A surfactant, its preparation method and use in oil displacement

Abstract

The application relates to the technical field of petroleum chemical industry, and provides a surfactant, a preparation method thereof and application of the surfactant in oil displacement. The structural formula of the surfactant provided by the application is shown as formula I. Compared with traditional double alkyl double quaternary ammonium salt cationic surfactants, the surfactant provided by the application has sulfonic acid groups at two ends, the molecular structure of the sulfonic acid group amphiphilic hydrophilic group endows the surfactant with better temperature resistance and salt resistance and better water solubility, an oil displacement system formed by the surfactant can reduce the crude oil / formation water interfacial tension to ultra-low under an alkali-free condition; and the oil displacement system has strong oil displacement capacity at a low concentration, is resistant to high formation temperature, and performs excellently in a heavy oil and high salinity environment.

Description

Technical Field

[0001] This invention relates to the field of petrochemical technology, and in particular to a surfactant, its preparation method, and its application in oil displacement. Background Technology

[0002] The main principle of surfactant-assisted enhanced oil recovery (EOR) technology is to use surfactants to reduce the interfacial tension between injected water and residual oil in the formation, thereby displacing the residual oil and improving oil recovery. Surfactant-assisted EOR is one of the most promising technologies and has been widely applied in my country.

[0003] Currently, anionic surfactants are most commonly used in tertiary oil recovery studies, especially sulfonate surfactants, with petroleum sulfonates being the most prevalent. Petroleum sulfonates offer advantages such as low cost, high interfacial activity, and good temperature resistance; however, they have poor salt resistance and a high critical micelle concentration (CMC). They are easily depleted through adsorption, stagnation, and interaction with multivalent ions in the formation, thus requiring higher concentrations for their use. Furthermore, these surfactants generally cannot reduce the crude oil / formation water interfacial tension to ultra-low levels under alkali-free conditions, and the use of alkali will bring a series of side effects to the formation. Summary of the Invention

[0004] In view of this, the present invention provides a surfactant, a method for preparing the same, and its application in oil displacement. The surfactant provided by the present invention has a strong oil displacement ability at low concentrations and can reduce the interfacial tension between crude oil and formation water to ultra-low levels under alkali-free conditions.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] A surfactant having the structure shown in Formula I:

[0007]

[0008] In formula I: R=Na, K, m=1~3, n=1~22.

[0009] The present invention also provides a method for preparing the surfactant described in the above-described scheme, comprising the following steps:

[0010] A reduction reaction is carried out by mixing a terminal hydroxyl diol, epichlorohydrin, and a Lewis acid catalyst to obtain a chlorinated polyether. The structural formula of the chlorinated polyether is shown in Formula II. The terminal hydroxyl diol is ethylene glycol, 1,3-propanediol, or 1,4-butanediol.

[0011]

[0012] The chlorinated polyether is subjected to a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated chlorinated polyether; the structural formula of the sulfonated chlorinated polyether is shown in Formula III:

[0013]

[0014] The sulfonated chlorinated polyether, long-chain aliphatic tertiary amine, organic solvent and base are mixed and subjected to a quaternization reaction to obtain a surfactant with the structure shown in Formula I; the structural formula of the long-chain aliphatic tertiary amine is shown in Formula IV.

[0015]

[0016] Preferably, the molar ratio of the terminal hydroxyl diol to epichlorohydrin is 1:(1-4).

[0017] Preferably, the Lewis acid catalyst is one or more selected from triisobutylaluminum, aluminum trichloride, boron trifluoride diethyl ether, and phosphoric acid; the amount of the Lewis acid catalyst is 0.1 to 0.8% of the mass of epichlorohydrin.

[0018] Preferably, the ring-opening reaction temperature is 30–80°C, the epichlorohydrin is added dropwise, the dropwise addition time is 2–8 hours, and the reaction is continued at the temperature for 2–6 hours after the dropwise addition is completed.

[0019] Preferably, the molar ratio of the chlorinated polyether to chlorosulfonic acid is 1:(1-4); the sulfonation reaction temperature is 30-50°C; the chlorosulfonic acid is added dropwise over a period of 2-8 hours; and the reaction is continued at this temperature for 2-6 hours after the addition is complete.

[0020] Preferably, the alkali comprises one or more of alkali metal carbonates and alkali metal hydroxides; the amount of alkali used is 15-45% of the mass of the chlorinated polyether.

[0021] Preferably, the molar ratio of the sulfonated chlorinated polyether to the long-chain aliphatic tertiary amine is 1:(1-4).

[0022] Preferably, the quaternization reaction is carried out at a temperature of 60–100°C for a time of 8–48 h.

[0023] The present invention also provides the application of the surfactant described in the above-described scheme or the surfactant prepared by the preparation method described in the above-described scheme in oil displacement.

[0024] This invention provides a surfactant with the structural formula shown in Formula I. Compared with traditional dialkyl bisquaternary ammonium cationic surfactants, the surfactant provided by this invention has sulfonic acid groups at both ends. The molecular structure of the sulfonic acid groups with amphiphilic properties endows the surfactant with better temperature and salt resistance as well as better water solubility. The resulting oil displacement system can reduce the interfacial tension of crude oil / formation water to ultra-low under alkali-free conditions; and it has strong oil displacement ability at low concentrations, resistance to high formation temperatures, and excellent performance in heavy oil and high salinity environments. Detailed Implementation

[0025] This invention provides a surfactant having the structure shown in Formula I:

[0026]

[0027] In formula I: R=Na, K, m=1~3, n=1~22.

[0028] In this invention, m is specifically 1, 2 or 3, and n is preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22.

[0029] The present invention also provides a method for preparing the surfactant described in the above-described scheme, comprising the following steps:

[0030] A reduction reaction is carried out by mixing a terminal hydroxyl diol, epichlorohydrin, and a Lewis acid catalyst to obtain a chlorinated polyether. The structural formula of the chlorinated polyether is shown in Formula II. The terminal hydroxyl diol is ethylene glycol, 1,3-propanediol, or 1,4-butanediol.

[0031]

[0032] The chlorinated polyether is subjected to a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated chlorinated polyether; the structural formula of the sulfonated chlorinated polyether is shown in Formula III:

[0033]

[0034] The sulfonated chlorinated polyether, long-chain aliphatic tertiary amine, organic solvent and base are mixed and subjected to a quaternization reaction to obtain a surfactant with the structure shown in Formula I; the structural formula of the long-chain aliphatic tertiary amine is shown in Formula IV.

[0035]

[0036] In this invention, the range of values ​​for m in formulas II and III is the same as that in formula I, and the range of values ​​for n in formula IV is the same as that in formula I.

[0037] This invention involves a reduction reaction of a terminal hydroxyl diol, epichlorohydrin, and a Lewis acid catalyst to obtain a chloropolyether. In this invention, the terminal hydroxyl diol is ethylene glycol, 1,3-propanediol, or 1,4-butanediol; the molar ratio of the terminal hydroxyl diol to epichlorohydrin is preferably 1:(1-4), more preferably 1:(1-2.5), and even more preferably 1:2; the Lewis acid catalyst is preferably one or more of triisobutylaluminum, aluminum trichloride, boron trifluoride diethyl ether, and phosphoric acid; and the amount of the Lewis acid catalyst is preferably 0.1-0.8% of the mass of epichlorohydrin.

[0038] In this invention, the ring-opening reaction temperature is preferably 30–80°C, more preferably 40–70°C; the epichlorohydrin is preferably added dropwise, and the dropwise addition time is preferably 2–8 hours, more preferably 3–7 hours. After the dropwise addition is completed, the reaction is preferably continued at the temperature for 2–6 hours, more preferably 3–5 hours. In a specific embodiment of this invention, the terminal hydroxyl diol and Lewis acid catalyst are preferably mixed first, and then the temperature is controlled at 30–80°C, and epichlorohydrin is added dropwise under stirring. After the dropwise addition is completed, the reaction is continued at the temperature.

[0039] The ring-opening reaction of this invention is carried out under anhydrous conditions. During the cationic ring-opening polymerization of epichlorohydrin and terminal hydroxyl diol catalyzed by a Lewis acid catalyst, a low molecular weight polymer is generally obtained under aqueous conditions. Under anhydrous conditions, epichlorohydrin ring-opens and forms a chloropolyether with hydroxyl groups, yielding the product almost quantitatively. When the molar ratio of epichlorohydrin to terminal hydroxyl diol is 2:1, the reaction formula is as follows:

[0040]

[0041] After the ring-opening reaction is completed, the residual Lewis acid catalyst in the system has no effect on the subsequent chlorosulfonation reaction and no treatment is required; the subsequent reaction can proceed directly.

[0042] After obtaining the chlorinated polyether, the present invention performs a sulfonation reaction between the chlorinated polyether and chlorosulfonic acid to obtain sulfonated chlorinated polyether. In the present invention, the molar ratio of the chlorinated polyether to chlorosulfonic acid is preferably 1:(1-4), more preferably 1:(1-2.5), and even more preferably 1:2; the temperature of the sulfonation reaction is preferably 30-50°C, more preferably 35-45°C; the chlorosulfonic acid is preferably added dropwise, and the dropwise addition time is preferably 2-8 hours, more preferably 3-7 hours; after the dropwise addition is completed, the reaction is preferably continued for 2-6 hours, preferably 3-5 hours. In a specific embodiment of the present invention, the chlorinated polyether product solution obtained by the ring-opening reaction is preferably first added to the reaction vessel, and then the temperature is controlled at 30-50°C, and the chlorinated polyether is added dropwise under stirring conditions.

[0043] In this invention, the reaction formula for the sulfonation reaction is as follows:

[0044]

[0045] After the sulfonation reaction is complete, the generated hydrogen chloride gas is removed by depressurization, and then subsequent reactions can be carried out directly.

[0046] After obtaining the sulfonated chlorinated polyether, the present invention mixes the sulfonated chlorinated polyether, a long-chain aliphatic tertiary amine, an organic solvent, and a base to carry out a quaternization reaction to obtain a surfactant having the structure shown in Formula I. In the present invention, the long-chain aliphatic tertiary amine is preferably one of tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, and docosyl dimethyl tertiary amine; the molar ratio of the sulfonated chlorinated polyether to the long-chain aliphatic tertiary amine is 1:(1-4), more preferably 1:(2-2.5), and even more preferably 1:2. In the present invention, the base preferably includes one or more of alkali metal carbonates and alkali metal hydroxides; the alkali metal carbonate is preferably potassium carbonate or sodium carbonate; the alkali metal hydroxide is preferably potassium hydroxide or sodium hydroxide; the amount of base is preferably 15-45% of the mass of the chlorinated polyether, more preferably 15-35%; the organic solvent preferably includes one or two of anhydrous ethanol, dichloromethane, dichloroethane, and ethyl acetate; the mass of the organic solvent is preferably 30-100% of the mass of the long-chain aliphatic tertiary amine.

[0047] In this invention, the temperature of the quaternization reaction is preferably 60–100°C, more preferably 70–90°C. In a specific embodiment of this invention, the quaternization reaction is preferably carried out under reflux conditions. The time of the quaternization reaction is preferably 8–48 h, more preferably 12–24 h. In a specific embodiment of this invention, it is preferred to take samples for testing during the reaction process, and the reaction can be terminated when the degree of quaternization is greater than 95%. In a specific embodiment of this invention, it is preferred to first add the product liquid obtained from the sulfonation reaction to the reaction vessel, then add an organic solvent, control the temperature at 30–40°C, add the alkali in batches, then add the long-chain aliphatic tertiary amine, and raise the temperature to the temperature of the quaternization reaction for the reaction.

[0048] In this invention, the reaction formula for the quaternization reaction is as follows:

[0049]

[0050] In the formula: R=Na, K

[0051] In this invention, no separation and purification process is required after the quaternization reaction is completed; the solid content of the product liquid obtained by the quaternization reaction is usually 55-85%, and this invention preferably prepares a product with a solid content of 50% by adding water.

[0052] This invention also provides the application of the surfactant described in the above-described scheme or the surfactant prepared by the above-described preparation method in oil displacement. This invention does not have special requirements for the specific operating method of the application; methods well known to those skilled in the art can be used. In a specific embodiment of this invention, it is preferable to prepare the surfactant of this invention into an aqueous solution and then inject it into the oil layer for oil displacement; the mass fraction of the aqueous solution of the surfactant is preferably 0.1–1.0%, more preferably 0.1–0.6%.

[0053] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0054] Example 1

[0055] In a dry and clean reaction vessel, add 62g of ethylene glycol and 1g of boron trifluoride ether. Start the stirrer and add 185g of epichlorohydrin dropwise. Control the temperature at 50℃~70℃ and the dropwise addition time is 4h. After the dropwise addition is completed, keep the temperature at 70℃ for 3h to obtain 247.5g of chlorinated polyether with hydroxyl groups at both ends.

[0056] In a dry and clean reaction vessel, add 247g of the chlorinated polyether obtained in the previous step, start the stirrer, add 233g of chlorosulfonic acid dropwise, control the temperature at 30℃~40℃, and add for 3 hours. After the addition is complete, keep at 40℃ for 3 hours, and remove the generated hydrogen chloride gas under reduced pressure to obtain 407g of chlorinated polyether with sulfonic acid groups at both ends.

[0057] In a dry and clean reactor, add 203.5g of the sulfonated chlorinated polyether obtained in the previous step and 300g of anhydrous ethanol. Attach a reflux condenser, start the stirrer, and add 40g of sodium hydroxide in batches. Control the temperature at 30℃~40℃ and the batching time is 2h. After the batching is complete, add 310g of octadecyl dimethyl tertiary amine (96%), raise the temperature to 80℃, and reflux at 80℃ for 24h. Take a sample and test the degree of quaternization to be greater than 95%, which yields the surfactant for oil displacement. Add 257g of water to prepare a 50% solids content solution.

[0058] Example 2

[0059] In a dry and clean reactor, add 76.1g of 1,3-propanediol and 1g of boron trifluoride ether. Start the stirrer and add 185g of epichlorohydrin dropwise. Control the temperature at 50℃~70℃ and the dropwise addition time is 4h. After the dropwise addition is completed, keep the temperature at 70℃ for 3h to obtain 261.4g of chlorinated polyether with hydroxyl groups at both ends.

[0060] In a dry and clean reactor, add 261g of the chlorinated polyether obtained in the previous step, start the stirrer, add 233g of chlorosulfonic acid dropwise, control the temperature at 30℃~40℃, and add for 3 hours. After the addition is complete, keep at 40℃ for 3 hours, and remove the generated hydrogen chloride gas under reduced pressure to obtain 421g of chlorinated polyether with sulfonic acid groups at both ends.

[0061] In a dry and clean reactor, add 210.5g of the sulfonated chlorinated polyether obtained in the previous step and 300g of anhydrous ethanol. Attach a reflux condenser, start the stirrer, and add 40g of sodium hydroxide in batches. Control the temperature at 30℃~40℃ and the batching time is 2h. After the batching is complete, add 310g of octadecyl dimethyl tertiary amine (96%), raise the temperature to 80℃, and reflux at 80℃ for 24h. Take a sample and test the degree of quaternization to be greater than 95%, which yields the surfactant for oil displacement. Add 264.6g of water to prepare a 50% solids content solution.

[0062] Example 3

[0063] In a dry and clean reactor, add 62g of ethylene glycol and 1g of boron trifluoride ether. Start the stirrer and add 185g of epichlorohydrin dropwise. Control the temperature at 50℃~70℃ and the dropwise addition time is 4h. After the dropwise addition is completed, keep it at 70℃ for 3h to obtain 247.5g of chlorinated polyether with hydroxyl groups at both ends.

[0064] In a dry and clean reactor, add 247g of the chlorinated polyether obtained in the previous step, start the stirrer, add 233g of chlorosulfonic acid dropwise, control the temperature at 30℃~40℃, and add for 3 hours. After the addition is complete, keep the temperature at 40℃ for 3 hours, and remove the generated hydrogen chloride gas under reduced pressure to obtain 407g of chlorinated polyether with sulfonic acid groups at both ends.

[0065] In a dry and clean reactor, add 203.5g of the sulfonated chlorinated polyether obtained in the previous step and 300g of anhydrous ethanol. Attach a reflux condenser, start the stirrer, and add 40g of sodium hydroxide in batches. Control the temperature at 30℃~40℃ and the batching time is 2h. After the batching is complete, add 364.6g of docosyldimethyl tertiary amine (97%), raise the temperature to 80℃, and reflux at 80℃ for 24h. Take a sample and test the degree of quaternization to be greater than 95%, which yields the surfactant for oil displacement. Add 312g of water to prepare a 50% solids content solution.

[0066] Test case

[0067] (1) Solubility test

[0068] At a given temperature, the maximum solubility of a surfactant in water is expressed as a mass percentage. This is usually represented by the Krafft point. The Krafft point of a surfactant is determined using the turbidimetric method. A 0.2% surfactant solution is prepared in water, and the temperature at which the solution suddenly changes from cloudy to clear is observed and recorded; this temperature is the Krafft point. The test results are shown in Table 1.

[0069] Table 1. Results of Kraf's Characteristic Measurement

[0070] project Reference sample Example 1 Example 2 Example 3 Kraf Features KP 28 8 10 6

[0071] Note: The reference sample is a commonly used alkyl sulfonate.

[0072] As can be seen from the data in Table 1, compared with the reference sample, the surfactants prepared in Examples 1-3 of this invention have significantly lower Kraft characteristics, indicating that they have lower critical dissolution temperatures and better solubility.

[0073] (2) Foam performance test

[0074] The Ross-Miles method was adopted, and the specific test procedures were performed in accordance with the provisions of section 11 of GB / T 13173-2008. At 60℃, the initial foam height and the foam height at 5 minutes were measured as measures of foaming power and foam-stabilizing power.

[0075] A. Preparation of test solution:

[0076] a. Preparation of 30% petroleum ether test solution: Measure 75 mL of petroleum ether and add distilled water to a 250 mL volumetric flask to prepare a 30% petroleum ether test solution. The petroleum ether test solution should be thoroughly stirred or shaken before transfer. (Because petroleum ether is insoluble in water, only one test volume should be prepared at a time).

[0077] b. Preparation of 250g / L mineralized water test solution: Weigh 50.0g calcium chloride and 200.0g sodium chloride, accurate to 0.1g, dissolve them in distilled water in a 500mL beaker and stir with a glass rod until completely dissolved. Transfer the entire solution to a 1000mL volumetric flask and make up to volume to prepare a 250g / L mineralized water test solution.

[0078] c. Preparation of a 20% methanol test solution: Measure 200 mL of methanol, transfer it to a 1000 mL volumetric flask, and dilute to volume with distilled water to prepare a 20% methanol test solution.

[0079] B. Sample preparation:

[0080] Preparation of oil-resistant sample: Weigh 1.25 g (based on the mass of the surfactant solution) of the oil displacement surfactant sample, accurate to 0.01 g, and add it to a 250 mL volumetric flask of 30% petroleum ether solution to prepare the sample. Place the prepared sample in a constant temperature water bath at 60 ± 0.5 °C for aging. The total time from the start of adding the test solution to dissolve the sample is 30 min.

[0081] Salt-resistant samples were prepared using 250 g / L mineralized water solution, and methanol-resistant samples were prepared using 20% ​​methanol solution. The sample preparation methods were the same as above.

[0082] The test results are shown in Table 2.

[0083] Table 2 Foam Performance Test Results

[0084]

[0085] Note: The reference sample is a commonly used alkyl aryl sulfonate with an active ingredient content of 40%.

[0086] As can be seen from the data in Table 2, compared with the reference sample, the samples prepared using the surfactants obtained in Examples 1 to 3 of this invention have higher initial foam height and higher foam height after 5 minutes, indicating that they have better resistance to oil, salt and methanol.

[0087] (3) Interfacial tension measurement

[0088] The surface tension of the surfactant solution at 25°C was determined using the rotating drop method.

[0089] Referring to the People's Republic of China Petroleum and Natural Gas Industry Standard SY / T5370—1999 "Methods for Determination of Surface and Interfacial Tension", the oil used in the experiment was Changqing crude oil with a density of 848.3 kg / m³. 3 Its kinematic viscosity at 50℃ is 27.04 mm² / s, its freezing point is 18–25℃, and its wax content is 10.5%, gum content is 6.5%, and asphaltene content is 2.95%.

[0090] Oil displacement surfactant solutions with mass fractions of 0.1%, 0.2%, 0.3%, and 0.5% were prepared. The interfacial tension between Changqing crude oil and the oil displacement surfactant solutions with different mass fractions was measured. The interfacial tension test results are shown in Table 3.

[0091] Table 3 Results of interfacial tension measurement

[0092]

[0093] Note: The reference sample is a commonly used alkyl aryl sulfonate.

[0094] As can be seen from the data in Table 3, the interfacial tension of the sample prepared with the surfactant of the present invention is lower than that of the reference sample. This indicates that the surfactant of the present invention has a strong oil displacement ability at low concentrations and can reduce the interfacial tension of crude oil / formation water to an ultra-low level under alkali-free conditions.

[0095] (4) Temperature and salt resistance test

[0096] Preparation of base solution: Weigh 484g of tap water and place it in a 1000mL beaker. Add 2.0g of polyacrylamide slowly to the tap water while stirring. After stirring for 5 minutes, add 16.0g of potassium chloride and stir until dissolved.

[0097] Weigh 0.5g of sodium salicylate aqueous solution (10wt%) and add it to the base solution, and continue stirring for 15min.

[0098] Weigh 4.0 g of the surfactant prepared in Example 3, add it to the base solution, stir for 15 min, and measure the viscosity at 170 s using a Brookfield DV-II rotational viscometer. -1 The viscosity changes with temperature when the temperature rises from 20℃ to 150℃ under shear conditions, as shown in Table 4.

[0099] Table 4 Viscosity data at different temperatures

[0100] Temperature (°C) 20 40 60 80 100 120 140 150 Viscosity (cps) 450 505 565 435 235 102.5 60 42.5

[0101] As shown in Table 4, the viscosity of the sample reaches its maximum at approximately 60°C, because at this temperature, it disperses in water to form more dense worm-like micelles. The viscosity remains greater than 100 cps at 120°C, indicating that the surfactant of this invention has good temperature and salt resistance.

[0102] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a surfactant, characterized in that, The surfactant has the structure shown in Formula I: Formula I; In Formula I: R is Na or K, m = 1~3, n = 1~22; The preparation method of this surfactant includes the following steps: A ring-opening reaction is carried out by mixing a terminal hydroxyl diol, epichlorohydrin and a Lewis acid catalyst to obtain a chlorinated polyether, the structural formula of which is shown in Formula II: the terminal hydroxyl diol is ethylene glycol, 1,3-propanediol or 1,4-butanediol. Formula II; The chlorinated polyether is subjected to a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated chlorinated polyether; the structural formula of the sulfonated chlorinated polyether is shown in Formula III: Formula III; The sulfonated chlorinated polyether, long-chain aliphatic tertiary amine, organic solvent and base are mixed and subjected to a quaternization reaction to obtain a surfactant with the structure shown in Formula I; the structural formula of the long-chain aliphatic tertiary amine is shown in Formula IV. Formula IV.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the terminal hydroxyl diol to epichlorohydrin is 1:(1~4).

3. The preparation method according to claim 1, characterized in that, The Lewis acid catalyst is boron trifluoride diethyl ether; the amount of the Lewis acid catalyst is 0.1~0.8% of the mass of epichlorohydrin.

4. The preparation method according to claim 1, characterized in that, The ring-opening reaction is carried out at a temperature of 30-80°C. The epichlorohydrin is added dropwise over a period of 2-8 hours. After the addition is complete, the reaction is continued at the temperature for another 2-6 hours.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the chlorinated polyether to chlorosulfonic acid is 1:(1~4); the sulfonation reaction temperature is 30~50℃; the chlorosulfonic acid is added dropwise over a period of 2~8 hours; and the reaction is continued at this temperature for 2~6 hours after the addition is complete.

6. The preparation method according to claim 1, characterized in that, The alkali is an alkali metal hydroxide; the amount of alkali used is 1‰ to 5% of the mass of the chlorinated polyether.

7. The preparation method according to claim 1, characterized in that, The molar ratio of the sulfonated chlorinated polyether to the long-chain aliphatic tertiary amine is 1:(1~4).

8. The preparation method according to claim 1, characterized in that, The quaternization reaction is carried out at a temperature of 60~100℃ for a time of 8~48h.

Images