能包含的N原子)直接键合的碳原子上，使所述碳原子呈现为羰基(即
Figure PCTCN2014000939-appb-000166
)的形式，由此在该基团中引入羰基与N原子直接键合的结构(比如酰亚氨基)。另外，为了获得更好的耐水解稳定性或者化学稳定性，优选的是，至少一部分(优选全部)与O或S原子(如果有的话)直接键合的碳原子上不存在该氧代取代基，和/或，至少一部 分(优选全部)处于链端(指的是分子链的自由端和/或待与其他原子键合的端部)位置的碳原子(如果基团Func是-NH-或者-NH2，该基团比如基团LA中与该基团Func直接键合的链端碳原子除外，见下文的实施方式B)上不存在该氧代取代基，和/或，两个直接键合的碳原子不同时被氧代取代。通过如此，可以避免在该基团中引入酯基或者醛基等化学活泼性或不稳定基团。具体举例而言，基团LA为被1个氧代取代基取代的2价直链烷基
Figure PCTCN2014000939-appb-000167
(其包括两个处于链端位置的碳原子，如式中箭头所示)时，则按照前述原则，该基团比如优选是
Figure PCTCN2014000939-appb-000168
或者
Figure PCTCN2014000939-appb-000169
等。或者，基团LA为被1个氧代取代基取代的2价支链杂烷基
Figure PCTCN2014000939-appb-000170
(其包括三个处于链端位置的碳原子，如式中箭头所示，还包括三个与N原子直接键合的碳原子)时，则按照前述原则，该基团比如优选是
Figure PCTCN2014000939-appb-000171
或者
Figure PCTCN2014000939-appb-000172
等。
根据本发明的一个实施方式(称为实施方式B)，当基团Func是-NH-或者-NH2时，在式(X)中，在存在氧代作为取代基时，优选至少有一个氧代取代基位于与该基团Func直接键合的碳原子上，或者说， 与该基团Func直接键合的碳原子中的至少一个上存在氧代取代基，由此在基团LA中引入羰基与N原子直接键合的结构(比如酰氨基)。具体举例而言，基团LA为被1个氧代取代基取代的2价直链烷基
Figure PCTCN2014000939-appb-000173
并且基团Func是-NH2时，式
Figure PCTCN2014000939-appb-000174
代表的基团除了实施方式A所优选的
Figure PCTCN2014000939-appb-000175
之外，还可以是
Figure PCTCN2014000939-appb-000176
根据本发明，希望所述多官能化合物与下文所述的式(A)所示的季铵化剂中的至少一个在其分子结构中必须包含(一个或多个)C8直链状部分(以下有时称为规定(1))。鉴于此，根据该规定(1)，还希望所述式(X)所示的胺化合物与所述季铵化剂中的至少一个在其分子结构中必须包含(一个或多个)C8直链状部分。具体而言，根据该规定(1)，基团R′1至R′3(来自于所述式(X)所示的胺化合物)与基团Rh(参见下文，来自于所述季铵化剂)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)C8直链状部分。
根据本发明，在步骤(1)中，作为所述式(X)所示的胺化合物，更具体比如可以举出下式(X-1)所示的化合物、下式(X-2)所示的化合物、下式(X-3)所示的化合物和下式(X-4)所示的化合物。这些化合物可以仅使用一种，也可以两种或多种组合使用。
Figure PCTCN2014000939-appb-000177
根据本发明，在式(X-1)中，各基团Ra彼此相同或不同，各自独立地选自氢、任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-20芳基，优选任选取代的C8-20直链或支链烷基和任选取代的C6-10芳基。
根据本发明，在式(X-1)中，各基团Ra′彼此相同或不同，各自 独立地选自单键、任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、羰基、任选取代的C1-10直链或支链亚烷基羰基和任选取代的C2-10直链或支链亚烯基羰基，优选各自独立地选自单键和任选取代的C1-6直链或支链亚烷基。
根据本发明，在式(X-1)中，b是1至3之间的任意整数，优选1。
根据本发明，在式(X-1)中，x1代表基团
Figure PCTCN2014000939-appb-000178
的数目，是1至5之间的任意整数，优选1至4之间的任意整数，比如1、2或者3。显然的是，b+x1≤6。
根据本发明，在式(X-1)中，各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a1＝1，当基团Y是O时，a1＝0。并且，至少一个基团Y是N。
根据本发明，在式(X-1)中，各(即x1个)基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个基团Rp′1是氢。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基 或者萘基。
根据本发明，在式(X-1)中，各(即x1×a1个)基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X-1)中，根据前述的规定(1)，希望基团Ra和基团Rh(涵盖所述式(X-1)所示的化合物所包含的全部基团Ra与下文所述的式(A)所示的季铵化剂所包含的全部基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)所述C8直链状部分。
Figure PCTCN2014000939-appb-000179
根据本发明，在式(X-2)中，基团Rb选自任选取代的C1-49直链或支链烷基、任选取代的C5-49单环或多环环烷基和任选取代的C2-49直链或支链烯基，优选选自任选取代的C1-29直链或支链烷基、任选取代的C5-10单环或多环环烷基和任选取代的C2-29直链或支链烯基，或者选自任选取代的C8-29直链或支链烷基、任选取代的C5-8单环或多环环烷基和任选取代的C8-29直链或支链烯基，或者选自任选取代的C8-19直链 或支链烷基、任选取代的C5-7单环环烷基(比如环己基)和任选取代的C8-19直链或支链烯基。
根据本发明，在式(X-2)中，各基团Rb′彼此相同或不同，各自独立地选自单键和羰基。
根据本发明，在式(X-2)中，各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a2＝1，当基团Y是O时，a2＝0。并且，至少一个基团Y是N。
根据本发明，在式(X-2)中，x2代表基团
Figure PCTCN2014000939-appb-000180
的数目，是1至10之间的任意整数，优选1至4之间的任意整数，比如1、2或者3。
根据本发明，在式(X-2)中，各(即x2个)基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个基团Rp′1是氢。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X-2)中，各(即x2×a2个)基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任 选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X-2)中，根据前述的规定(1)，希望基团Rb和基团Rh(涵盖所述式(X-2)所示的化合物所包含的全部基团Rb与下文所述的式(A)所示的季铵化剂所包含的全部基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)所述C8直链状部分。
Figure PCTCN2014000939-appb-000181
根据本发明，在式(X-3)中，各基团Rc彼此相同或不同，各自独立地选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基，或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选 自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基。
根据本发明，在式(X-3)中，各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基。
根据本发明，在式(X-3)中，x3代表单元
Figure PCTCN2014000939-appb-000182
的数目，是1至10之间的任意整数，优选1至4之间的任意整数，比如1、2或者3。
根据本发明，在式(X-3)中，各(即x3个)基团Rp′彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个基团Rp′是氢。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者 萘基。
根据本发明，在式(X-3)中，根据前述的规定(1)，希望基团Rc和基团Rh(涵盖所述式(X-3)所示的化合物所包含的全部基团Rc与下文所述的式(A)所示的季铵化剂所包含的全部基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)所述C8直链状部分。
Figure PCTCN2014000939-appb-000183
根据本发明，在式(X-4)中，基团Rc选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基，或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基。
根据本发明，在式(X-4)中，各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基，优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基。
根据本发明，在式(X-4)中，基团Y是N或O，前提是当基团Y是N时，a4＝1，当基团Y是O时，a4＝0。
根据本发明，在式(X-4)中，x4代表单元
Figure PCTCN2014000939-appb-000184
的数目，是1至9之间的任意整数，优选1至3之间的任意整数，更优选1或2。
根据本发明，在式(X-4)中，各(即x4个)基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基，前提是至少一个基团Rp′1是氢。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X-4)中，基团Rp′2选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基 和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X-4)中，各(即a4个)基团Rp′3彼此相同或不同，各自独立地选自氢、任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。在此，作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(X-4)中，根据前述的规定(1)，希望基团Rc和基团Rh(涵盖所述式(X-4)所示的化合物所包含的全部基团Rc与下文所述的式(A)所示的季铵化剂所包含的全部基团Rh)中的至少一个(比如1个、2个或3个等)在其结构中必须包含(一个或多个)所述C8直链状部分。
根据本发明，在式(X-1)、式(X-2)、式(X-3)和式(X-4)中，在没有其他明确定义的情况下，所谓任选取代，指的是任选被一个或多个(比如1至5个、1至4个、1至3个、1至2个或者1个)选自 氧代、羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，作为前述的多官能化合物、式(X)所示的胺化合物、式(X-1)所示的化合物、式(X-2)所示的化合物、式(X-3)所示的化合物和式(X-4)所示的化合物等，可以直接使用市售的产品，也可以通过本领域已知的任何方法进行制造。举例而言，作为所述式(X-2)所示的化合物(其中，Y＝N，Rb′为羰基、基团Rp′1和基团Rp′2是氢)，即
Figure PCTCN2014000939-appb-000185
可以通过使下式(X-2-1)所示的化合物与酰胺化剂(比如二异丙醇胺)在碱性催化剂的存在下反应而获得(称为酰胺化步骤)。
Figure PCTCN2014000939-appb-000186
式中，基团Rb和数值x2与式(X-2)中的定义相同，基团Rac是H或C1-4直链或支链烷基。
根据本发明，该酰胺化步骤可以按照本领域已知的任何方式进行，但反应温度一般为100-200℃，反应时间一般为1-10小时，反应压力可以是常压或者任何适宜该反应进行的压力。
根据本发明，在所述酰胺化步骤中，作为所述碱性催化剂，可以直接使用现有技术为此目的而常规使用的任何碱性催化剂，其中优选碱金属氢氧化物，尤其是氢氧化钠或者氢氧化钾。这些碱性催化剂可以仅使用一种，也可以两种或多种组合使用。作为所述碱性催化剂的用量，可以直接适用本领域的常规用量，但一般使得所述碱性催化剂达到所述式(X-2-1)所示的化合物与所述酰胺化剂总重量的0.2-20wt％，优选0.5-15wt％。
根据本发明，在所述酰胺化步骤中，所述式(X-2-1)所示的化合物与所述酰胺化剂的摩尔比一般为1∶1-15、1∶1-10、1∶1-8、1∶1-5或者1∶2-4，但有时并不限于此，可以是能够将x2个基团-COORac全部转化为酰胺基的任何摩尔比。
根据本发明，在所述酰胺化步骤结束后，通过常规已知的分离方式(比如真空抽吸)从反应产物混合物中除去未反应的酰胺化剂，即可获得式(X-2)所示的化合物(比如，Y＝N，Rb′为羰基、基团Rp′1和基团Rp′2是氢)，而不需要进一步的纯化或者分离。
Figure PCTCN2014000939-appb-000187
根据本发明，在式(Y)中，基团Ru′选自C2-6直链或支链亚烷基，其中优选-CH2-CH2-和/或-CH2-CH(CH3)-，更优选-CH2-CH2-与-CH2-CH(CH3)-的组合。
根据本发明，在步骤(1)中，作为所述式(Y)所示的烯化氧，比如可以举出环氧乙烷、环氧丙烷、环氧丁烷、环氧己烷等。这些烯化氧可以仅使用一种，也可以两种或多种组合使用，比如环氧乙烷与环氧丙烷的组合。
根据本发明，使用一种或多种式(Y)所示的烯化氧，优选其中至少一种烯化氧是环氧丙烷。该环氧丙烷可以根据需要与其他式(Y)所示的的烯化氧(尤其是环氧乙烷)组合使用。在组合使用时，环氧丙烷与其他式(Y)所示的的烯化氧(尤其是环氧乙烷)的摩尔比比如可以是1∶0.1-10，但并不限于此。
根据本发明，在步骤(1)中，作为所述碱性催化剂，可以直接使用现有技术为此目的而常规使用的任何碱性催化剂，其中优选碱金属氢氧化物，尤其是氢氧化钾。这些碱性催化剂可以仅使用一种，也可以两种或多种组合使用。
根据本发明，在步骤(1)中，作为所述碱性催化剂的用量，可以直接适用本领域的常规用量，但一般使得所述多官能化合物(比如式(X)所示的胺化合物)与所述碱性催化剂的摩尔比达到1∶1-10，优选达到1∶1-5。
根据本发明，在步骤(1)中，所述多官能化合物(比如式(X)所示的胺化合物)与所述烯化氧的摩尔比一般为1∶0-200，优选1∶0-100，但不包括0，更优选1∶0.1-50。
根据本发明，在步骤(1)中，反应温度一般为室温至300℃，优选100-200℃，反应时间一般为1-20小时，优选1-10小时，而反应压力可以是任何适合该反应进行的压力，比如常压。
根据本发明的一个优选实施方式，在步骤(1)中，作为所述式(Y)所示的烯化氧，如果两种以上(优选其中至少包括环氧丙烷)组合使用时，使所述多官能化合物(比如式(X)所示的胺化合物)先与(至少一部分量或者全部量的)环氧丙烷反应，然后(优选在与所述环氧丙烷的反应至少部分或者完全结束之后)再与其他的烯化氧(比如环 氧乙烷)反应。
根据本发明，在步骤(1)结束之后，所获得的反应产物混合物可以直接作为醚化产物进行随后的步骤(2)，而不需要经过任何的分离或纯化，或者仅需要分离出(比如通过水洗)所述碱性催化剂即可。
步骤(2)：使所述醚化产物与下式(A)所示的季铵化剂进行反应，由此获得所述阳离子-非离子表面活性剂。
Rh-X′         (A)
根据本发明，在式(A)中，基团Rh选自任选取代的C1-50直链或支链烷基、任选取代的C5-50单环或多环环烷基、任选取代的C2-50直链或支链烯基和任选取代的C6-50芳基。作为所述C1-50直链或支链烷基，比如可以举出C1-20直链或支链烷基或者C8-20直链或支链烷基，具体比如十八烷基、月桂基、辛基、十六烷基、己基、甲基或者乙基等。作为所述C5-50单环或多环环烷基，比如可以举出C5-10单环或多环环烷基、C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-50直链或支链烯基，比如可以举出C2-20直链或支链烯基或者C8-20直链或支链烯基，具体比如十八碳烯基、十二碳烯基、亚油基、乙烯基、丙烯基或者烯丙基等。作为所述C6-50芳基，比如可以举出C6-20芳基或者C6-10芳基，具体比如苯基或者萘基。在此，所谓“任选取代”，指的是任选被一个或多个(比如1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在式(A)中，基团X′选自卤素，包括氟、氯、溴和碘，其中优选氯。
根据本发明，在步骤(2)中，使得所述多官能化合物(比如式(X)所示的胺化合物)与所述式(A)所示的季铵化剂的摩尔比一般达到1∶0.1-200，优选1∶0.1-50，但有时并不限于此，只要所述季铵化剂的用量使得所述醚化产物分子结构中的至少一个N原子形成季铵盐基团即可。
根据本发明，在步骤(2)中，反应温度一般为0至300℃，优选50-150℃，反应时间一般为1-20小时，优选4-15小时，而反应压力可 以是任何适合该反应进行的压力，比如常压。
根据本发明，所述步骤(2)可以在催化剂的存在下进行，也可以不使用催化剂。作为所述催化剂，可以直接使用本领域为此目的而常规使用的催化剂，具体比如可以举出碘化钾。作为所述催化剂的用量，可以直接适用本领域的常规用量，具体比如可以举出0.5-3.0wt％，尤其是1.0-2.0wt％。
根据本发明，在步骤(2)结束后，可以通过常规的分离方式对步骤(2)获得的反应产物混合物进行处理，由此分离出所述阳离子-非离子表面活性剂。作为所述分离方式，比如可以举出在碱性条件下萃取。
步骤(3)：使所述阳离子-非离子表面活性剂与一种或多种下式(Z)所示的化合物在碱性催化剂的存在下反应，由此获得本发明的阴离子-阳离子-非离子型表面活性剂(包括基本上如前述式(I)所示的化合物、基本上如前述式(I-1)所示的化合物、基本上如前述式(I-2)所示的化合物、基本上如前述式(I-3)所示的化合物或者基本上如前述式(I-4)所示的化合物等)。
根据本发明，在步骤(3)中，作为所述碱性催化剂，可以直接使用现有技术为此目的而常规使用的任何碱性催化剂，其中优选碱金属氢氧化物，尤其是氢氧化钠或者氢氧化钾。这些碱性催化剂可以仅使用一种，也可以两种或多种组合使用。
根据本发明，在步骤(3)中，作为所述碱性催化剂的用量，可以直接适用本领域的常规用量，但一般使得所述多官能化合物(比如式(X)所示的胺化合物)与所述碱性催化剂的摩尔比达到1∶1-10，优选达到1∶1-5。
G-L-AS   (Z)
根据本发明，在式(Z)中，基团G选自卤素和羟基，优选卤素。作为所述卤素，比如可以举出氟、氯、溴和碘，优选氯。
根据本发明，在式(Z)中，基团L选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基，优选选自任选取代的C1-5直链或支链亚烷基。
根据本发明，在式(Z)中，基团AS选自由-A-(M′)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)，基团M′选自氢、碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)，优选碱金属(优选Li、Na和K)和碱土金属(优选Mg和Ca)。
根据本发明，当基团M′为氢、碱金属或铵根时，r＝1；当基团M′为碱土金属时，r＝0.5。
根据本发明的一个实施方式，在式(Z)中，当基团A-是羧酸根(COO-)时，基团G是卤素，而当基团A-是磺酸根(SO3 -)时，基团 G是卤素或者羟基。
根据本发明的一个实施方式，使用一种或多种式(Z)所示的化合物，其中在至少一种式(Z)所示的化合物中，基团A-是羧酸根(COO-)。鉴于此，在进行所述步骤(3)时，优选至少使用带有羧酸根(COO-)的式(Z)所示的化合物。
根据本发明，在式(Z)中，所谓任选取代，指的是任选被一个或多个(比如1至5个、1至4个、1至3个、1至2个或者1个)选自羟基、C1-20直链或支链烷基、C5-10单环或多环环烷基、C2-20直链或支链烯基和C6-20芳基的取代基取代。作为所述C1-20直链或支链烷基，比如可以举出C1-10直链或支链烷基或者C1-6直链或支链烷基，或者甲基或者乙基等。作为所述C5-10)单环或多环环烷基，比如可以举出C5-8单环或多环环烷基或者C5-7单环或多环环烷基，尤其是C5-7单环环烷基，具体比如环戊基或环己基。作为所述C2-20直链或支链烯基，比如可以举出C2-10直链或支链烯基，具体比如乙烯基、丙烯基或者烯丙基等。作为所述C6-20芳基，比如可以举出C6-10芳基，具体比如苯基或者萘基。
根据本发明，在步骤(3)中，一般使得所述多官能化合物(比如式(X)所示的胺化合物)与所述式(Z)所示的化合物的摩尔比达到1∶1-10，优选1∶1-3。
根据本发明，在步骤(3)中，反应温度一般为0-300℃，优选50-200℃，反应时间一般为1-20小时，优选4-10小时，而反应压力可以是任何适合该反应进行的压力，比如常压。
根据本发明，在步骤(3)结束后，可以通过常规的分离方式对步骤(3)获得的反应产物混合物进行处理，由此分离出所述表面活性剂。作为所述分离方式，比如可以举出先向步骤(3)获得的反应产物混合物中加入酸性水溶液(比如盐酸水溶液、硫酸水溶液、磷酸水溶液、硫酸氢钠水溶液、硫酸氢钾水溶液等)，将其pH值调节至1-3，然后进行油水分离，由此以油相的形式获得本发明的阴离子-阳离子-非离子型表面活性剂的方法。
根据本发明，在步骤(3)结束后，根据需要，可以使如前所述获得的阴离子-阳离子-非离子型表面活性剂进一步与中和剂接触，由此将该表面活性剂中可能含有的游离酸性基团(比如游离的羧基或者磺酸基)转化为其盐的形式(以下称为中和步骤)。作为所述中和剂，比如可以举出碱金属(优选Li、Na和K)氢氧化物、碱土金属(优选Mg和Ca)氢氧化物或者氨水。这些中和剂可以仅使用一种，也可以两种或多种组合使用。作为所述中和步骤的进行方式，比如可以举出向所述阴离子-阳离子-非离子型表面活性剂中加入一定量的所述中和剂的水溶液或水悬浊液，将其中和至pH值为7-9或者8-10，然后除去水分 (比如通过加热蒸发、真空脱除等方法)的方法，但并不限于此。
步骤(4)：根据需要，将本发明的制造方法的任一步骤(包括前述的步骤(3)和中和步骤，以及下文所述的步骤(5)等)所获得的阴离子-阳离子-非离子型表面活性剂分子结构中的至少一部分(或者全部)季铵盐基团转换为相应的季铵碱基团，和/或，将所述获得的阴离子-阳离子-非离子型表面活性剂分子结构中的至少一部分(或者全部)季铵碱基团转换为相应的季铵盐基团。
根据本发明，该步骤(4)是任选步骤，而不是必要步骤。
根据本发明，所述步骤(4)可以按照常规已知的任何方式进行，比如可以举出电解法或者离子交换法等，并没有特别的限定。
步骤(5)：从本发明的制造方法的任意步骤(包括前述的步骤(3)、步骤(4)和中和步骤)所获得的阴离子-阳离子-非离子型表面活性剂中分离出至少一部分(优选全部)以游离形式存在的化合物(M′)rX′(相应于前文所述的式(M)r +X-所示的无机化合物)。在此，基团(M′)r衍生自前述式(Z)所示的化合物，基团X′衍生自前述式(A)所示的季铵化剂。该化合物(M′)rX′主要在前述步骤(3)或步骤(4)等的进行过程中因为彼此反应活性较高的离子性基团(M′)r +和离子性基团X′-相遇而生成。通过该分离，如前文所述，获得实质上以或者至少部分以内铵盐形式存在的本发明阴离子-阳离子-非离子型表面活性剂。当然，也可以不分离出该化合物(M′)rX′(即使其以游离形式存在于所述阴离子-阳离子-非离子型表面活性剂中)，而使其作为本发明的阴离子-阳离子-非离子型表面活性剂的组成成分(混合组分或无害杂质)。无论是否经过该分离，前述获得的所有阴离子-阳离子-非离子型表面活性剂都统称为本发明的阴离子-阳离子-非离子型表面活性剂而不加以区分，并且都包括在本发明的保护范围之内。
根据本发明，该步骤(5)是任选步骤，而不是必要步骤，而且也不视为对本发明的阴离子-阳离子-非离子型表面活性剂的纯化步骤。
根据本发明，作为所述化合物(M′)rX′的分离方法，比如可以举出将从本发明的制造方法的任意步骤(包括前述的步骤(3)、步骤(4)和中和步骤等)所获得的阴离子-阳离子-非离子型表面活性剂溶解于大量的无水乙醇中，然后通过过滤除去该化合物的方法等，但本发明并不限于此。由于所述化合物(M′)rX′具有较强的水溶性，因此其至少一部分可能已经在本发明的阴离子-阳离子-非离子型表面活性剂的制造过程(比如在步骤(3)中)中通过溶解于水而被分离除去。由于该化合物(M′)rX′的存在与否或含量的多少对本发明制造的所述阴离子-阳离子-非离子型表面活性剂的各种性能(比如界面活性和稳定性)没有实质性影响，因此本发明无意特定通过该制造方法所获得的阴离子-阳离子- 非离子型表面活性剂中该化合物(M′)rX′的含量或者存在形式等，当然也不存在将该化合物(M′)rX′从本发明前述获得的任何阴离子-阳离子-非离子型表面活性剂中除去的必要性。
根据本发明，作为所述阴离子-阳离子-非离子型表面活性剂(包括基本上如前述式(I)所示的化合物、基本上如前述式(I-1)所示的化合物、基本上如前述式(I-2)所示的化合物、基本上如前述式(I-3)所示的化合物或者基本上如前述式(I-4)所示的化合物等)，可以是单一一种化合物，也可以是包含多种化合物的混合物，甚至还进一步包含前述的化合物(M′)rX′，这些都是本发明所预期的。鉴于此，根据本发明，并不存在进一步纯化所述阴离子-阳离子-非离子型表面活性剂，或者从所述获得的阴离子-阳离子-非离子型表面活性剂(混合物)中进一步分离出某一特定结构的化合物的必要性。虽然如此，作为所述纯化或分离方法，比如可以举出柱层析方法或制备色谱等方法。
根据本发明，在本发明的阴离子-阳离子-非离子型表面活性剂中，不同的阴离子-阳离子-非离子型表面活性剂分子之间可以是各自单独存在的，也可以是阴阳离子因为相互吸引而缔合甚至发生化学反应(比如通过消除化合物(M)r +X-或化合物(M′)rX′等)而形成新的化合物，并没有特别的限制。这些存在状态均属于本发明的保护范围，而不限于此字面表述。
在本发明的阴离子-阳离子-非离子型表面活性剂中，一方面由于阴、阳离子表面活性剂相反电荷极性基之间强烈的静电吸引作用，使得表面活性剂分子在界面上吸附量增大，临界胶束浓度显著降低，从而具有单一表面活性剂无法比拟的高表面活性；同时由于该表面活性剂超高的界面活性，其水溶液可与原油形成超低界面张力，从而有效克服原油间的内聚力，有利于原油的流出，进而大幅提高驱油效率。另一方面，该表面活性剂可以改变油层表面的润湿性，比如其中的阳离子部分通过与吸附在固体表面上的带负电的基团相互作用，使其脱附下来，使油润湿表面改变为中性润湿或水润湿表面，降低原油在固体表面的粘附功，从而有利于原油的剥离。同时，阴、阳离子部分混合对原油具有增溶作用，可以进一步将粘附在岩层沙石上的原油洗下，提高原油采收率。鉴于此，本发明的阴离子-阳离子-非离子型表面活性剂特别适合用于制造三次采油用驱油组合物(驱替液)。
根据本发明的一个实施方式，还涉及一种三次采油用驱油组合物，其包含本发明前述的阴离子-阳离子-非离子型表面活性剂，以及水。
根据本发明，在所述三次采油用驱油组合物中，本发明的阴离子-阳离子-非离子型表面活性剂占所述三次采油用驱油组合物的总重量(以100wt％计)一般为0.001-10wt％，优选0.005-5wt％，更优选 0.02-1wt％。
根据本发明，所述三次采油用驱油组合物中还可以根据需要包括本领域在制造时常规使用的各种添加剂，包括但不限于阳离子水溶性聚合物、阴离子水溶性聚合物或者脂肪醇醚溶剂等。这些添加剂可以仅使用一种，也可以两种或多种组合使用，其用量也可以直接参照本领域的常规用量。
根据本发明，作为所述阳离子水溶性聚合物，比如可以举出聚丙烯酰胺。该聚丙烯酰胺的数均分子量一般为1000万至4000万，优选1000万至3000万，其用量一般为所述三次采油用驱油组合物总重量的0.05-5.0wt％，优选0.1-0.5wt％，但有时并不限于此。
根据本发明，所述三次采油用驱油组合物即使不包含无机碱作为组分，也可以获得高的驱油效率和洗油能力。因此，根据本发明一个优选的实施方式，所述三次采油用驱油组合物不包含(或不有意添加)无机碱作为组分。作为所述无机碱，比如可以举出本领域在三次采油用驱油组合物中常规使用的无机碱性化合物，尤其是碱金属的碳酸盐比如碳酸钠、碳酸氢钠等。
根据本发明，所述三次采油用驱油组合物可以通过以下制造方法进行制造。
根据本发明，所述三次采油用驱油组合物的制造方法包括使本发明前述的阴离子-阳离子-非离子型表面活性剂与水(以及根据需要使用的添加剂)混合(至均匀)的步骤。此时，所述阴离子-阳离子-非离子型表面活性剂和所述添加剂的用量从前规定。
根据本发明，所述阴离子-阳离子-非离子型表面活性剂或者所述三次采油用驱油组合物可以用于三次采油方法，并显示出与现有技术相比改善的驱油效率和洗油能力(比如对原油的洗油率可以超过40％)，由此可以显著提高原油采收率。鉴于此，本发明还涉及一种三次采油方法，包括使用本发明前述的阴离子-阳离子-非离子型表面活性剂或者本发明前述的三次采油用驱油组合物作为驱替液进行三次采油的步骤。
根据本发明的一个优选实施方式，在进行所述三次采油方法时，不使用或者不有意添加无机碱。因此，本发明的三次采油方法对地层和油井没有伤害，避免了设备和管道的腐蚀，并且不会造成破乳困难。
根据本发明，所述阴离子-阳离子-非离子型表面活性剂或三次采油用驱油组合物易溶于水，即使是在高温下，在水中也能够形成稳定而澄清透明的水溶液，并且没有沉淀产生，化学组成和界面活性的稳定性优异。另外，该水溶液的澄清透明状态可以(即使是在高温下)长期稳定地保持，由此表现出优异的长期化学组成稳定性。而且，根据 本发明优选的是，所述阴离子-阳离子-非离子型表面活性剂、三次采油用驱油组合物或其水溶液即使经过长期(特别是在高温下)贮存，其界面活性也基本上保持稳定，由此表现出优异的长期界面活性稳定性。
根据本发明，所述阴离子-阳离子-非离子型表面活性剂在使用过程中(基本上)不会出现色谱分离现象(即，不会出现组分分离现象)，使用中化学组成和界面活性的稳定性优异。
实施例
以下采用实施例和比较例进一步详细地说明本发明，但本发明并不限于这些实施例。
【实施例1】
将20摩尔十二烷基苯胺和2摩尔氯甲烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯(4-十二烷基苯基)甲基胺。将1摩尔(4-十二烷基苯基)甲基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将1摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯甲烷，将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯甲烷和溶剂乙醇得到季铵化产物(即阳离子-非离子型表面活性剂，以下同)。将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中升温至80℃，不断搅拌，利用共沸除去反应体系中的水分将季铵化产物转化成相应的钾盐，然后加入1.1摩尔羧化剂氯乙酸钠反应5小时后用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐，然后将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂乙醇后得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-1，其核磁共振氢谱见表5。
【实施例2】
将20摩尔4-壬基苯胺和2摩尔氯甲烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯(4-壬基苯基)甲基胺。将1摩尔(4-壬基苯基)甲基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将1摩尔环氧乙烷加入反应釜中，反应5小 时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯甲烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯甲烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物和10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾，将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氨水将产物转化成相应的铵盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-2，其核磁共振氢谱见表5。
【实施例3】
将20摩尔9-十八碳烯胺和2摩尔烯丙基氯加入反应釜中升温至80℃反应5小时后利用层析技术提纯(9-十八碳烯基)烯丙基胺。将1摩尔(9-十八碳烯基)烯丙基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将49摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将37摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-3，其核磁共振氢谱见表5。
【实施例4】
将20摩尔异十三烷基苯胺和2摩尔氯化苄加入反应釜中升温至80℃反应5小时后利用层析技术提纯异十三烷基苄基胺。将1摩尔异十三烷基苄基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4 次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将39摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将41摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯化苄。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯化苄和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钙水溶液将产物转化成相应的钙盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-4，其核磁共振氢谱见表5。
【实施例5】
将20摩尔二壬基苄胺和2摩尔2-氯丙烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯异(二壬基苄基)异丙基胺。将1摩尔二壬基苄胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将1摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将39摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入季铵化试剂1.1摩尔2-氯丙烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂2-氯丙烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将11摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氢氧化镁水溶液将产物转化成相应的镁盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-5，其核磁共振氢谱见表5。
【实施例6】
将20摩尔十二烷基苄胺和2摩尔氯乙烷加入反应釜中升温至80 ℃反应5小时后利用层析技术提纯(十二烷基苄基)乙基胺。将1摩尔(十二烷基苄基)乙基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将21摩尔环氧乙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将17摩尔环氧丙烷加入反应釜中反应5小时得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯乙烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯乙烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-6，其核磁共振氢谱见表5。
【实施例7】
将1摩尔十二烷基-3-氨基苯甲酸甲酯、2摩尔异丙醇胺以及0.1摩尔氢氧化钾加入反应釜中，升温到180℃，反应5小时后利用层析技术提纯十二烷基-3-氨基苯甲酰基异丙醇基胺。将1摩尔十二烷基-3-氨基苯甲酰基异丙醇基胺和0.1摩尔氢氧化钾加入反应釜并减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将11摩尔环氧丙烷加入反应釜中，反应5小时后再用0.8MPa压力的氮气将27摩尔环氧乙烷加入反应釜中反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氨水将产物转化成相应的铵盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性 剂，其具体化学结构见表1中的1-7，其核磁共振氢谱见表5。
【实施例8】
将10摩尔5-二十烷基间苯二胺和20摩尔氯化苄加入反应釜中升温至80℃反应5小时后利用层析技术提纯N，N’-二苄基-5-二十烷基间苯二胺。将1摩尔N，N’-二苄基-5-二十烷基间苯二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将2摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将48摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂氯化苄。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯化苄和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔磺化剂氯甲基磺酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表1中的1-8，其核磁共振氢谱见表5。
【实施例9】
将20摩尔十二烷基胺和2摩尔氯甲烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯十二烷基甲基胺。将1摩尔十二烷基甲基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将1摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯甲烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯甲烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成 相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-1，其核磁共振氢谱见表6。
【实施例10】
将20摩尔油胺和2摩尔氯甲烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯9-十八碳烯基甲基胺。将1摩尔9-十八碳烯基甲基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将I摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯甲烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯甲烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氨水将产物转化成相应的铵盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-2，其核磁共振氢谱见表6。
【实施例11】
将20摩尔松香胺和2摩尔1-氯代辛烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯松香基辛基胺。将1摩尔松香基辛基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将49摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将37摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1摩尔季铵化试剂1-氯代辛烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水 洗涤反应产物两次，用氢氧化镁水溶液将产物转化成相应的镁盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-3，其核磁共振氢谱见表6。
【实施例12】
将20摩尔异十三烷基胺和2摩尔烯丙基氯加入反应釜中升温至80℃反应5小时后利用层析技术提纯异十三烷基烯丙基胺。将1摩尔异十三烷基烯丙基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将25摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将17摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钙水溶液将产物转化成相应的钙盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-4，其核磁共振氢谱见表6。
【实施例13】
将5摩尔赖氨酸甲酯和10摩尔单乙醇胺加入反应釜中升温到180℃反应5小时后利用层析技术提纯得到赖氨酸单乙醇酰胺。将5摩尔赖氨酸单乙醇酰胺和10摩尔1-氯代辛烷加入反应釜中升温至80℃反应5小时后利用层析技术提纯得到N，N’-二辛基赖氨酸单乙醇酰胺。将1摩尔N，N’-二辛基赖氨酸单乙醇酰胺和氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将39摩尔环氧乙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将15摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2摩尔季铵化 试剂1-氯代辛烷。将反应体系升温至80℃后反应3～10小时，减压除去溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及3.3摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将3.3摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氢氧化镁水溶液将产物转化成相应的镁盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子表面活性剂，其具体化学结构见表2中的2-5，其核磁共振氢谱见表6。
【实施例14】
将20摩尔十八胺和2摩尔氯化苄加入反应釜中升温至80℃反应5小时后利用层析技术提纯得到十八烷基苄基胺。将1摩尔十八烷基苄基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将25摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将17摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯化苄。将反应体系升温至80℃后反应3～10小时，减压除去多余溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钠将产物转化成相应的铵盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-6，其核磁共振氢谱见表6。
【实施例15】
将1摩尔十二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将39摩尔环氧乙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将1摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂 氯代环己烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯代环己烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-7，其核磁共振氢谱见表6。
【实施例16】
将1摩尔软脂胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将1摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将39摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物。将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔磺化剂氯甲基磺酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钙水溶液将产物转化成相应的钙盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表2中的2-8，其核磁共振氢谱见表6。
【实施例17】
将10摩尔1-氯代十二烷和5摩尔氨加入反应釜中升温至80℃，反应5小时后利用层析技术提纯二(十二烷基)胺，然后将1摩尔二(十二烷基)胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将14摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将9摩尔环氧乙烷加入反应釜中，反应5小时后得 到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯甲烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯甲烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-1，其核磁共振氢谱见表7。
【实施例18】
将2摩尔1-氯代十八烷和20摩尔二乙醇胺加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯十八烷基二羟乙基胺，然后将1摩尔十八烷基二羟乙基胺和0.1摩尔氢氧化钾加入反应釜升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将4摩尔环氧乙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将22摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1摩尔季铵化试剂1-氯代十二烷。将反应体系升温至80℃后反应3～10小时，减压除去多余溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-2，其核磁共振氢谱见表7。
【实施例19】
将20摩尔油胺和2摩尔1-氯代十二烷加入反应釜中升温至80℃，反应5小时后利用层析技术提纯1-(9-十八碳烯基)十二烷基胺，然后将1摩尔1-(9-十八碳烯基)十二烷基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应 体系的温度升至220℃，用0.8MPa压力的氮气将17摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将38摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯代环己烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯代环己烷和溶剂乙醇得到季铵化产物。然后将季1摩尔铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氢氧化钙水溶液将产物转化成相应的钙盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-3，其核磁共振氢谱见表7。
【实施例20】
将2摩尔1-氯代-9-十八碳烯和20摩尔二乙醇胺加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯(9-十八碳烯基)二羟乙基胺，然后将1摩尔(9-十八碳烯基)二羟乙基胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将16摩尔环氧乙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将49摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1摩尔季铵化试剂1-氯代十二烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-4，其核磁共振氢谱见表7。
【实施例21】
将11摩尔油酸甲酯和100摩尔乙二胺加入反应釜中升温至180℃， 反应5小时后利用层析技术提纯得油酰基乙二胺，然后将10摩尔油酰基乙二胺与1摩尔1-氯代十二烷加入反应釜中升温至80℃，反应5小时后利用层析技术提纯1-油酰基-4-月桂基乙二胺。将1摩尔1-油酰基-4-月桂基乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将2摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将39摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯代环己烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯代环己烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-5，其核磁共振氢谱见表7。
【实施例22】
将15摩尔月桂酸甲酯和150摩尔乙二胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯1-月桂酰基乙二胺，然后将12摩尔1-月桂酰基乙二胺与1摩尔1-氯代十二烷基加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯1-月桂酰基-4-十二烷基乙二胺。将1摩尔1-月桂酰基-4-十二烷基乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系温度升至220℃，用0.8MPa压力的氮气将16摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将22摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯乙烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯乙烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反 应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-6，其核磁共振氢谱见表7。
【实施例23】
将20摩尔月桂酸甲酯和200摩尔二乙烯三胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯1-月桂酰基二乙烯三胺，然后将2摩尔月桂酸甲酯与10摩尔1-月桂酰基二乙烯三胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯1，7-二月桂酰基二乙烯三胺。将1摩尔1，7-二月桂酰基二乙烯三胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将16摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将37摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯乙烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯乙烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及1.1摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将1.1摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氨水将产物转化成相应的铵盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-7，其核磁共振氢谱见表7。
【实施例24】
将30摩尔1-氯代十二烷和300摩尔三乙烯四胺加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯1-月桂基三乙烯四胺，然后将2摩尔月桂酸甲酯与20摩尔1-月桂基三乙烯四胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯1-月桂酰基-10-月桂基三乙烯四胺。将1摩尔1-月桂酰基-10-月桂基三乙烯四胺和氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将31摩尔环氧丙 烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将9摩尔环氧乙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入3.3摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及3.3摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将3.3摩尔磺化剂2-氯乙基磺酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钙水溶液将产物转化成相应的钙盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表3中的3-8，其核磁共振氢谱见表7。
【实施例25】
将2摩尔1-氯代十二烷和20摩尔乙二胺加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯1-月桂基乙二胺。然后将1摩尔1-月桂基乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将23摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将19摩尔环氧乙烷加入反应釜中反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入3.3摩尔季铵化试剂氯乙烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯乙烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及3.3摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将3.3摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-1，其核磁共振氢谱见表8。
【实施例26】
将2摩尔1-氯代-9-十八碳烯和20摩尔乙二胺加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯(9-十八碳烯基)乙二胺。然 后将1摩尔(9-十八碳烯基)乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将11摩尔环氧丙烷加入反应釜中，反应5小时后0.8MPa压力的氮气将9摩尔环氧乙烷加入反应釜中反应5小时得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及3.3摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将3.3摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-2，其核磁共振氢谱见表8。
【实施例27】
将2摩尔月桂酸甲酯与20摩尔乙二胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯月桂酰基乙二胺。然后将1摩尔月桂酰基乙二胺加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将1摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂氯化苄。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯化苄和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氨水将产物转化成相应的铵盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-3，其核磁共振氢谱见表8。
【实施例28】
将2摩尔油酸甲酯和20摩尔乙二胺加入反应釜中升温至80℃，反应5小时后，利用层析技术提纯1-油酰基乙二胺。然后将1摩尔1-油酰基基乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将47摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将32摩尔环氧乙烷加入反应釜中反应5小时得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入1.1摩尔季铵化试剂氯代环己烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯代环己烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、2010升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-4，其核磁共振氢谱见表8。
【实施例29】
将2摩尔1-氯代十二烷和20摩尔单乙醇胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯N-月桂基单乙醇胺。然后将1摩尔N-月桂基单乙醇胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将41摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将21摩尔环氧乙烷加入反应釜中反应5小时得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂烯丙基氯。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂烯丙基氯和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、20升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化镁水溶液将产物转化成相应的镁盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳 离子-非离子型表面活性剂，其具体化学结构见表4中的4-5，其核磁共振氢谱见表8。
【实施例30】
将2摩尔1-氯代-9-十八碳烯和20摩尔单乙醇胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯N-十八碳烯基单乙醇胺。然后将1摩尔N-十八碳烯基单乙醇胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将31摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将11摩尔环氧乙烷加入反应釜中反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂氯代环己烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯代环己烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaBr盐水洗涤反应产物两次，用氢氧化钙水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-6，其核磁共振氢谱见表8。
【实施例31】
将2摩尔月桂酸甲酯和20摩尔羟乙基乙二胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯N-月桂酰基-N’-羟乙基乙二胺。然后将1摩尔N-月桂酰基-N’-羟乙基乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃，减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将42摩尔环氧丙烷加入反应釜中，反应5小时后用0.8MPa压力的氮气将17摩尔环氧乙烷加入反应釜中反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂氯代环己烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯代环己烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、20升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的 水份直至季铵化产物转化成相应的醇钾。将2.2摩尔羧化剂氯乙酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaI盐水洗涤反应产物两次，用氢氧化钾水溶液将产物转化成相应的钾盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-7，其核磁共振氢谱见表8。
【实施例32】
将2摩尔油酸甲酯和20摩尔羟乙基乙二胺加入反应釜中升温至180℃，反应5小时后，利用层析技术提纯N-油酰基-N’-羟乙基乙二胺。然后将1摩尔N-油酰基-N’-羟乙基乙二胺和0.1摩尔氢氧化钾加入反应釜中升温至80℃减压至真空度0.9，搅拌30分钟除去易挥发组分，用氮气置换反应釜内气体4次，调节反应釜内压力为0.2MPa。将反应体系的温度升至220℃，用0.8MPa压力的氮气将2摩尔环氧丙烷加入反应釜中，反应5小时后得到醚化产物，将所有醚化产物溶于无水乙醇中配制成40％的溶液加入到反应釜中，用0.8MPa压力的氮气加入2.2摩尔季铵化试剂氯甲烷。将反应体系升温至80℃后反应3～10小时，减压除去多余的季铵化试剂氯甲烷和溶剂乙醇得到季铵化产物。然后将1摩尔季铵化产物、10升溶剂苯以及2.2摩尔氢氧化钾加入反应釜中，升温至80℃不断搅拌，利用共沸带走反应产生的水份直至季铵化产物转化成相应的醇钾。将2.2摩尔磺化剂氯甲基磺酸钠加入反应釜中，反应5小时后，用盐酸将反应物调节成酸性，用15％NaCl盐水洗涤反应产物两次，用氢氧化钠水溶液将产物转化成相应的钠盐。将反应产物溶于大量无水乙醇中，过滤除去产物中的无机盐，减压蒸馏除去溶剂得到阴离子-阳离子-非离子型表面活性剂，其具体化学结构见表4中的4-8，其核磁共振氢谱见表8。
【实施例33】
将0.30wt％实施例19制备的阴离子-阳离子-非离子型表面活性剂与0.15wt％聚丙烯酰胺(分子量2600万)水溶液混合均匀，得到三次采油用驱油组合物。
Figure PCTCN2014000939-appb-000188
Figure PCTCN2014000939-appb-000189
Figure PCTCN2014000939-appb-000190
Figure PCTCN2014000939-appb-000191
Figure PCTCN2014000939-appb-000192
Figure PCTCN2014000939-appb-000193
Figure PCTCN2014000939-appb-000194
Figure PCTCN2014000939-appb-000195
Figure PCTCN2014000939-appb-000196
Figure PCTCN2014000939-appb-000197
Figure PCTCN2014000939-appb-000198
Figure PCTCN2014000939-appb-000199
Figure PCTCN2014000939-appb-000200
表5 阴离子-阳离子-非离子型表面活性剂核磁共振氢谱
Figure PCTCN2014000939-appb-000201
Figure PCTCN2014000939-appb-000202
表6 阴离子-阳离子-非离子型表面活性剂核磁共振氢谱
Figure PCTCN2014000939-appb-000203
表7 阴离子-阳离子-非离子型表面活性剂核磁共振氢谱
Figure PCTCN2014000939-appb-000204
Figure PCTCN2014000939-appb-000205
表8 阴离子-阳离子-非离子型表面活性剂核磁共振氢谱
Figure PCTCN2014000939-appb-000206
Figure PCTCN2014000939-appb-000207
【实施例34】表面活性剂界面活性测试
用TX-500C旋转滴界面张力仪测定表面活性剂与河南双河油田IV5-11层系油水界面张力。测定温度为81℃，地层水为NaHCO3型，矿化度为7947mg/L，氯离子含量2002mg/L，Ca2+含量20mg/L，Mg2+含量12.2mg/L，表面活性剂用量为0.3wt％。
表9 表面活性剂与双河油田IV5-11层系油水界面张力
实施例编号 界面张力(mN/m)
1 0.01
2 0.02
3 0.0006
4 0.0004
5 0.0007
6 0.004
7 0.0007
8 0.0006
9 0.009
10 0.0009
11 0.0004
12 0.0005
13 0.0006
14 0.0007
15 0.005
16 0.0007
17 0.0004
18 0.005
19 0.0003
20 0.006
21 0.0007
22 0.0005
23 0.0006
24 0.0007
25 0.0006
26 0.0004
27 0.04
28 0.0008
29 0.0007
30 0.0006
31 0.0005
32 0.08
33 0.0003
由表9可知，除了1、2、27、32实施例以外的表面活性剂对于河南油田都具有良好的界面活性。实施例33表明，本发明制备的表面活性剂与聚合物复配后，其界面活性依然良好。
将实施例33制备的表面活性剂配制成不同浓度，分别测试与河南 双河油田IV5-11层系油水界面张力，结果见表10。
表10 不同浓度表面活性剂19与河南双河油田IV5-11层系油水界面张力
表面活性剂用量(wt％) 0.01 0.02 0.05 0.1 0.2 0.3
界面张力(毫牛/米) 0.006 0.003 0.0009 0.0004 0.0003 0.0003
上述结果表明，本发明表面活性剂对于河南油田原油具有很高的油水界面活性。
用TX-500C旋转滴界面张力仪再次测定实施例1-4制备的复合型表面活性剂与***采油三厂油水界面张力。测定温度为80℃，地层水矿化度为79439mg/L，Ca2+含量592mg/L，Mg2+含量2871mg/L，表面活性剂用量为0.3wt％。油水界面张力为0.003mN/m，表明本发明的表面活性剂不仅对于低矿化度油藏，同时对于高温高盐油藏依然具有良好的界面活性，具有适用范围宽的优点。
【实施例35】表面活性剂洗油能力测试
取河南双河油田IV5-11层系油砂，按照油∶砂＝1∶4(重量比)在81℃老化7天，每2小时搅拌5分钟；而后取出上述老化后的油砂5g，与0.3wt％的表面活性剂溶液按油砂∶溶液重量比＝1∶10混合均匀，在油藏温度下老化48小时后，用石油醚萃取溶液中的原油，用50ml比色管定容，分光光度计在波长430nm处比色分析。利用标准曲线计算表面活性剂溶液中原油浓度。
表11 表面活性剂洗油结果
实施例编号 洗油率％
1 39％
2 31％
3 68％
4 77％
5 66％
6 51％
7 65％
8 67％
9 49％
10 61％
11 73％
12 71％
13 66％
14 64％
15 49％
16 65％
17 73％
18 46％
19 81％
20 48％
21 63％
22 73％
23 67％
24 66％
25 69％
26 78％
27 28％
28 60％
29 63％
30 66％
31 74％
32 25％
33 81％
【实施例36】表面活性剂驱油性能研究
在长度为30厘米，直径为2.5厘米，渗透率为1.5微米2的岩心上进行驱油试验。先用河南双河油田IV5-11层系地层水驱至无油产生，转注0.3PV(岩心孔隙体积)的表面活性剂后，再水驱至无油产生，提高原油采收率结果见表7。
表12 表面活性剂驱油试验结果
实施例编号 提高采收率％
1 2.8％
2 2.5％
3 4.9％
4 8.9％
5 4.7％
6 4.1％
7 5.5％
8 5.6％
9 4.0％
10 5.0％
11 7.5％
12 7.1％
13 6.7％
14 6.4％
15 4.0％
16 6.5％
17 7.1％
18 4.2％
19 9.7％
20 4.1％
21 6.4％
22 7.0％
23 5.6％
24 6.7％
25 6.9％
26 9.0％
27 1.8％
28 6.1％
29 6.5％
30 6.8％
31 7.2％
32 1.2％
33 10.9％
【实施例37】表面活性剂的长期稳定性研究
将实施例中的表面活性剂用河南油田双河IV5-11层系地层水配制成0.3％wt的溶液，放置于恒温烘箱中，81℃分别老化1天、1个月、2个月、3个月后从恒温箱中取出观察溶液的外观并测试溶液的界面张力。用TX-500C旋转滴界面张力仪测定表面活性剂降低河南双河油田IV5-11层系油/水界面张力的能力。测定温度为81℃，地层水为NaHCO3型，矿化度为7947mg/L，氯离子含量2002mg/L，Ca2+含量20mg/L，Mg2+含量122mg/L结果见表13，其中界面张力的单位是mN/m。
表13 表面活性剂的长期稳定性试验结果
Figure PCTCN2014000939-appb-000208
Figure PCTCN2014000939-appb-000209
根据这些实验数据可以看出，本发明的阴离子-阳离子-非离子表面活性剂即使是在高温下，在水中也具有很好的溶解性，并且在优选的情况下，显示出优异的长期界面活性稳定性。
【实施例38】阴离子-阳离子-非离子表面活性剂的色谱效应研究
将实施例中的表面活性剂用河南油田双河IV5-11层系地层水配制成0.3％wt的溶液。用30％河南油田双河IV5-11层系油砂+70％石英砂混合填充细管模型，细管内径为0.4cm，长度为4.5米。在混合砂模型上进行了如下色谱效应实验：1)(1#实验)注入配制的表面活性剂溶液2PV；2)(2#实验)注入表面活性剂溶液+碱的复合体系(碱的浓度：NaOH，2000mg/L)；3)(3#实验)先注入2000mg/l NaOH的地层 水溶液1PV，再注入表面活性剂溶液+碱的复合体系(碱的浓度：NaOH；2000mg/L)，注入流速：0.2mL/min。在注入一定段塞的复配体系后用同样流量的地层水进行水驱，收集流出液。用高效液相色谱(HPLC)和总有机碳分析仪(TOC)联合测定流出液中表面活性剂浓度随着注入液体积的变化。如果出现被分开的表面活性剂组分，根据注入量和产出量分别计算每个表面活性剂组分的回收率。公式如下
Figure PCTCN2014000939-appb-000210
如果出现多个表面活性剂组分，则以其中一个为标准，其它所有的组份都与作为标准的表面活性剂组份相比较。实验结果见表14。
表14 阴离子-阳离子-非离子表面活性剂的色谱效应实验结果
Figure PCTCN2014000939-appb-000211
Figure PCTCN2014000939-appb-000212
根据这些实验结果可知，本发明的阴离子-阳离子-非离子表面活性剂不会出现色谱分离现象。
【比较例1】
按照西北大学学报(自然科学版)2000年2月第30卷第1期，28～31巩育军等方法将十六烷基三甲基溴化铵(CTAB)与十二烷基硫酸钠(SDS)配制成混合体系(摩尔比1∶1.5)，分别测试其在0.3wt％用量时与河南双河油田IV5-11层系原油油水界面张力、洗油率及驱油性能，结果如下：
表15 参比驱油剂性能
界面张力(毫牛/米) 洗油率％ 提高采收率％
0.03 45.6 2.8
【比较例2】
按照石油天然气学报2007年8月第29卷第4期，黄宏度等(101～104)方法等将0.01wt％十六烷基三甲基溴化铵与0.02wt％阴离子表面 活性剂石油磺酸盐及1.8wt％Na2CO3配制成混合体系，分别测试其在0.3wt％用量时与河南双河油田IV5-11层系原油油水界面张力、洗油率及驱油性能，结果如下：
表16 参比驱油剂性能
界面张力(毫牛/米) 洗油率％ 提高采收率％
0.008 56.3 4.2
以上虽然已结合实施例对本发明的具体实施方式进行了详细的说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。本领域技术人员可在不脱离本发明的技术思想和主旨的范围内对这些实施方式进行适当的变更，而这些变更后的实施方式显然也包括在本发明的保护范围之内。

Claims (13)

  1. 一种阴离子-阳离子-非离子型表面活性剂，其特征在于，选自基本上如下式(I)所示的化合物中的至少一种，
    Figure PCTCN2014000939-appb-100001
    式(I)中，基团N+是季氮阳离子；基团R1至R3彼此相同或不同，各自独立地选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基、任选取代的C6-50(优选C6-20)芳基和由式
    Figure PCTCN2014000939-appb-100002
    代表的基团，前提是基团R1至R3中的至少一个是由式
    Figure PCTCN2014000939-appb-100003
    代表的基团，此处所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、由式
    Figure PCTCN2014000939-appb-100004
    代表的基团、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-)；基团Link选自任选取代的x+1价C1-50(优选C1-20)直链或支链烷基、任选取代的x+1价C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的x+1价C2-50(优选C2-20)直链或支链烯基、任选取代的x+1价C6-50(优选C6-20)芳基和任选取代的x+1价C3-50(优选C3-20)直链或支链杂烷基；各基团Poly彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100005
    代表的基团；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根 (COO-)和磺酸根(SO3 -)；x是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；在各基团Poly之间，各数值y彼此相同或不同，各自独立地选自0至200之间的任意数值(优选0至100之间的任意数值)，前提是x个数值y之和大于0；在各基团Poly之间，各基团Ru彼此相同或不同，各自独立地选自C2-6直链或支链亚烷基(优选各自独立地选自-CH2-CH2-和-CH2-CH(CH3)-)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
    其中，在没有特别明确的情况下，所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代，并且，所述直链或支链杂烷基选自直链或支链烷基分子结构内部的一个或多个基团-CH2-被选自-O-、-S-、-NR′-(其中，基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基)和
    Figure PCTCN2014000939-appb-100006
    (其中，基团N+是季氮阳离子；基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))之一的替代基团直接替代而获得的基团；以及直链或支链烷基分子结构内部的一个或多个基团
    Figure PCTCN2014000939-appb-100007
    被替代基团
    Figure PCTCN2014000939-appb-100008
    或
    Figure PCTCN2014000939-appb-100009
    (其中，基团N+是季氮阳离子；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、 氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))直接替代而获得的基团，
    前提是，所述基团R1、所述基团R2、所述基团R3和所述基团Rh中的至少一个在其结构中包含C8直链状部分。
  2. 权利要求1所述的阴离子-阳离子-非离子型表面活性剂，其中各基团Poly各自独立地选自式
    Figure PCTCN2014000939-appb-100010
    代表的醚链段；在各基团Poly之间，各数值m彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值；在各基团Poly之间，各数值n彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m与全部数值n之和大于0；优选的是，全部数值m之和大于0且不超过100(优选不超过50)和/或全部数值n之和大于0且不超过100(优选不超过50)。
  3. 权利要求1所述的阴离子-阳离子-非离子型表面活性剂，选自基本上如下式(I-1)所示的化合物、基本上如下式(I-2)所示的化合物、基本上如下式(I-3)所示的化合物和基本上如下式(I-4)所示的化合物中的至少一种，并且附加条件是：这些化合物分子结构中的至少一个N原子与另外的基团Rh和基团X键合而呈现为式
    Figure PCTCN2014000939-appb-100011
    (其中，基团N+是所述至少一个N原子的季氮阳离子形式；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))所示的季铵盐和/或季铵碱的形式，
    Figure PCTCN2014000939-appb-100012
    式(I-1)中，各基团Ra彼此相同或不同，各自独立地选自氢、任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-10芳基；各基团Ra′彼此相同或不同，各自独立地选自单键、 任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、羰基、任选取代的C1-10直链或支链亚烷基羰基和任选取代的C2-10直链或支链亚烯基羰基，优选各自独立地选自单键和任选取代的C1-6直链或支链亚烷基；b是1至3之间的任意整数，优选1；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0，并且至少一个基团Y是N；x′是1至5之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp1彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100013
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp1是式
    Figure PCTCN2014000939-appb-100014
    代表的基团；各基团Rp2彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100015
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′、全部数值m″、全部数值n′与全部数值n″之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金 属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
    前提是，所述基团Ra和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
    Figure PCTCN2014000939-appb-100016
    式(I-2)中，基团Rb选自任选取代的C1-49直链或支链烷基、任选取代的C5-49单环或多环环烷基和任选取代的C2-49直链或支链烯基(优选选自任选取代的C1-29直链或支链烷基、任选取代的C5-10单环或多环环烷基和任选取代的C2-29直链或支链烯基，或者选自任选取代的C8-29直链或支链烷基、任选取代的C5-8单环或多环环烷基和任选取代的C8-29直链或支链烯基，或者选自任选取代的C8-19直链或支链烷基、任选取代的C5-7单环环烷基(比如环己基)和任选取代的C8-19直链或支链烯基)；各基团Rb′彼此相同或不同，各自独立地选自单键和羰基；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0，并且至少一个基团Y是N；x″是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp1彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100017
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp1是式
    Figure PCTCN2014000939-appb-100018
    代表的基团；各基团Rp2彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100019
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选 C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′、全部数值m″、全部数值n′与全部数值n″之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
    前提是，所述基团Rb和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
    Figure PCTCN2014000939-appb-100020
    式(I-3)中，各基团Rc彼此相同或不同，各自独立地选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯 基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；x″′是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100021
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp是式
    Figure PCTCN2014000939-appb-100022
    代表的基团；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′与全部数值n′之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
    前提是，所述基团Rc和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
    Figure PCTCN2014000939-appb-100023
    式(I-4)中，基团Rc选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基 和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；基团Y是N或O，前提是当基团Y是N时，a＝1，当基团Y是O时，a＝0；x″″是1至9之间的任意整数(优选1至3之间的任意整数，更优选1或2)；各基团Rp1彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100024
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp1是式
    Figure PCTCN2014000939-appb-100025
    代表的基团；各基团Rp2彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100026
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各基团Rp3彼此相同或不同，各自独立地选自式
    Figure PCTCN2014000939-appb-100027
    代表的基团、氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10 或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各数值m′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值m″′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，各数值n″′彼此相同或不同，各自独立地选自0至100之间的任意数值，优选0至50之间的任意数值，前提是全部数值m′、全部数值m″、全部数值m″′、全部数值n′、全部数值n″与全部数值n″′之和大于0且不超过200(优选大于0且不超过100)；各基团L彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基)；各基团Salt彼此相同或不同，各自独立地选自由-A-(M)r +代表的基团，其中基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M选自碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M为碱金属或铵根时，r＝1；当基团M为碱土金属时，r＝0.5，
    前提是，所述基团Rc和所述基团Rh中的至少一个在其结构中包含C8直链状部分，
    其中，所述任选取代指的是任选被一个或多个选自羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代。
  4. 权利要求1所述的阴离子-阳离子-非离子型表面活性剂，其中所述基团X-与所述基团(M)r +中的至少一部分以(M)r +X-的形式独立于所述阴离子-阳离子-非离子型表面活性剂而存在，优选的是，在所述阴离子-阳离子-非离子型表面活性剂的整个分子结构中，设所述基团X-的总个数为e1，所述基团N+的总个数为e2，所述基团A-的总个数为e3，所述基团(M)r +的总个数为e4，当e2＝e3时，0≤e1≤e2，0≤e4≤e3，当e2＞e3时，0＜e1≤e2，0≤e4≤e3，当e2＜e3时，0≤e1≤e2，0＜e4≤e3，但前提是e1+e3＝e2+e4，或者，e2＝e3，e1＝0，e4＝0。
  5. 一种阴离子-阳离子-非离子型表面活性剂的制造方法，其特征在于，包括以下步骤：
    步骤(1)：使一种或多种含氮且带有一个或多个选自-OH、-NH2 和-NH-的官能团的多官能化合物与一种或多种下式(Y)所示的烯化氧在碱性催化剂(优选碱金属氢氧化物)的存在下反应，获得醚化产物，
    Figure PCTCN2014000939-appb-100028
    式(Y)中，基团Ru′选自C2-6直链或支链亚烷基(优选选自-CH2-CH2-和-CH2-CH(CH3)-)，
    步骤(2)：使所述醚化产物与下式(A)所示的季铵化剂进行反应，由此获得阳离子-非离子型表面活性剂，其中所述季铵化剂的用量使得所述醚化产物分子结构中的至少一个N原子形成季铵盐基团，
    Rh-X′   (A)
    式(A)中，基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X′选自卤素(优选氟、氯、溴和碘，更优选氯)，
    前提是，所述多官能化合物与所述季铵化剂中的至少一个在其分子结构中包含C8直链状部分，
    步骤(3)：使所述阳离子-非离子型表面活性剂与一种或多种下式(Z)所示的化合物在碱性催化剂(优选碱金属氢氧化物)的存在下反应，由此获得阴离子-阳离子-非离子型表面活性剂，
    G-L-AS   (Z)
    式(Z)中，基团G选自卤素(优选氟、氯、溴和碘，更优选氯)和羟基；基团L选自任选取代的C1-10直链或支链亚烷基和任选取代的C2-10直链或支链亚烯基(优选选自任选取代的C1-5直链或支链亚烷基)；基团AS选自由-A-(M′)r +代表的基团；基团A-选自羧酸根(COO-)和磺酸根(SO3 -)；基团M′选自氢、碱金属(优选Li、Na和K)、碱土金属(优选Mg和Ca)和铵根(NH4)；当基团M′为氢、碱金属或铵根时，r＝1；当基团M′为碱土金属时，r＝0.5，
    任选，步骤(4)：将所述制造方法的任意步骤所获得的阴离子-阳离子-非离子型表面活性剂中的至少一部分季铵盐基团转换为相应的季铵碱基团，和/或，将所述阴离子-阳离子-非离子型表面活性剂中的至少一部分季铵碱基团转换为相应的季铵盐基团，
    任选，步骤(5)：从所述制造方法的任意步骤所获得的阴离子-阳离子-非离子型表面活性剂中分离出至少一部分(优选全部)以游离形式存在的化合物(M′)rX′，
    其中，所述任选取代指的是任选被一个或多个选自羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷 基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代。
  6. 权利要求5所述的制造方法，其中所述多官能化合物选自下式(X)所示的化合物中的至少一种，
    Figure PCTCN2014000939-appb-100029
    式(X)中，基团R′1至R′3彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基、任选取代的C6-50(优选C6-20)芳基和由式
    Figure PCTCN2014000939-appb-100030
    代表的基团，前提是基团R′1至R′3中的至少一个是氢或由式
    Figure PCTCN2014000939-appb-100031
    代表的基团，此处所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、由式
    Figure PCTCN2014000939-appb-100032
    代表的基团、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代；基团LA选自任选取代的x0+1价C1-50(优选C1-20)直链或支链烷基、任选取代的x0+1价C5-50(优选C5-10或者C5-8)单环或多环环烷基(优选C5-7单环环烷基比如环己基)、任选取代的x0+1价C2-50(优选C2-20)直链或支链烯基、任选取代的x0+1价C6-50(优选C6-20)芳基和任选取代的x0+1价C3-50(优选C3-20)直链或支链杂烷基；x0是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Func彼此相同或不同，各自独立地选自-OH、＞NH和-NH2，并且，所述直链或支链杂烷基选自直链或支链烷基分子结构内部的一个或多个基团-CH2-被选自-O-、-S-、-NR′-(其中，基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基)和
    Figure PCTCN2014000939-appb-100033
    (其中，基团N+是季氮阳离子；基团R′选自任选取代的C1-20(优选C1-10)直链或支链烷基、 任选取代的C5-10(优选C5-8或C5-7)单环或多环环烷基、任选取代的C2-20(优选C2-10)直链或支链烯基和任选取代的C6-20(优选C6-10)芳基；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))之一的替代基团直接替代而获得的基团；以及直链或支链烷基分子结构内部的一个或多个基团
    Figure PCTCN2014000939-appb-100034
    被替代基团
    Figure PCTCN2014000939-appb-100035
    或
    Figure PCTCN2014000939-appb-100036
    (其中，基团N+是季氮阳离子；基团Rh选自任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；基团X-选自卤素离子(优选氟离子、氯离子、溴离子和碘离子，更优选氯离子)和氢氧根离子(OH-))直接替代而获得的基团，
    所述多官能化合物优选选自下式(X-1)所示的化合物、下式(X-2)所示的化合物、下式(X-3)所示的化合物和下式(X-4)所示的化合物中的至少一种，
    Figure PCTCN2014000939-appb-100037
    式(X-1)中，各基团Ra彼此相同或不同，各自独立地选自氢、任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基和任选取代的C6-20芳基；各基团Ra′彼此相同或不同，各自独立地选自单键、任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、羰基、任选取代的C1-10直链或支链亚烷基羰基和任选取代的C2-10直链或支链亚烯基羰基，优选各自独立地选自单键和任选取代的C1-6直链或支链亚烷基；b是1至3之间的任意整数，优选1；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a1＝1，当基团Y是O时，a1＝0，并且至少一个基团Y是N；x1是1至5之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优 选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′1是氢；各基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，
    Figure PCTCN2014000939-appb-100038
    式(X-2)中，基团Rb选自任选取代的C1-49直链或支链烷基、任选取代的C5-49单环或多环环烷基和任选取代的C2-49直链或支链烯基(优选选自任选取代的C1-29直链或支链烷基、任选取代的C5-10单环或多环环烷基和任选取代的C2-29直链或支链烯基，或者选自任选取代的C8-29直链或支链烷基、任选取代的C5-8单环或多环环烷基和任选取代的C8-29直链或支链烯基，或者选自任选取代的C8-19直链或支链烷基、任选取代的C5-7单环环烷基(比如环己基)和任选取代的C8-19直链或支链烯基)；各基团Rb′彼此相同或不同，各自独立地选自单键和羰基；各基团Y彼此相同或不同，各自独立地选自N和O，前提是当基团Y是N时，a2＝1，当基团Y是O时，a2＝0，并且至少一个基团Y是N；x2是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′1是氢；各基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，
    Figure PCTCN2014000939-appb-100039
    式(X-3)中，各基团Rc彼此相同或不同，各自独立地选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；x3是1至10之间的任意整数(优选1至4之间的任意整数，比如1、2或者3)；各基团Rp′彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′是氢，
    Figure PCTCN2014000939-appb-100040
    式(X-4)中，基团Rc选自任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C1-20直链或支链烷基羰基和任选取代的C2-20直链或支链烯基羰基(或者各自独立地选自任选取代的C1-10直链或支链烷基、任选取代的C2-10直链或支链烯基、任选取代的C1-10直链或支链烷基羰基和任选取代的C2-10直链或支链烯基羰基，或者各自独立地选自任选取代的C8-20直链或支链烷基、任选取代的C8-20直链或支链烯基、任选取代的C8-20直链或支链烷基羰基和任选取代的C8-20直链或支链烯基羰基)；各基团Rd彼此相同或不同，各自独立地选自任选取代的C1-10直链或支链亚烷基、任选取代的C2-10直链或支链亚烯基、任选取代的C1-10直链或支链亚烷基羰基、任选取代的 C2-10直链或支链亚烯基羰基、任选取代的羰基C1-10直链或支链亚烷基羰基和任选取代的羰基C2-10直链或支链亚烯基羰基(优选各自独立地选自任选取代的C1-5直链或支链亚烷基和任选取代的C1-5直链或支链亚烷基羰基)；基团Y是N或O，前提是当基团Y是N时，a4＝1，当基团Y是O时，a4＝0；x4是1至9之间的任意整数(优选1至3之间的任意整数，更优选1或2)；各基团Rp′1彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，前提是至少一个基团Rp′1是氢；各基团Rp′2彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基；各基团Rp′3彼此相同或不同，各自独立地选自氢、任选取代的C1-50(优选C1-20)直链或支链烷基、任选取代的C5-50(优选C5-10或者C5-8)单环或多环环烷基(比如环己基)、任选取代的C2-50(优选C2-20)直链或支链烯基和任选取代的C6-50(优选C6-20)芳基，
    其中，在没有特别明确的情况下，所谓“任选取代”，指的是任选被一个或多个选自氧代、羟基、C1-20(优选C1-10)直链或支链烷基、C5-10(优选C5-8或者C5-7)单环或多环环烷基(比如环己基)、C2-20(优选C2-10)直链或支链烯基和C6-20(优选C6-10)芳基的取代基取代。
  7. 权利要求5所述的制造方法，其中所述多官能化合物与所述烯化氧的摩尔比为1∶0-200(优选1∶0-100)，但不包括0；所述多官能化合物与所述式(Z)所示的化合物的摩尔比为1∶1-10(优选1∶1-3)；所述步骤(1)的反应条件包括：反应温度为室温至300℃(优选100-200℃)，反应时间为1-20小时(优选1-10小时)；所述步骤(2)的反应条件包括：反应温度为0-300℃(优选50-150℃)，反应时间为1-20小时(优选4-15小时)；所述步骤(3)的反应条件包括：反应温度为0-300℃(优选50-200℃)，反应时间为1-20小时(优选4-10小时)。
  8. 权利要求5所述的制造方法，其中所述烯化氧至少包括环氧丙烷，并且使所述多官能化合物先与所述环氧丙烷反应。
  9. 一种三次采油用驱油组合物，其特征在于，包含权利要求1至4任一项所述的阴离子-阳离子-非离子型表面活性剂或者按照权利要求5至8任一项所述的制造方法制造的阴离子-阳离子-非离子型表面活性剂，以及水，其中以所述三次采油用驱油组合物的总重量为100wt％计，所述阴离子-阳离子-非离子型表面活性剂的重量百分含量为0.001-10wt％，优选0.005-5wt％，更优选0.02-1wt％。
  10. 权利要求9所述的三次采油用驱油组合物，其中不包含无机碱。
  11. 一种三次采油用驱油组合物的制造方法，其特征在于，使权利要求1至4任一项所述的阴离子-阳离子-非离子型表面活性剂或者按照权利要求5至8任一项所述的制造方法制造的阴离子-阳离子-非离子型表面活性剂至少与水混合，其中以所述三次采油用驱油组合物的总重量为100wt％计，所述阴离子-阳离子-非离子型表面活性剂的重量百分含量为0.001-10wt％，优选0.005-5wt％，更优选0.02-1wt％。
  12. 一种三次采油方法，其特征在于，包括使用权利要求1至4任一项所述的阴离子-阳离子-非离子型表面活性剂、按照权利要求5至8任一项所述的制造方法制造的阴离子-阳离子-非离子型表面活性剂、权利要求9或10所述的三次采油用驱油组合物或者按照权利要求11所述的制造方法制造的三次采油用驱油组合物作为驱替液进行三次采油的步骤。
  13. 权利要求12所述的三次采油方法，其中不使用无机碱。
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