CN108558691B - Star-shaped compound carrying dense charges and preparation method thereof - Google Patents

Star-shaped compound carrying dense charges and preparation method thereof Download PDF

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CN108558691B
CN108558691B CN201810387407.2A CN201810387407A CN108558691B CN 108558691 B CN108558691 B CN 108558691B CN 201810387407 A CN201810387407 A CN 201810387407A CN 108558691 B CN108558691 B CN 108558691B
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王晨
杨通
辛燕
王霞
杨晓武
费贵强
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Shaanxi University of Science and Technology
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    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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Abstract

The invention discloses a star-shaped compound carrying dense charges and a preparation method thereof, wherein the compound is prepared by the following steps: dropwise adding a quantitative trimethylolpropane-tri (3-aziridinyl propionate) reaction solution into a reaction bottle filled with methylamine (or ethylamine) aqueous solution and an acid catalyst to perform a first step aziridine ring-opening reaction; then adding quantitative 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride into the reaction solution to carry out second quaternization reaction, and obtaining a star-shaped compound carrying dense charges.

Description

Star-shaped compound carrying dense charges and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of multi-quaternary ammonium salt cationic surfactants, in particular to a star-shaped compound carrying dense charges and a preparation method thereof.
Background
The aziridine ring structure in the aziridine crosslinking agent has larger tension and higher activity, can react with amino, carboxyl and hydroxyl to form a compound with a star structure or a net structure, and how to introduce polycation quaternary ammonium salt groups into the compound to prepare a new compound for application in oil and gas exploitation is a difficult point of current research.
Clay minerals such as montmorillonite, kaolin, chlorite and the like exist in the oil and gas reservoir, when the clay minerals are contacted with incompatible external fluid, hydration expansion and dispersion migration can occur to block the oil and gas reservoir channel, and the use of the clay stabilizer can prevent and reduce the damage of the clay expansion and dispersion to the stratum. At present, clay stabilizers are various in types, such as inorganic salts, inorganic alkalis, inorganic polymers, nonionic polymers, cationic polymers and the like, the most used cationic polymers with the best effect are cationic polymers, particularly quaternary ammonium salt cationic polymers, the quaternary ammonium salt cationic clay stabilizers are easily and preferentially adsorbed by clay, dehydration among clay crystal layers can be promoted, the expansive force is reduced, hydration of the clay is effectively inhibited, the clay crystal layers can be embedded, water molecules are prevented from entering, the hydration and expansion effects of the clay are reduced, and the clay has a long-term stabilizing effect due to firm adsorption on clay particles. However, the prior quaternary ammonium salt clay stabilizer has the problems of large dosage, low anti-swelling rate, large damage to stratum and the like,
disclosure of Invention
In order to expand the variety of the polycation quaternary ammonium salt surfactant and the quantity of the polycation quaternary ammonium salt, the invention uses the reaction of the high-activity aziridine crosslinking agent and the active amine group to form the star-shaped surfactant carrying active secondary amine, and then introduces the quaternary ammonium salt reagent carrying quaternary ammonium salt for reaction to obtain the star-shaped compound carrying dense charges. The invention aims at providing a star-shaped compound carrying dense charges, and aims at providing a preparation method of the compound.
In order to achieve the purpose, the invention adopts the following technical scheme:
a star-shaped compound carrying dense charges, which has a structural formula as follows:
Figure GDA0002521191010000021
wherein R1-is-CH3or-CH2CH3。
A method for preparing the densely charged star-shaped compound of claim 1, comprising the steps of:
adding trimethylolpropane-tri (3-aziridinyl propionate) reaction liquid into methylamine (or ethylamine) water solution and an acid catalyst to perform aziridine ring opening reaction, and reacting for 5-7 h at 40-70 ℃;
under the alkalescent condition, adding 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution into the reactant to carry out quaternization reaction, and reacting for 4-8 h at 50-70 ℃; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
In the aziridine ring-opening reaction, trimethylolpropane-tris (3-aziridinylpropionate) and methylamine (or ethylamine) were in a molar ratio of 1: 3.
In the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.
In the quaternization reaction, the pH value is 9-10 under the alkalescent condition, and K is used for reaction liquid2CO3And adjusting to alkalescence.
In the quaternization reaction, the amount of 3-chloro-2-hydroxypropyl-trimethylammonium chloride material was 6 times that of trimethylolpropane-tris (3-aziridinyl propionate).
The application of star-shaped compound carrying dense charges as clay stabilizer in oil and gas exploitation.
The addition amount of the clay stabilizer is 0.2-1% of the total mass.
Compared with the prior art, the invention has the following advantages:
in order to introduce a multi-cation quaternary ammonium salt group into the compound, the invention uses the aziridine crosslinking agent with high activity to react with an active amine group to form an independent star structure, and then introduces a quaternization reagent carrying a quaternary ammonium salt group to react, thereby obtaining the star compound with novel structure and dense charges. The star-shaped compound carrying the dense charges can be widely applied to the fields of preparing new materials and bactericides, inhibiting metal corrosion, dyeing and finishing fabrics, petroleum exploitation and the like.
According to the invention, the star-shaped surfactant carrying active secondary amine is formed by the reaction of the high-activity aziridine crosslinking agent and the active amine group, and the quaternary ammonium salt reagent carrying quaternary ammonium salt is introduced for reaction to obtain the star-shaped compound carrying dense charges.
The clay stabilizer carrying dense charges can simultaneously act on negatively charged clay particles at multiple points due to eighteen quaternary ammonium salt groups in molecules, and has high adsorption degree, thereby realizing the purposes of low dosage and high anti-swelling rate.
Drawings
FIG. 1 is a chemical structural formula of the present invention;
FIG. 2 is a scheme of the synthesis of the reaction of the present invention.
Detailed Description
As shown in fig. 1 and 2, the reaction equation of the present invention is:
Figure GDA0002521191010000041
wherein R is1is-CH3or-CH2CH3。
According to the reaction mechanism, the invention adopts the following technical scheme
A star-shaped compound carrying dense charges, which has the structural formula:
Figure GDA0002521191010000042
wherein R is1is-CH3or-CH2CH3。
The preparation method of the star-shaped compound carrying the dense charges comprises the following steps:
dropwise adding trimethylolpropane-tri (3-aziridinyl propionate) reaction liquid into a reaction bottle filled with a methylamine (or ethylamine) water solution with the mass fraction of 20-70% and an acid catalyst to carry out aziridine ring-opening reaction, wherein the mol ratio of the hydroxymethylpropane-tri (3-aziridinyl propionate) to methylamine (or ethylamine)The molar ratio is 1:3, and the reaction is carried out for 5-7 h at the temperature of 40-70 ℃; then using K to react the reaction solution2CO3Adjusting to be alkaline (pH is 9-10), adding 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to perform a second quaternization reaction, wherein the amount of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 6 times that of trimethylolpropane-tris (3-aziridinyl propionate), and reacting at 50-70 ℃ for 4-8 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
Example 1
In a reactor containing 20% by mass of methylamine water solution (23.25g, containing 4.65g, 0.15mol of methylamine) and acidic catalyst (85% H)3PO40.25g), heated to 40 ℃, and then added dropwise with a 70% by mass fraction aqueous solution (35.42g, containing 21.25g, 0.05mol of trimethylolpropane-tris (3-aziridinyl propionate) over 40 min. After the dropwise addition, heating to 50 ℃ and reacting for 7 hours; using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding 80% by mass of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution (70.50g, wherein 56.40g of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is contained, 0.30mol), dropwise adding for 60min, and reacting at 50 ℃ for 8 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum to constant weight to obtain the product.
The structural formula of the product obtained in example 1 is:
Figure GDA0002521191010000061
1H NMR(300MHz，DMSO)：4.77～4.84(m，24H)，3.94(s，6H)，3.63～3.68(m，18H)，3.25～3.51(m，48H)，3.30(s，117H)，2.70(t，6H)，1.69(m，2H)，0.84(t，3H)ppm。
13C NMR(300MHz，DMSO)：173.2，68.1，65.7，58.4，55.1，50.7，35.7，27.3，22.9，7.1ppm。
example 2
In a 70% ethylamine water solution (9.54g, containing 6.75g of ethylamine and 0.15mol) and an acid catalyst (85% H)3PO40.25g), heated to 50 ℃, and then added dropwise with a 70% by mass fraction aqueous solution (35.42g, containing 21.25g, 0.05mol of trimethylolpropane-tris (3-aziridinyl propionate) over 40 min. After the dropwise addition is finished, heating to 70 ℃ and reacting for 5 hours; using K as the reaction solution2CO3Adjusting to be alkalescent (pH is 9-10), dropwise adding 80% by mass of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution (70.50g, wherein 56.40g of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is contained, 0.30mol), dropwise adding for 60min, and reacting at 70 ℃ for 4 h; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.
The structural formula of the product obtained in example 2 is:
Figure GDA0002521191010000071
1H NMR(300MHz，DMSO)：4.84(m，12H)，4.77(d，12H)，3.63～3.68(m，18H)，3.25～3.51(m，54H)，3.30(s，108H)，2.69(t，6H)，1.69(m，2H)，1.25(t，9H)，0.84(t，3H)ppm。
13C NMR(300MHz，DMSO)：173.1，72.5，65.6，58.4，55.6，35.7，27.3，22.9，7.7～8.3ppm。
characterization of Clay stabilizer Properties
(1) Clay stabilizer swelling resistance and washing resistance test
The expansion prevention rate is evaluated by measuring the expansion increment of the sodium bentonite in a clay stabilizer solution and distilled water according to a centrifugal method in a standard SY/T5971-2016 clay stabilizer performance evaluation method for oil and gas field fracturing acidification and water injection and Q/SH 0053-2010 clay stabilizer technical requirement. The clay stabilizers of example 1 and example 2 were measured for their anti-swelling rate and water washing resistance in water. The results are shown in Table 1.
TABLE 1 Clay stabilizer swell prevention and Water washing resistance
Figure GDA0002521191010000072
Figure GDA0002521191010000081
As can be seen from the table, the clay stabilizer of the invention has the anti-swelling rate higher than 85% and the water washing resistance rate higher than 90% in the clear water fracturing fluid under the addition of 0.2%; under the addition of 0.5 percent of clay stabilizer, the anti-swelling rate in the clear water fracturing fluid is higher than 90 percent, and the water washing resistance rate is more than 94 percent; the clay stabilizers (potassium chloride and ammonium chloride) of the control inorganic salts showed less than 70% anti-swelling at 2.0% addition.
(2) Compatibility test
The clay stabilizers of examples 1 and 2 were observed for compatibility with the base fluid and acid fluid of the fracturing fluid, and the results are shown in table 2.
TABLE 2 compatibility test of Clay stabilizers
Figure GDA0002521191010000082
Figure GDA0002521191010000091
As can be seen from Table 2, the clay stabilizer of the present invention has no delamination, sedimentation and suspension phenomena when mixed with a fracturing fluid base and an acid solution, and has good compatibility.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.

Claims (3)

1. The preparation method of the star-shaped compound carrying dense charges is characterized in that the structural formula of the star-shaped compound is as follows:
Figure FDA0002521191000000011
wherein R1-is-CH3or-CH2CH3；
The preparation method of the star-shaped compound comprises the following steps:
adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into methylamine or ethylamine water solution and an acid catalyst to perform aziridine ring-opening reaction, and reacting at 40-70 ℃ for 5-7 h;
under the alkalescent condition, adding 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution into the reactant to carry out quaternization reaction, and reacting for 4-8 h at 50-70 ℃; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating a product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product;
in the aziridine ring opening reaction, trimethylolpropane-tris (3-aziridinylpropionate) and methylamine or ethylamine were in a molar ratio of 1: 3.
2. The method of claim 1 for preparing a star-shaped compound carrying dense charges, comprising: in the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.
3. The method for preparing a star-shaped compound with dense charges according to claim 1, wherein the pH value is 9-10 under weak alkaline condition in the quaternization reaction, and the reaction solution is K2CO3And adjusting to alkalescence.
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CN102942493A (en) * 2012-11-09 2013-02-27 西南石油大学 Terquaternary cation surface active agent and preparation method
WO2016172436A1 (en) * 2015-04-23 2016-10-27 Temple University-Of The Commonwealth System Of Higher Education Polycationic amphiphiles and polymers thereof as antimicrobial agents and methods using same

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CN102942493A (en) * 2012-11-09 2013-02-27 西南石油大学 Terquaternary cation surface active agent and preparation method
WO2016172436A1 (en) * 2015-04-23 2016-10-27 Temple University-Of The Commonwealth System Of Higher Education Polycationic amphiphiles and polymers thereof as antimicrobial agents and methods using same

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Title
含三个硬脂酰胺基的树枝状季铵盐的制备;徐冬梅 等;《化学研究与应用》;20060630;第18卷(第6期);第603-606页 *

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