CN110483299B - Polymerizable surfactant containing aromatic hydrocarbon structure and preparation method thereof - Google Patents
Polymerizable surfactant containing aromatic hydrocarbon structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polymerizable surfactant containing an aromatic hydrocarbon structure and a preparation method thereof. The surfactant has a structure represented by the following formula (I):
R1、R2each independently is one of hydrogen atoms or alkyl groups with 1-20 carbon atoms; n is 1 to 30. The raw materials used in the invention are easy to obtain, the preparation is simple, the use is safe, and the storage is convenient. The preparation method provided by the invention has the advantages of mild reaction conditions, high yield and simple product post-treatment process.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a polymerizable surfactant containing an aromatic hydrocarbon structure and a preparation method thereof.
Background
Crude oil is composed mainly of light components (saturated hydrocarbons, arylhydrocarbons) and heavy components (gums, asphaltenes). Heavy components of the thickened oil are more, and light components are less. The viscosity of heavy oil is closely related to the content of colloid and asphaltene in the heavy oil reported in the literature (oilfield chemistry, 1995, 12(4): 347-: (1) the basic structure of asphaltene and colloid is that a condensed aromatic ring (with larger effect between molecular planes) is taken as a core, a plurality of cycloparaffins and heterocycles are connected around the core, and the ring is provided with a normal (isomeric) alkyl side chain; (2) the molecules contain hydroxyl, amido, carboxyl, carbonyl and the like which can form hydrogen bonds, so that the hydrogen bonding effect and the molecular plane effect between colloid and asphaltene molecules are larger, the colloid and the asphaltene are stacked in an overlapping way, and the internal friction force is larger. The chemical agent with the aromatic hydrocarbon structure is similar to the heavy component of the thick oil, and can be complexed with the heavy component of the thick oil, break the association structure of the original colloid asphaltene in the crude oil, change the binding force among the colloid asphaltenes and reduce the viscosity of the thick oil. However, no method for preparing a polymerizable surfactant having an aromatic hydrocarbon structure is provided.
In recent years, polymer surfactants are hot spots for research, and the preparation of polymerizable surfactants is a key link for the preparation of polymer surfactants. Patent document CN 104250356 provides a preparation method and application of polymerizable surfactant, wherein the surfactant is fatty alcohol polyoxyethylene acrylate, and the surfactant is subjected to aqueous solution polymerization with AMPS in the document and is applied to emulsified crude oil; patent document CN 104140507 provides a hydrophobic sheetThe behenyl polyoxyethylene ether methacrylate participates in aqueous solution polymerization and can be applied to the fields of oil and gas exploitation, paint and the like; WO 85/03510A1 discloses a water-soluble hydrophobically associative copolymer and its use in tertiary mineral oil recovery2＝CHCOO(EO)5～40R, wherein R is an alkyl group having 8 to 16 carbon atoms. However, the above documents do not provide a method for preparing a polymerizable surfactant having an aromatic structure (structurally matched with heavy components of the heavy oil).
Disclosure of Invention
In order to solve the problems, the invention provides a polymerizable surfactant containing an aromatic hydrocarbon structure matched with a heavy component structure in the thick oil. The surfactant can be copolymerized with monomers such as acrylamide and the like to synthesize a polymer surfactant with excellent emulsification and viscosity reduction performance on thick oil under the condition of low shearing of stratum, and has wide application prospect and development space.
To achieve the above object, in one aspect, the present invention provides a polymerizable surfactant containing an aromatic hydrocarbon structure, wherein the surfactant has a structure represented by the following formula (I):
R1、R2each independently is one of hydrogen atoms or alkyl groups with 1-20 carbon atoms;
n＝1～30。
according to some embodiments of the invention, wherein R1、R2Each independently is one selected from a hydrogen atom or a straight chain alkyl or branched chain alkyl with 3 to 10 carbon atoms.
According to some embodiments of the invention, wherein R1、R2Each independently selected from hydrogen atom, propyl group, isopropyl group, tert-butyl group, sec-butyl group, isobutyl group, n-butyl group, n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 3-methylbutyl group, 1, 2-dimethylpropyl group, 1-dimethylpropyl group, 2-methylbutyl group, neopentyl groupOne of a group consisting of a hexyl group, a n-hexyl group, a 1-methylpentyl group, a 2-ethylbutyl group, a 4-methylpentyl group, a1, 3-dimethylbutyl group, a 2-methyl-1-ethylpropyl group, a1, 1-dimethylbutyl group, a 2-methylpentyl group, a 3-methylpentyl group, a1, 2-dimethylbutyl group, a 1-methyl-1-ethylpropyl group, a 2-ethylbutyl group, a 3, 3-dimethylbutyl group, a1, 2, 2-trimethylpropyl group, a2, 2-dimethylbutyl group, a2, 3-dimethylbutyl group, a1, 1, 2-trimethylpropyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
According to some embodiments of the invention, n is 1 to 10.
On the other hand, the invention also provides a method for preparing the polymerizable surfactant containing the aromatic hydrocarbon structure, wherein the method comprises the steps of taking the aromatic hydrocarbon polyoxyethylene ether shown in the formula (II) as a raw material, and reacting the aromatic hydrocarbon polyoxyethylene ether with acrylic acid in a solvent in the presence of a catalyst and a polymerization inhibitor to obtain the surfactant; or comprises that aromatic alkyl polyethenoxy ether shown in formula (II) is used as raw material, and reacts in solvent in the presence of acid-binding agent and acryloyl chloride to obtain the surfactant;
r1, R2 and n are the same as in formula (I).
According to some specific embodiments of the present invention, the method comprises the following steps (method one):
(a1) aromatic polyoxyethylene ether is used as a raw material and reacts with acrylic acid in a solvent in the presence of a catalyst and a polymerization inhibitor;
(a2) after the reaction is finished, washing the reaction solution obtained in the step (a1) by using a 1-10 wt% sodium bicarbonate solution and a saturated sodium chloride solution, and concentrating to obtain the surfactant;
alternatively, the method comprises the following steps (method two):
(b1) dissolving aromatic polyoxyethylene ether and an acid-binding agent in a solvent to obtain a mixed solution;
(b2) dropwise adding acryloyl chloride into the mixed solution obtained in the step (b1), and heating for reaction after dropwise adding is finished;
(b3) and (b2) washing the reaction solution obtained in the step (b2) with a saturated sodium sulfate solution, and concentrating to obtain the surfactant.
According to some specific embodiments of the present invention, the method comprises the following steps (method one):
(a1) adding aryl polyoxyethylene ether and a solvent into a reaction device with a water separator, stirring and dissolving, then adding a catalyst and a polymerization inhibitor, stirring and dissolving, finally adding acrylic acid, and heating for reaction;
(a2) after the reaction is finished, washing the reaction solution obtained in the step (a1) by using a 1-10 wt% sodium bicarbonate solution and a saturated sodium chloride solution, and concentrating to obtain the surfactant;
alternatively, the method comprises the following steps (method two):
(b1) adding aromatic polyoxyethylene ether, an acid-binding agent and a solvent into a reaction device, and stirring at a low temperature until the aromatic polyoxyethylene ether, the acid-binding agent and the solvent are dissolved to obtain a mixed solution;
(b2) dropwise adding acryloyl chloride into the mixed solution obtained in the step (b1), heating the system after dropwise adding is finished, and keeping the temperature until the reaction is finished;
(b3) and (b2) washing the reaction solution obtained in the step (b2) with a saturated sodium sulfate solution, and concentrating to obtain the surfactant.
According to some embodiments of the invention, wherein the solvent in which the surfactant is prepared in the presence of the catalyst and the polymerization inhibitor is selected from a mixture of one or more of toluene, benzene, and p-xylene; the solvent for preparing the surfactant in the presence of the acid-binding agent and the acryloyl chloride is one or a mixture of more of dichloromethane, chloroform, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, cyclohexane and carbon tetrachloride.
According to some embodiments of the invention, wherein the solvent in which the surfactant is prepared in the presence of the catalyst and the polymerization inhibitor is toluene; the solvent for preparing the surfactant in the presence of the acid-binding agent and the acryloyl chloride is dichloromethane.
According to some embodiments of the invention, the catalyst is selected from the group consisting of p-toluenesulfonic acid, phosphoric acid, sulfuric acid, and hydrochloric acid.
According to some embodiments of the invention, the catalyst is p-toluenesulfonic acid.
According to some embodiments of the present invention, the amount of the catalyst is 0.5-2.5% by weight of the total amount of the aromatic polyoxyethylene ether and the acrylic acid.
According to some embodiments of the present invention, the amount of the catalyst is 1% to 2% of the total amount of the aromatic polyoxyethylene ether and the acrylic acid.
According to some embodiments of the invention, the polymerization inhibitor is selected from the group consisting of hydroquinone, p-benzoquinone, phenothiazine, β -phenylnaphthylamine, p-tert-butylcatechol, methylene blue, cuprous chloride, and a mixture of one or more of ferric chloride.
According to some embodiments of the invention, the polymerization inhibitor is hydroquinone.
According to some embodiments of the invention, the amount of the polymerization inhibitor is 5-9% by mass of the acrylic acid.
According to some embodiments of the invention, the amount of the polymerization inhibitor is 6-8% by mass of the acrylic acid.
According to some specific embodiments of the present invention, the mass ratio of the acrylic acid to the aromatic polyoxyethylene ether is 1-4: 1.
According to some embodiments of the invention, the mass ratio of the acrylic acid to the aromatic-based polyoxyethylene ether is 1.5-2.2: 1.
According to some embodiments of the present invention, the reaction temperature for preparing the surfactant in the presence of the catalyst and the polymerization inhibitor is 80 to 150 ℃.
According to some embodiments of the present invention, the reaction temperature for preparing the surfactant in the presence of the catalyst and the polymerization inhibitor is 115 to 130 ℃.
According to some embodiments of the invention, the acid-binding agent is selected from one or more of trimethylamine, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate and sodium carbonate.
According to some embodiments of the invention, the acid scavenger is triethylamine.
According to some embodiments of the present invention, the amount ratio of the triethylamine to the aromatic polyoxyethylene ether is 0.5-2.5: 1.
According to some embodiments of the present invention, the amount ratio of the triethylamine to the aromatic polyoxyethylene ether is 1.7-2.2: 1.
According to some embodiments of the present invention, the step (b1) comprises adding aromatic polyoxyethylene ether, an acid-binding agent and a solvent into a reaction apparatus, and stirring at-5 to 10 ℃ until the aromatic polyoxyethylene ether, the acid-binding agent and the solvent are dissolved.
According to some embodiments of the present invention, the step (b1) includes adding aromatic polyoxyethylene ether, acid-binding agent and solvent into the reaction apparatus, and stirring at 0-5 ℃ until the aromatic polyoxyethylene ether, acid-binding agent and solvent are dissolved.
According to some specific embodiments of the present invention, the mass ratio of the acryloyl chloride to the aromatic group polyoxyethylene ether is 1 to 3: 1.
According to some specific embodiments of the present invention, the mass ratio of the acryloyl chloride to the arene-based polyoxyethylene ether is 1.8 to 2.2: 1.
According to some specific embodiments of the present invention, the step (b2) includes adding acryloyl chloride dropwise to the mixed solution obtained in the step (b1), heating the system to 30-50 ℃ after the dropwise addition is completed, and then carrying out a reaction under a heat preservation condition.
According to some specific embodiments of the present invention, the step (b2) includes adding acryloyl chloride dropwise to the mixed solution obtained in the step (b1), heating the system to 35-45 ℃ after the dropwise addition is completed, and then carrying out a reaction under a heat preservation condition.
According to some embodiments of the invention, the method of the invention comprises:
the method comprises the following steps:
(1) adding aryl polyoxyethylene ether and a solvent into a reflux reaction device with a water separator, stirring until the aromatic polyoxyethylene ether and the solvent are dissolved, sequentially adding a catalyst and a polymerization inhibitor, stirring until the aromatic polyoxyethylene ether and the solvent are completely dissolved, finally adding acrylic acid into a reaction solution, and heating for reaction for a certain time;
(2) after the reaction is finished, washing the reaction solution obtained in the step (1) by using a 1-10 wt% sodium bicarbonate solution and a saturated sodium chloride solution, and concentrating to obtain an oily substance, namely the aromatic polyoxyethylene ether acrylate;
the second method comprises the following steps:
(1) adding aromatic polyoxyethylene ether, an acid-binding agent and a solvent into a reflux reaction device, and stirring at low temperature until the aromatic polyoxyethylene ether, the acid-binding agent and the solvent are dissolved;
(2) dripping acryloyl chloride into the reaction liquid in the step (1), heating the system after finishing dripping, and preserving heat until the reaction is finished;
(3) washing the reaction liquid obtained in the step (2) with a saturated sodium sulfate solution, and concentrating to obtain an oily substance, namely the aromatic polyoxyethylene ether acrylate;
in conclusion, the invention provides a polymerizable surfactant containing an aromatic hydrocarbon structure and a preparation method thereof. The surfactant of the invention has the following advantages:
1. the raw materials used in the invention are easy to obtain, the preparation is simple, the use is safe, and the storage is convenient.
2. The preparation method provided by the invention has the advantages of mild reaction conditions, high yield and simple product post-treatment process.
3. The aryl polyoxyethylene ether acrylate provided by the invention is a polymerizable surfactant and is characterized in that: (1) the structure contains a benzene ring structure, is similar to the structure of heavy components of the thick oil, and can be complexed with the heavy components of the thick oil, so that the association structure of the original colloid asphaltenes in the crude oil is broken, the binding force among the colloid asphaltenes is changed, and the viscosity of the thick oil is reduced; (2) the structure contains branched alkyl, so that the wetting and penetrating performances are excellent; (3) the double bond in the structure can participate in polymerization as a monomer, and the double bond can be polymerized with other monomers under the condition of micelle polymerization to form the polymer surfactant.
Drawings
FIG. 1 is a schematic view of an embodimentDi-tert-butylphenoxypolyoxyethylene ether acrylate (DPP) of example 16AA) liquid phase mass spectrum (LC-MS).
FIG. 2 shows di-tert-butylphenoxypolyoxyethylene ether acrylate (DPP) of example 16AA nuclear magnetic resonance hydrogen spectrum (1H NMR) graph.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1 (method one)
(1) In a 50mL three-necked flask equipped with a water separator and a reflux condenser, 3.0000g (6.383mmol) of di-t-butylphenoxypolyoxyethylene ether (n ═ 6) containing 6 ethyleneoxy EO units and 40mL of toluene were charged and stirred until completely dissolved, and then 0.0600g (0.545mmol) of hydroquinone and 0.0572g (0.332mmol) of p-toluenesulfonic acid were added and stirred until dissolved, and finally 0.8100g (11.241mmol) of acrylic acid was charged, and heated to 120 ℃ and reacted at this temperature for 6 hours, and water generated by the reaction was removed.
(2) Pouring the reaction liquid in the step (1) into a separating funnel, respectively washing with a 5 wt% sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution for several times, removing the solvent from the obtained organic phase, and drying in vacuum for 24 hours to obtain a light yellow oily substance which is di-tert-butylphenoxy polyoxyethylene ether acrylate (DPP) containing 6 ethylene oxide EO units6AA)2.85g。
The liquid chromatography-mass spectrometry (LC-MS) pattern of the pale yellow oil prepared in this example is shown in FIG. 1, where M/z 565 is [ M + CH ]3CN]+The molecular weight of the synthesized product is determined to be 524, which is consistent with DPP6AA in the formula.
Nuclear magnetic resonance hydrogen spectrum (1H NMR,400MHz,CDCl3) As shown in fig. 2, chemical shifts δ (ppm) are 6.9 to 7.3(3H, hydrogen on benzene ring), 6.39(1H, hydrogen on double bond C ═ CH)2) 6.12(1H, double bond hydrogen C ═ CH — CO),5.80(1H, double bond hydrogen C ═ CH2) 3.0-4.5(24H, 6-OCH)2CH2O-),0.5-2.2(18H, is tert-butylhydrogen), corresponds to DPP6AA in the structural formula.
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is di-tert-butyl phenoxy polyoxyethylene ether acrylate (DPP) containing 6 ethylene oxide EO units6AA)。
Example 2 (method one)
The preparation method is the same as that in the embodiment 1, except that: in step (1) 5.0000g (14.793mmol) of di-tert-butylphenoxypolyoxyethylene ether containing 3 ethyleneoxy EO units (n ═ 3), 0.1200g (1.090mmol) of hydroquinone, 0.1366g (0.793mmol) of p-toluenesulfonic acid and 1.8300g (25.396mmol) of acrylic acid were added.
The obtained yellow oily substance is di-tert-butyl phenoxy polyoxyethylene ether acrylate (DPP) containing 3 ethylene oxide EO units3AA)4.7g。
The nuclear magnetic resonance hydrogen spectrum data are as follows:
1H NMR(400MHz,CDCl3): δ (ppm)6.9-7.3(3H, hydrogen on phenyl ring), 6.39(1H, hydrogen on double bond C ═ CH)2) 6.13(1H, double bond hydrogen C ═ CH-CO),5.81(1H, double bond hydrogen C ═ CH2) 3.0-4.5(12H, is 3-OCH)2CH2O-),0.5-2.2(18H, is tert-butylhydride).
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is di-tert-butyl phenoxy polyoxyethylene ether acrylate (DPP) containing 3 ethylene oxide EO units3AA)。
Example 3 (method one)
The preparation method is the same as that in the embodiment 1, except that: in step (1) 5.0000g (8.993mmol) 3-ethyl-5-nonylphenoxypolyoxyethylene ether containing 7 ethyleneoxy EO units (n ═ 7), 0.0842g (0.7647mmol) hydroquinone, 0.0693g (0.402mmol) p-toluenesulfonic acid, 1.2961g (17.986mmol) acrylic acid were added.
The yellow oil obtained was 4.83g of 3-ethyl-5-nonylphenoxypolyoxyethylene ether acrylate containing 7 ethyleneoxy EO units.
The nuclear magnetic resonance hydrogen spectrum data are as follows:
1H NMR(400MHz,CDCl3)：δ(ppm)6.9-7.3(3h, hydrogen on the phenyl ring), 6.39(1H, hydrogen on the double bond C ═ CH)2) 6.13(1H, double bond hydrogen C ═ CH-CO),5.81(1H, double bond hydrogen C ═ CH2) 3.0-4.5(28H, 7-OCH2CH2O-),0.5-2.2(24H, alkyl hydrogen on benzene ring).
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is 3-ethyl-5-nonylphenoxy polyoxyethylene ether acrylate containing 7 ethylene oxide EO units.
Example 4 (method two)
(1) 5.0000g (7.740mmol) of di-tert-butylphenoxypolyoxyethylene ether (n ═ 10) containing 10 ethyleneoxy EO units and 1.5600g (15.417mmol) of triethylamine were added to a three-necked flask at 0 ℃ and stirred with 20mL of dichloromethane until dissolved.
(2) And (2) dripping 1.2700g (14.032mmol) of acryloyl chloride into the reaction liquid in the step (1) at the temperature of 0-5 ℃, heating the system to 35 ℃ after dripping is finished, and reacting for 4 hours.
(3) After the reaction is finished, filtering to remove triethylamine hydrochloride in the reaction liquid, then adding saturated sodium sulfate solution to wash the reaction liquid for a plurality of times, and concentrating to obtain yellow oily matter which is di-tert-butylphenol polyoxyethylene ether acrylate (DPP) containing 10 ethylene oxide EO units10AA)4.5g。
The nuclear magnetic resonance hydrogen spectrum data are as follows:
1H NMR(400MHz,CDCl3) Delta (ppm)6.9-7.3(3H, hydrogen on benzene ring), 6.39(1H, hydrogen on double bond C ═ CH)2) 6.13(1H, double bond hydrogen C ═ CH-CO),5.81(1H, double bond hydrogen C ═ CH2) 3.0-4.5(40H, 10-OCH)2CH2O-),0.5-2.2(18H, is tert-butylhydride).
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is di-tert-butylphenol polyoxyethylene ether acrylate containing 10 ethylene oxide EO units.
Example 5 (method two)
The preparation method is the same as that in the embodiment 4, except that: 5.0000g (6.983mmol) of 3-pentyl-5-octylphenoxypolyoxyethylene ether containing 10 ethyleneoxy EO units, 1.2718g (12.569mmol) of triethylamine were added in step (1); 1.2009g (13.268mmol) of acryloyl chloride were added in step (2).
The yellow oil obtained was 4.76g of 3-pentyl-5-octylphenoxypolyoxyethylene ether acrylate containing 10 ethyleneoxy EO units.
The nuclear magnetic resonance hydrogen spectrum data are as follows:
1H NMR(400MHz,CDCl3) Delta (ppm)6.9-7.3(3H, hydrogen on phenyl ring), 6.40(1H, hydrogen on double bond C ═ CH)2) 6.14(1H, double bond hydrogen C ═ CH — CO),5.82(1H, double bond hydrogen C ═ CH2) 3.0-4.5(40H, 10-OCH)2CH2O-),0.5-2.2(28H, alkyl hydrogen on benzene ring).
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is 3-amyl-5-octylphenoxyl polyoxyethylene ether acrylate containing 10 ethylene oxide EO units.
ADVANTAGEOUS EFFECTS OF INVENTION
(1) Interfacial activity test
The interface activity test conditions and steps are as follows: the surface tension of the aqueous solution was measured by the hanging strip method using a K-12 interfacial tensiometer from Kruss, Germany, at an experimental temperature of 25 ℃ and the results are shown in Table 1 below.
TABLE 1
| Surface active agent | Water (W) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Surface tension/mN/m | 72 | 34.5 | 33.6 | 32.8 | 35.3 | 36.2 |
(2) Permeability, wettability test
The permeability is tested according to the chemical industry standard HG/T4027-; the contact angle of a 1% aqueous solution with a wax surface (oil-wet surface) was measured using a contact angle meter model ODG20P from germany deflenberg, and the results are shown in table 2.
TABLE 2
(3) Viscosity reduction test for thickened oils
The monomer prepared in the embodiment 1, monomer acrylic acid and monomer 2-acrylamide-2-methylpropanesulfonic acid are copolymerized under the micelle polymerization condition to obtain a copolymer, and the copolymer can be applied to thick oil exploitation to reduce the viscosity of thick oil.
Mixing heavy oil (Liaohe heavy oil) and water (containing 1000mg/L of the copolymer) in a mass ratio of 4:6, and simulating the low shear rate of the stratum for 5-50s at the temperature of 50 DEG C-1To form a stable oil-in-water emulsion. The viscosity (50 ℃) of the thick oil and oil-in-water emulsion is measured by an MCR301 type modular intelligent rheometer, and the results are shown in the following table 3 (the viscosity of the thick oil is 635 mPa.s).
TABLE 3
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (29)
1. A polymerizable surfactant containing an aromatic hydrocarbon structure, wherein the surfactant has a structure represented by the following formula (I):
R1、R2each independently is one selected from alkyl with 2 to 10 carbon atoms;
n＝3～10。
2. the surfactant of claim 1, wherein R1、R2Each independently selected from propyl, isopropyl, tert-butyl, sec-butyl, isobutyl, n-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 2-methylbutyl, neopentyl, n-hexyl, 1-methylpentyl, 2-ethylbutyl, 4-methylpentyl, 1, 3-dimethylbutyl, 2-methyl-1-ethylpropyl, 1-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, 1-methylpropyl, 1, 2-dimethylpropyl, 1, 2-methylpentyl, 1-methylpentyl, and 1-methylpentylOne of 2-dimethylbutyl, 1-methyl-1-ethylpropyl, 2-ethylbutyl, 3-dimethylbutyl, 1,2, 2-trimethylpropyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 1, 2-trimethylpropyl, heptyl, octyl, nonyl and decyl.
3. A method for preparing the polymerizable surfactant containing the aromatic hydrocarbon structure as claimed in any one of claims 1 to 2, wherein the method comprises the steps of taking the aromatic hydrocarbon polyoxyethylene ether shown as the formula (II) as a raw material, and reacting the aromatic hydrocarbon polyoxyethylene ether with acrylic acid in a solvent in the presence of a catalyst and a polymerization inhibitor to obtain the surfactant; or comprises that aromatic alkyl polyethenoxy ether shown in formula (II) is used as raw material, and reacts in solvent in the presence of acid-binding agent and acryloyl chloride to obtain the surfactant;
R1、R2the same as defined in claim 1 or 2, wherein n is 3 to 10.
4. A method according to claim 3, wherein the method comprises the steps of:
(a1) aromatic polyoxyethylene ether is used as a raw material and reacts with acrylic acid in a solvent in the presence of a catalyst and a polymerization inhibitor;
(a2) after the reaction is finished, washing the reaction solution obtained in the step (a1) by using a 1-10 wt% sodium bicarbonate solution and a saturated sodium chloride solution, and concentrating to obtain the surfactant;
alternatively, the method comprises the steps of:
(b1) dissolving aromatic polyoxyethylene ether and an acid-binding agent in a solvent to obtain a mixed solution;
(b2) dropwise adding acryloyl chloride into the mixed solution obtained in the step (b1), and heating for reaction after dropwise adding is finished;
(b3) and (b2) washing the reaction solution obtained in the step (b2) with a saturated sodium sulfate solution, and concentrating to obtain the surfactant.
5. A method according to claim 3, wherein the method comprises the steps of:
(a1) adding aryl polyoxyethylene ether and a solvent into a reaction device with a water separator, stirring and dissolving, then adding a catalyst and a polymerization inhibitor, stirring and dissolving, finally adding acrylic acid, and heating for reaction;
(a2) after the reaction is finished, washing the reaction solution obtained in the step (a1) by using a 1-10 wt% sodium bicarbonate solution and a saturated sodium chloride solution, and concentrating to obtain the surfactant;
alternatively, the method comprises the steps of:
(b1) adding aromatic polyoxyethylene ether, an acid-binding agent and a solvent into a reaction device, and stirring at low temperature until the aromatic polyoxyethylene ether, the acid-binding agent and the solvent are dissolved to obtain a mixed solution;
(b2) dropwise adding acryloyl chloride into the mixed solution obtained in the step (b1), heating the system after dropwise adding is finished, and keeping the temperature until the reaction is finished;
(b3) and (b2) washing the reaction solution obtained in the step (b2) with a saturated sodium sulfate solution, and concentrating to obtain the surfactant.
6. A process according to any one of claims 3 to 5, wherein the solvent for preparing the surfactant in the presence of the catalyst and the inhibitor is selected from a mixture of one or more of toluene, benzene and p-xylene; the solvent for preparing the surfactant in the presence of the acid-binding agent and the acryloyl chloride is one or a mixture of more of dichloromethane, chloroform, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, cyclohexane and carbon tetrachloride.
7. The process according to claim 6, wherein the solvent for preparing the surfactant in the presence of the catalyst and the polymerization inhibitor is toluene; the solvent for preparing the surfactant in the presence of the acid-binding agent and the acryloyl chloride is dichloromethane.
8. A process according to any one of claims 3 to 5 wherein the catalyst is selected from a mixture of one or more of p-toluenesulphonic acid, phosphoric acid, sulphuric acid and hydrochloric acid.
9. The process of claim 8, wherein the catalyst is p-toluenesulfonic acid.
10. The method according to any one of claims 3 to 5, wherein the mass amount of the catalyst is 0.5 to 2.5 percent of the total mass amount of the aromatic polyoxyethylene ether and the acrylic acid.
11. The method according to claim 10, wherein the mass amount of the catalyst is 1-2% of the total mass amount of the aromatic polyoxyethylene ether and the acrylic acid.
12. The method according to any one of claims 3 to 5, wherein the polymerization inhibitor is one or more selected from hydroquinone, p-benzoquinone, phenothiazine, beta-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, cuprous chloride and ferric chloride.
13. The method of claim 12, wherein the polymerization inhibitor is hydroquinone.
14. A process according to any one of claims 3 to 5, wherein the amount of the polymerization inhibitor is 5 to 9% by mass based on the mass of acrylic acid.
15. The method according to claim 14, wherein the amount of the polymerization inhibitor is 6 to 8% by mass based on the mass of acrylic acid.
16. The method according to any one of claims 3 to 5, wherein the mass ratio of acrylic acid to the aromatic polyoxyethylene ether is 1 to 4: 1.
17. The method according to claim 16, wherein the mass ratio of acrylic acid to aralkyl polyoxyethylene ether is 1.5-2.2: 1.
18. A process according to any one of claims 3 to 5, wherein the reaction temperature for preparing the surfactant in the presence of the catalyst and the polymerization inhibitor is from 80 to 150 ℃.
19. The method according to claim 18, wherein the reaction temperature for preparing the surfactant in the presence of the catalyst and the polymerization inhibitor is 115 to 130 ℃.
20. The method of any one of claims 3 to 5, wherein the acid scavenger is selected from one or more of trimethylamine, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate and sodium carbonate.
21. The method of claim 20, wherein the acid scavenger is triethylamine.
22. A process as claimed in any one of claims 3 to 5, wherein the mass ratio of triethylamine to aryl polyoxyethylene ether is 0.5 to 2.5: 1.
23. The method of claim 22, wherein the mass ratio of triethylamine to aryl polyoxyethylene ether is 1.7-2.2: 1.
24. The method according to claim 5, wherein the step (b1) comprises adding the aromatic polyoxyethylene ether, the acid-binding agent and the solvent into a reaction device, and stirring at-5-10 ℃ until the aromatic polyoxyethylene ether, the acid-binding agent and the solvent are dissolved.
25. The method according to claim 5, wherein the step (b1) comprises adding the aromatic polyoxyethylene ether, the acid-binding agent and the solvent into a reaction device, and stirring at 0-5 ℃ until the aromatic polyoxyethylene ether, the acid-binding agent and the solvent are dissolved.
26. The method according to any one of claims 3 to 5, wherein the mass ratio of acryloyl chloride to aromatic polyoxyethylene ether is 1 to 3: 1.
27. The method according to claim 26, wherein the mass ratio of acryloyl chloride to aryl polyoxyethylene ether is 1.8-2.2: 1.
28. The method according to any one of claims 4 to 5, wherein the step (b2) comprises adding acryloyl chloride dropwise to the mixed solution of the step (b1), heating the system to 30 to 50 ℃ after the dropwise addition is completed, and then carrying out the reaction under heat preservation.
29. The method according to claim 28, wherein the step (b2) comprises the steps of dropwise adding acryloyl chloride into the mixed solution obtained in the step (b1), heating the system to 35-45 ℃ after the dropwise adding is finished, and then carrying out heat preservation for reaction.
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