阅读说明：本技术 一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法 (Synthesis method of alkyl polyoxyethylene ether quaternary ammonium salt surfactant ) 是由 肖胜志 李国利 王志强 王宗文 刘平 冯超 刘玉君 于 2021-10-20 设计创作，主要内容包括：本发明涉及一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,其特征在于,先制备烯丙基聚氧乙烯醚,然后合成溴丙基聚氧乙烯醚,最终制得烷基聚氧乙烯醚季铵盐。本发明产品具有复配能力强、界面活性高、硬水中易分散的特点。本发明产品具有优良的乳化、润湿性能,在酸碱及高盐环境中不受影响,适合油田酸化、钻井、注水、稠油降粘等作业施工中使用。(The invention relates to a synthesis method of an alkyl polyoxyethylene ether quaternary ammonium surfactant, which is characterized in that firstly, allyl polyoxyethylene ether is prepared, then, bromopropyl polyoxyethylene ether is synthesized, and finally, the alkyl polyoxyethylene ether quaternary ammonium salt is prepared. The product of the invention has the characteristics of strong compounding capability, high interfacial activity and easy dispersion in hard water. The product of the invention has excellent emulsification and wetting properties, is not influenced in acid-base and high-salt environments, and is suitable for operation and construction such as oil field acidification, well drilling, water injection, thick oil viscosity reduction and the like.)

1. A synthetic method of an alkyl polyoxyethylene ether quaternary ammonium surfactant is characterized by comprising the following steps:

1) preparation of allyl Polyoxyethylene Ether

Adding allyl alcohol and a catalyst potassium hydroxide into a stainless steel reaction kettle, introducing nitrogen for replacement for 5min, starting stirring, setting the rotating speed to be 300r/min, setting the reaction temperature to be 130-135 ℃, starting a feed pump when the temperature in the kettle is stabilized at the set temperature, injecting ethylene oxide into the reaction kettle, keeping the mass ratio of the ethylene oxide to the allyl alcohol to be 2-5: 1, keeping the temperature to be 130-135 ℃, reacting for 5-6 h, and cooling to 30 ℃ to obtain allyl polyoxyethylene ether; the mass ratio of the propylene alcohol to the potassium hydroxide is 99.5-99.9: 0.1-0.5;

2) preparation of bromopropyl polyoxyethylene ether ethanol solution

Adding a 45% hydrobromic acid aqueous solution, allyl polyoxyethylene ether and ethanol into a three-neck flask according to a mass ratio of 1: 2-5; installing a reflux condenser pipe, and starting cold water; starting electric stirring, wherein the rotating speed is 200r/min, reacting for 1-1.5 h at the temperature of 20-30 ℃, heating to 80 ℃, and performing reflux reaction for 1-2 h to obtain a bromopropyl polyoxyethylene ether ethanol solution;

3) preparation of alkyl polyoxyethylene ether quaternary ammonium salt

Adding dodecatetradecyl dimethyl tertiary amine or hexadecadecyl tertiary amine, bromopropyl polyoxyethylene ether ethanol solution and water into a three-neck flask according to the mass ratio of 1: 2-7: 1-5, installing a reflux condenser pipe, and opening cold water; starting electric stirring, and setting the rotating speed to be 200 r/min; carrying out reflux reaction for 4-6 h at the temperature of 80 ℃, and adding NaOH aqueous solution to adjust the pH to 7.5-8 when the pH of the material is 6-6.5; raising the reaction temperature to 105 ℃, and carrying out reflux reaction for 4 hours to obtain the alkyl dimethyl polyoxyethylene ether quaternary ammonium salt.

2. The method for synthesizing the alkyl polyoxyethylene ether quaternary ammonium surfactant according to claim 1, wherein the heating in the step 1) is performed to a temperature of 130-135 ℃; and the temperature is reduced to 30-50 ℃.

3. The method for synthesizing alkyl polyoxyethylene ether quaternary ammonium salt surfactant according to claim 1, wherein the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 32%.

Technical Field

The invention relates to a synthesis method of an alkyl polyoxyethylene ether quaternary ammonium surfactant.

Background

The cationic surfactant is a surfactant widely used in the fields of daily chemicals, oilfield chemistry and industrial cleaning.

In the fields of daily chemicals and industrial cleaning, the cationic surfactant has excellent performances of decontamination, sterilization, air bubble and the like, and can also make fabrics soft and elastic, so the cationic surfactant is widely used in products such as fabric softeners, shampoos, hair conditioners, sterilization hand washing solutions and the like. However, the cationic surfactant cannot be used in combination with anionic surfactants such as sodium dodecylbenzene sulfonate, sodium fatty acid methyl ester sulfonate and fatty acid soap, which are used in the largest amount, during the use process, so that the use amount and the performance of the cationic surfactant in daily chemicals are limited to a great extent.

In the field of oilfield chemistry, the cationic surfactant can generate interfacial reaction with colloid and asphaltene in crude oil, so that the cationic surfactant has good capabilities of reducing interfacial tension, reducing emulsification viscosity, washing oil, displacing oil and the like, and has a good application prospect. However, the cationic surfactant is easy to react with a polymer (partially hydrolyzed polyacrylamide) for oil displacement, so that the viscosity of the polymer is reduced, and the cationic surfactant cannot be used in binary composite flooding of an oil field; the surface of the stratum rock is electronegative, and the cationic surfactant is easily adsorbed on the surface of the rock, so that the cationic surfactant is ineffective, and therefore, the cationic surfactant cannot be used under most working conditions; the cationic surfactant cannot be compounded with anionic surfactants such as sodium dodecyl benzene sulfonate, heavy alkyl benzene sulfonic acid, petroleum sulfonate and the like which are commonly used in oilfield chemical flooding.

Based on the problems of the cationic surfactant in the using process, the invention develops the quaternary ammonium salt cationic surfactant containing the polyoxyethylene ether structure, and polyoxyethylene ether with a certain degree of polymerization is grafted on the tail part of the conventional quaternary ammonium salt surfactant through chemical reaction, so that the hydrophilicity of the quaternary ammonium salt cationic surfactant is improved, the charge strength of a positive center of the quaternary ammonium salt cationic surfactant is reduced, and the steric hindrance strength of the reaction of the positive center of the quaternary ammonium salt cationic surfactant and other anionic surfactants is improved.

The anionic surfactant can be compounded with the anionic surfactant, the hard water resistance of the anionic surfactant is improved, and the adsorption quantity of the anionic surfactant and stratum rock in the chemical flooding process of an oil field is reduced, so that the application range of the anionic surfactant is widened.

Disclosure of Invention

The invention aims to provide a synthesis method of an alkyl polyoxyethylene ether quaternary ammonium surfactant, and the product prepared by the method has the characteristics of strong compounding capability, high interfacial activity and easy dispersion in hard water.

In order to solve the technical problems, the invention adopts the following technical scheme:

a method for synthesizing alkyl polyoxyethylene ether quaternary ammonium surfactant comprises the following steps:

1) preparation of allyl Polyoxyethylene Ether

Adding allyl alcohol and a catalyst potassium hydroxide into a stainless steel reaction kettle, introducing nitrogen for replacement for 5min, starting stirring, setting the rotating speed to be 300r/min, setting the reaction temperature to be 130-135 ℃, starting a feed pump when the temperature in the kettle is stabilized at the set temperature, injecting ethylene oxide into the reaction kettle, keeping the mass ratio of the ethylene oxide to the allyl alcohol to be 2-5: 1, keeping the temperature to be 130-135 ℃, reacting for 5-6 h, and cooling to 30 ℃ to obtain allyl polyoxyethylene ether; the mass ratio of the propylene alcohol to the potassium hydroxide is 99.5-99.9: 0.1-0.5;

2) preparation of bromopropyl polyoxyethylene ether ethanol solution

Adding a 45% hydrobromic acid aqueous solution, allyl polyoxyethylene ether and ethanol into a three-neck flask according to a mass ratio of 1: 2-5; installing a reflux condenser pipe, and starting cold water; starting electric stirring, wherein the rotating speed is 200r/min, reacting for 1-1.5 h at the temperature of 20-30 ℃, heating to 80 ℃, and performing reflux reaction for 1-2 h to obtain the bromopropyl polyoxyethylene ether ethanol solution.

3) Preparation of alkyl polyoxyethylene ether quaternary ammonium salt

Adding dodecatetradecyl dimethyl tertiary amine or hexadecadecyl tertiary amine, bromopropyl polyoxyethylene ether ethanol solution and water into a three-neck flask according to the mass ratio of 1: 2-7: 1-5, installing a reflux condenser pipe, and opening cold water; starting electric stirring, and setting the rotating speed to be 200 r/min; carrying out reflux reaction for 4-6 h at the temperature of 80 ℃, and adding NaOH aqueous solution to adjust the pH to 7.5-8 when the pH of the material is 6-6.5; raising the reaction temperature to 105 ℃, and carrying out reflux reaction for 4 hours to obtain alkyl dimethyl polyoxyethylene ether quaternary ammonium salt;

in the step 1), heating is carried out until the temperature is 130-135 ℃; and the temperature is reduced to 30-50 ℃.

The concentration of sodium hydroxide in the sodium hydroxide aqueous solution was 32%.

The invention has the following beneficial technical effects:

1. the alkyl polyoxyethylene ether quaternary ammonium salt prepared by the method can be compounded with a conventional anionic active agent for use, and a compounding system has very low surface tension and interfacial activity.

2. The alkyl polyoxyethylene ether quaternary ammonium salt prepared by the method can be compounded in daily chemicals, and the washing performance of the original components is not influenced while the sterilization, softening and moisture retention performances of the alkyl polyoxyethylene ether quaternary ammonium salt are ensured.

3. The alkyl polyoxyethylene ether quaternary ammonium salt prepared by the method can be added into oil field chemicals for use, can improve the interfacial activity, the oil washing capability and the emulsifying capability of products to a great extent, and does not react with polymers, anionic active agents, petroleum sulfonate and other products.

4. The alkyl polyoxyethylene ether quaternary ammonium salt prepared by the method has good water solubility and hard water resistance, and can be applied to environments with high calcium and magnesium contents.

Detailed Description

The present invention is further illustrated by the following specific examples.

EXAMPLE 1 Synthesis of 12/14 Alkyldimethylpolyoxyethylene ether n5 Aminochloride

(1) 200g of allyl alcohol and 0.4g of catalyst potassium hydroxide are added into a stainless steel reaction kettle, nitrogen is introduced for replacement for 5min, stirring is started, and the rotation speed is set to be 300 r/min. The reaction temperature was set at 130 ℃ and when the temperature in the reactor was stabilized at the set temperature, the feed pump was started and 900g of ethylene oxide was injected into the reactor from an ethylene oxide cylinder. Maintaining the temperature at 130 ℃ for reaction for 5-6 h, and cooling to 40 ℃ to obtain allyl polyoxyethylene ether n 5;

(2) preparation of bromopropyl polyoxyethylene ether ethanol solution

114g of hydrobromic acid aqueous solution (45%), n 5200 g allyl polyoxyethylene ether and 188g of ethanol are added into a three-neck flask; installing a reflux condenser pipe, and starting cold water; starting electric stirring at the rotating speed of 200 r/min; setting the reaction temperature to be 30 ℃, and reacting for 1-h; heating to 80 ℃, and carrying out reflux reaction for 2h to obtain a bromopropyl polyoxyethylene ether ethanol solution.

And (2) taking 5-8 g of bromopropyl polyoxyethylene ether ethanol solution, putting the bromopropyl polyoxyethylene ether ethanol solution into a conical flask, adding 150ml of pure water, shaking for dissolution, adding 2-3 drops of phenolphthalein indicator and 0.0988mol/L NaOH standard solution for titration, and stopping titration when the solution is changed from colorless to pink. The reaction yield was calculated by taking the average value of three parallel titrations.

(3) Preparation of alkyl polyoxyethylene ether quaternary ammonium salt

12/14 g of alkyldimethyl tertiary amine, 211.8g of bromopropylpolyoxyethylene ether n5 ethanol solution and 80g of water are added into a three-neck flask. Installing a reflux condenser pipe and opening cold water; starting electric stirring, and setting the rotating speed to be 200 r/min; the temperature is 80 ℃, and the reflux reaction is carried out for 4 hours; the reaction temperature is increased to 105 ℃, and the reflux reaction is carried out for 4 hours. The preparation of 12/14 alkyl dimethyl polyoxyethylene ether quaternary ammonium salt is completed;

and (4) calculating the content of the residual tertiary amine by acid-base titration, and further calculating the yield. And (3) taking 5-7 g of 12/14 alkyl dimethyl polyoxyethylene ether quaternary ammonium salt, putting the mixture into a conical flask, adding 50ml of ethanol and 100ml of water, and shaking to dissolve. And adding 2-3 drops of phenolphthalein indicator, titrating with 0.0988mol/L NaOH standard solution, and stopping titration when the solution changes from colorless to pink. Titration was carried out with 0.1036mol/L HCl standard solution and was stopped when the pink color had just subsided. And adding 2-3 drops of methyl red-methylene blue indicator, titrating with 0.1036mol/L HCl standard solution, stopping titrating when the solution is changed from green to red, and recording the volume of the consumed HCl standard solution. Titrate three times, take the average value to calculate.

After 4h of reaction, no pH adjustment was performed with NaOH solution, and the final product yield was low, only 76.40%.

EXAMPLE 2 Synthesis of 12/14 Alkyldimethylpolyoxyethylene ether n5 Aminochloride

The bromopropyl polyoxyethylene ether n5 synthesized in the embodiment 1 is selected to directly carry out quaternization reaction.

12/14 g of alkyldimethyl tertiary amine, 211.8g of bromopropylpolyoxyethylene ether n5 ethanol solution and 80g of water are added into a three-neck flask. Installing a reflux condenser pipe and opening cold water; starting electric stirring, and setting the rotating speed to be 200 r/min; the temperature is 80 ℃, and the reflux reaction is carried out for 4 hours; the pH was measured 6.3 and 5.17g aqueous naoh (32%) was added, at which time the pH was 7.8; the reaction temperature is increased to 105 ℃, and the reflux reaction is carried out for 4 hours. The preparation of 12/14 alkyl dimethyl polyoxyethylene ether quaternary ammonium salt is completed;

and (4) calculating the content of the residual tertiary amine by acid-base titration, and further calculating the yield. And (3) taking 5-7 g of 12/14 alkyl dimethyl polyoxyethylene ether quaternary ammonium salt, putting the mixture into a conical flask, adding 50ml of ethanol and 100ml of water, and shaking to dissolve. And adding 2-3 drops of phenolphthalein indicator, titrating with 0.0988mol/L NaOH standard solution, and stopping titration when the solution changes from colorless to pink. Titration was carried out with 0.1036mol/L HCl standard solution and was stopped when the pink color had just subsided. And adding 2-3 drops of methyl red-methylene blue indicator, titrating with 0.1036mol/L HCl standard solution, stopping titrating when the solution is changed from green to red, and recording the volume of the consumed HCl standard solution. Titrate three times, take the average value to calculate.

After 4h of reaction, the pH of the reaction solution is adjusted by NaOH, then the reaction temperature is increased to continue the reaction, and finally the tertiary amine conversion rate of 12/14 is increased to 91.77%. It can be seen that the pH adjustment during the reaction has a direct influence on the conversion rate.

EXAMPLE 3 Synthesis of 16/18 Alkyldimethylpolyoxyethylene ether n10 Aminochloride

(1) Adding 100g of allyl alcohol and 0.4g of catalyst potassium hydroxide into a stainless steel reaction kettle, introducing nitrogen for replacement for 5min, starting stirring, and setting the rotating speed to be 300 r/min. The reaction temperature was set at 130 ℃ and when the temperature in the reactor was stabilized at the set temperature, the feed pump was started and 900g of ethylene oxide was injected into the reactor from an ethylene oxide cylinder. Maintaining the temperature at 130 ℃ for reaction for 5-6 h, and cooling to 40 ℃ to obtain allyl polyoxyethylene ether n 10;

(2) preparation of ethanol solution of bromopropyl polyoxyethylene ether n10

114g of hydrobromic acid aqueous solution (45%), n 10400 g allyl polyoxyethylene ether and 390g of ethanol are added into a three-neck flask; installing a reflux condenser pipe, and starting cold water; starting electric stirring at the rotating speed of 200 r/min; setting the reaction temperature to be 30 ℃, and reacting for 1-h; heating to 80 ℃, and carrying out reflux reaction for 2h to obtain a bromopropyl polyoxyethylene ether n10 ethanol solution.

And (3) putting 5-8 g of bromopropyl polyoxyethylene ether n10 ethanol solution into a conical flask, adding 150ml of pure water, shaking for dissolution, adding 2-3 drops of phenolphthalein indicator and 0.0988mol/L NaOH standard solution for titration, and stopping titration when the solution is changed from colorless to pink. The reaction yield was calculated by taking the average value of three parallel titrations.

(3) Preparation of alkyl polyoxyethylene ether quaternary ammonium salt

16/18 g of alkyldimethyl tertiary amine, 295g of bromopropyl polyoxyethylene ether n10 ethanol solution and 100g of ethanol are added into a three-neck flask. Installing a reflux condenser pipe and opening cold water; starting electric stirring, and setting the rotating speed to be 200 r/min; the temperature is 80 ℃, and the reflux reaction is carried out for 4 hours; the pH was measured to 6.3, 2.9g of aqueous naoh (32%) was added and the pH was adjusted to 7.7; the reaction temperature is increased to 105 ℃, and the reflux reaction is carried out for 4 hours. The preparation of 12/14 alkyl dimethyl polyoxyethylene ether quaternary ammonium salt n10 is completed;

and (4) calculating the content of the residual tertiary amine by acid-base titration, and further calculating the yield. Taking 105-7 g of 16/18 alkyl dimethyl polyoxyethylene ether quaternary ammonium salt n, putting the n into a conical flask, adding 50ml of ethanol and 100ml of water, and shaking to dissolve. And adding 2-3 drops of phenolphthalein indicator, titrating with 0.0988mol/L NaOH standard solution, and stopping titration when the solution changes from colorless to pink. Titration was carried out with 0.1036mol/L HCl standard solution and was stopped when the pink color had just subsided. And adding 2-3 drops of methyl red-methylene blue indicator, titrating with 0.1036mol/L HCl standard solution, stopping titrating when the solution is changed from green to red, and recording the volume of the consumed HCl standard solution. Titrate three times, take the average value to calculate.

After 8h of reaction, the yield was 93.83%, calculated as 16/18 alkyldimethyl tertiary amine. The concentration of effective substances in the product reaches 33.98 percent.

EXAMPLE 4 Synthesis of Amidopropyl dimethyl polyoxyethylene oleate n10 amine chloride

The bromopropyl polyoxyethylene ether n10 synthesized in example 3 was directly used.

60g of oleamidopropyl dimethyl tertiary amine, 228g of bromopropyl polyoxyethylene ether n10 ethanol solution and 100g of ethanol are added into a three-neck flask. Installing a reflux condenser pipe and opening cold water; starting electric stirring, and setting the rotating speed to be 200 r/min; the temperature is 80 ℃, and the reflux reaction is carried out for 4 hours; the pH was measured to 6.4, 3.5g of aqueous naoh (32%) was added, and the pH was adjusted to 7.6; the reaction temperature is increased to 105 ℃, and the reflux reaction is carried out for 4 hours. The preparation of the oleic acid amide propyl dimethyl polyoxyethylene ether quaternary ammonium salt n10 is completed;

and (4) calculating the content of the residual tertiary amine by acid-base titration, and further calculating the yield. Taking 105-7 g of oleamide propyl dimethyl polyoxyethylene ether quaternary ammonium salt n, putting the oleamide propyl dimethyl polyoxyethylene ether quaternary ammonium salt n into a conical flask, adding 50ml of ethanol and 100ml of water, and shaking to dissolve. And adding 2-3 drops of phenolphthalein indicator, titrating with 0.0988mol/L NaOH standard solution, and stopping titration when the solution changes from colorless to pink. Titration was carried out with 0.1036mol/L HCl standard solution and was stopped when the pink color had just subsided. And adding 2-3 drops of methyl red-methylene blue indicator, titrating with 0.1036mol/L HCl standard solution, stopping titrating when the solution is changed from green to red, and recording the volume of the consumed HCl standard solution. Titrate three times, take the average value to calculate.

The preparation method can also be used for preparing polyoxyethylene ether quaternary ammonium salt in amide tertiary amine.

The beneficial effects of the present invention are further illustrated below in conjunction with experimental data:

the product of the invention is used for the viscosity reduction oil displacement agent of thick oil:

the 12/14 alkyl dimethyl polyoxyethylene ether n5 amine chloride is applied to the thickened oil viscosity-reducing oil displacement agent in certain block of the victory oil field. The block is injected with water with mineralization degree of 82506mg/L, the mineralization degree is high, the relative density of the thickened oil is 0.985, and the viscosity of the thickened oil is 12800mPa & s. The product is required to have the capability of emulsifying and reducing viscosity of thick oil, and simultaneously has ultralow oil and water interfacial tension, thereby having the function of displacing oil. 12/14 alkyldimethylpolyoxyethylene n5 amine chloride) was prepared as a 0.3% strength solution with water for performance testing. The results are shown in the following table:

the 12/14 alkyl dimethyl polyoxyethylene ether n5 amine chloride has high interfacial activity, and can reduce the interfacial tension of thickened oil and injected water to 4.9 multiplied by 10^～2mN/m. At the same time, the cation watchThe surfactant can generate an interfacial chemical action with colloid and asphaltene in the thick oil, and is more beneficial to emulsification and viscosity reduction of the thick oil. Is particularly suitable for the use of the viscosity-reducing oil displacement agent for the thick oil in the oil field.

The product of the invention is used for binary compound flooding:

binary composite flooding is a yield increasing means which is superior to large-scale use in oil fields, and requires that an oil displacement agent product has ultralow interfacial tension and excellent oil washing capacity, and cannot generate negative influence on polymer viscosity.

12/14 alkyl dimethyl polyoxyethylene ether n5 amine chloride prepared in the patent product example 2 is compounded with a conventional anionic activator, and is used for binary compound flooding, so that the effect is obvious.

The formula is as follows:

name (R)	Concentration of%	Amount of addition%
			12/14 Alkyldimethyl polyoxyethylene ether n5 Aminochlorid	33	30
Sodium dodecyl benzene sulfonate	40	20
			Sodium fatty alcohol Ether sulfate	75	15
Fatty acid diethanolamine	100	10
			Water (W)		25

The various surfactants in the table are mixed evenly according to the proportion to prepare the product, the solution with the concentration of 0.3 percent is prepared by using the injected water, the binary flooding solution containing 0.18 percent of polymer and 0.3 percent of product is prepared by using the injected water, and the performance test is carried out. In order to compare the performance of 12/14 alkyldimethyl polyoxyethylene ether n5 amine chloride, two sets of parallel tests were performed, test 1 was performed according to the formulation; test 2 was performed after removing 12/14 alkyldimethylethylenevinylether n5 amine chloride. The test results were as follows:

as shown in the table, after 12/14 alkyldimethyl polyoxyethylene ether n5 amine chloride is added, the interfacial tension and the polyaddition tension of the product are obviously improved. This is because 12/14 alkyldimethyl polyoxyethylene ether n5 amine chloride and sodium dodecyl benzene sulfonate form an ion pair surfactant with very strong interfacial activity, and the ion pair surfactant is more easily adsorbed on the oil and water interface, so that the surfactant has very high capability of reducing interfacial tension. Along with the reduction of the interfacial tension, the oil washing efficiency is obviously improved by adding the product of 12/14 alkyl dimethyl polyoxyethylene ether n5 amine chloride.