阅读说明：本技术 一种阳离子型油污清洗剂的制备方法 (Preparation method of cationic oil stain cleaning agent ) 是由 魏立新 李哲 卢梦真 董航 赵健 于 2020-12-13 设计创作，主要内容包括：一种阳离子型油污清洗剂的制备方法。包括如下步骤：将定量叔丁基苯酚与催化剂氢氧化钾投入高温高压反应釜中密封,通入氮气吹扫后抽至真空,向反应釜中通入环氧乙烷,升温至140℃反应生成中间产物1；再向反应釜中通入环氧丙烷,升温至140℃反应生成中间产物2；再向反应釜中通入环氧乙烷,升温至140℃反应生成嵌段聚醚A。取定量聚醚A与催化剂氢氧化钾加入到三分瓶中,水浴加热80℃,缓慢滴加3-氯-2羟丙基三甲基氯化铵水溶液,反应得到一种阳离子型油污清洗剂。该油污清洗剂具有用量少、清洗速度快、效率高等优点,是一种高效油污清洗剂。(A preparation method of a cationic oil stain cleaning agent. The method comprises the following steps: putting quantitative tert-butylphenol and catalyst potassium hydroxide into a high-temperature high-pressure reaction kettle, sealing, introducing nitrogen, purging, vacuumizing, introducing ethylene oxide into the reaction kettle, and heating to 140 ℃ to react to generate an intermediate product 1; then introducing propylene oxide into the reaction kettle, heating to 140 ℃ and reacting to generate an intermediate product 2; and introducing ethylene oxide into the reaction kettle, and heating to 140 ℃ to react to generate the block polyether A. And (2) adding a certain amount of polyether A and a catalyst potassium hydroxide into a trisection bottle, heating in a water bath at 80 ℃, and slowly dropwise adding a 3-chloro-2 hydroxypropyl trimethyl ammonium chloride aqueous solution to react to obtain the cationic oil stain cleaning agent. The oil stain cleaning agent has the advantages of small using amount, high cleaning speed, high efficiency and the like, and is a high-efficiency oil stain cleaning agent.)

1. A preparation method of a cationic oil stain cleaning agent comprises the following steps:

the preparation method comprises the following steps:

the method comprises the steps of firstly, putting quantitative tert-butyl phenol and a catalyst into a high-temperature high-pressure reaction kettle for sealing, replacing air in the kettle in a nitrogen purging mode, vacuumizing by using a vacuum pump until the reading of a pressure gauge is-0.09 MPa, heating to 120 ℃, opening a feed valve of the high-temperature high-pressure reaction kettle, and slowly introducing ethylene oxide, wherein the mass ratio of the p-tert-butyl phenol to the ethylene oxide is 1: 69-159, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing a feed valve when the addition of the ethylene oxide is finished; after the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 1;

and step two, opening the feeding valve of the high-temperature high-pressure reaction kettle, and slowly introducing propylene oxide into the reaction kettle, wherein the mass ratio of the total reaction materials to the propylene oxide is 1: 2, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing a feed valve when the addition of the propylene oxide is finished; after the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 2;

and step three, opening a feed valve of the high-temperature high-pressure reaction kettle, and slowly introducing ethylene oxide into the reaction kettle, wherein the mass ratio of the total reaction materials to the ethylene oxide is 3: 1, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of a reaction kettle to be 0.24-0.26 MPa, and closing a feed valve when the addition of ethylene oxide is finished;

after the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and obtaining block polyether A;

and fourthly, putting the block polyether A obtained quantitatively in the third step into a three-way bottle, continuously stirring and heating in a water bath until the temperature is 50-60 ℃, adding a catalyst into the three-way bottle, wherein the mass of the catalyst is 1.3-1.5% of that of the polyether A, heating in the water bath until the temperature is 65-70 ℃, slowly dropwise adding an aqueous solution of 3-chloro-2 hydroxypropyl trimethyl ammonium chloride with the concentration of 30% into the three-way bottle, wherein the mass of the 3-chloro-2 hydroxypropyl trimethyl ammonium chloride is 4% of the mass of the total reaction materials, heating to 75-85 ℃ after dropwise adding, fully reacting for 9-10 hours, after the first-stage reaction is finished, cooling the temperature in the bottle to room temperature, continuing to react for 0.5-1.5 hours, discharging, diluting with water to prepare a 50% aqueous solution of the oil stain cleaning agent, and preparing the cationic oil stain cleaning agent.

2. The preparation method of the cationic oil stain cleaning agent according to claim 1, characterized by comprising the following steps:

in the first step, the mass ratio of p-tert-butylphenol to ethylene oxide is 1: 69-159, specifically 1: 69. 1: 99. 1: 159;

in the first step, the used catalyst is potassium hydroxide, and the dosage of the catalyst is 0.1-0.2 percent of the total mass of the ethylene oxide and the propylene oxide in the first step, the second step and the third step, and is specifically 0.2 percent;

in the second step, the mass ratio of the total materials in the high-temperature high-pressure reaction kettle to the propylene oxide is 1: 2;

in the third step, the mass ratio of the total materials in the high-temperature high-pressure reaction kettle to the ethylene oxide is 3: 1;

in the first step, the second step and the third step, the pressure of the high-temperature high-pressure reaction kettle is between 0.24MPa and 0.26MPa during reaction, and the reaction is continued for 30 to 60min, specifically 45min after the pressure in the reaction kettle falls back;

in the fourth step, the reaction catalyst is potassium hydroxide, and the mass of the catalyst is 1.3-1.5 percent of that of the polyether A, specifically 1.5 percent;

in the fourth step, the reaction is heated to 50-60 ℃ in a water bath for the first time; heating in a water bath for the second time to 65-70 ℃; heating in a water bath for the third time to 75-85 ℃, and keeping the temperature for 9-10 hours, specifically 10 hours; when the temperature is recovered to the room temperature, the continuous reaction time is 0.5 h-1.5 h, in particular 1 h;

in the fourth step, the mass of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in the reaction accounts for 4% of the mass of the total reaction materials, and water is added into the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to prepare a 30% aqueous solution; the dropping time of the aqueous solution of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 4-6 hours, specifically 5 hours;

in the fourth step, after the reaction is finished, the obtained oil stain cleaning agent is supplemented with a solvent to prepare a 50% solution, wherein the added solvent is water.

Technical Field

The invention belongs to the technical field of industrial cleaning, and particularly relates to a preparation method of a cationic surfactant for cleaning oil stains.

Background

With the increasing development of social economy, the use of various metal materials is more and more extensive. With steel only, the world's steel production has rapidly increased from 50 s, 1.89 million tons in 1950 to 7.4 million tons in 1979, with an average increase of 1900 ten thousand tons per year. After 70 s, the yield of Chinese steel is rapidly increased, and the demand and yield of Chinese steel are also rapidly increased due to economic soaring. With the rise of the second economic body of China in the world since the 21 st century, a great amount of various metal materials are used in the fields of petrochemical industry, automobiles, transportation and the like, and oil removal is needed no matter the metal is used or a key process before the metal leaves a factory. As a metal used in the field of petrochemical industry, various crude oil, thick oil and other oil stains and oil dirt are inevitably contaminated in the using process. The oil stain and the oil dirt are remained for a long time to cause solidification and wax precipitation, thereby causing various potential safety hazards to equipment. Therefore, the metal degreasing problem is also becoming more severe. The traditional metal oil removing methods comprise a high-temperature chemical method, a high-temperature alkaline solution method, an organic solution oil removing method and the like, the traditional methods are gradually eliminated due to the problems of high cost, large consumption, serious harm to human bodies and environment and the like, and the water-based metal cleaning agent gradually enters the visual field of people.

The water-based metal cleaner takes water as a solvent, has the characteristics of strong detergency, good stability, small using amount, good permeability, no harm to human bodies, low cost, small environmental pollution and the like, and gradually replaces the traditional oil stain cleaner at present. The cationic oil stain cleaning agent has wider application and better effect on negatively charged organic particles compared with anionic and nonionic cleaning agents.

Disclosure of Invention

In order to solve the technical problems mentioned in the background technology, the invention provides a preparation method of a cationic oil stain cleaning agent. The novel oil stain cleaning agent is characterized in that: the detergent belongs to the derivatives of organic nitrogen compounds, nitrogen groups have positive charges, and organic matter particles generally have negative charges, so that the detergent can play a role in neutralizing charges, adsorbing and bridging, and the purpose of cleaning oil stains is achieved. In addition, the oil stain cleaning agent also has the advantages of small dosage, high cleaning speed, high efficiency and the like, and is a high-efficiency oil stain cleaning agent. Has wider application prospect in the aspect of more and more complex components of oil stains and oil stains.

The technical scheme of the invention is as follows: the cationic oil stain cleaning agent has the following structural general formula:

the preparation method comprises the following steps:

the method comprises the steps of firstly, putting quantitative tert-butyl phenol and a catalyst into a high-temperature high-pressure reaction kettle for sealing, replacing air in the kettle in a nitrogen purging mode, vacuumizing by using a vacuum pump until the reading of a pressure gauge is-0.09 MPa, heating to 120 ℃, opening a feed valve of the high-temperature high-pressure reaction kettle, and slowly introducing ethylene oxide, wherein the mass ratio of the p-tert-butyl phenol to the ethylene oxide is 1: 69-159, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing the feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 1;

and step two, opening the feeding valve of the high-temperature high-pressure reaction kettle, and slowly introducing propylene oxide into the reaction kettle, wherein the mass ratio of the total reaction materials to the propylene oxide is 1: 2, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing the feeding valve when the addition of the propylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, finishing the reaction, and obtaining an intermediate product 2

And step three, opening a feed valve of the high-temperature high-pressure reaction kettle, and slowly introducing ethylene oxide into the reaction kettle, wherein the mass ratio of the total reaction materials to the ethylene oxide is 3: 1, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing a feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and obtaining block polyether A;

and fourthly, putting the block polyether A obtained quantitatively in the third step into a three-way bottle, continuously stirring and heating in a water bath until the temperature is 50-60 ℃, adding a catalyst into the three-way bottle, wherein the mass of the catalyst is 1.3-1.5% of that of the polyether A, heating in the water bath until the temperature is 65-70 ℃, slowly dropwise adding an aqueous solution of 3-chloro-2 hydroxypropyl trimethyl ammonium chloride with the concentration of 30% into the three-way bottle, wherein the mass of the 3-chloro-2 hydroxypropyl trimethyl ammonium chloride is 4% of the mass of the total reaction materials, heating to 75-85 ℃ after dropwise adding, fully reacting for 9-10 hours, after the first-stage reaction is finished, cooling the temperature in the bottle to room temperature, continuing to react for 0.5-1.5 hours, discharging, diluting with water to prepare a 50% aqueous solution of the oil stain cleaning agent, and preparing the cationic oil stain cleaning agent.

The invention has the following beneficial effects:

compared with the conventional surfactants in the market, the oil stain cleaning agent prepared by the preparation method has the following excellent effects: the water-based cationic oil stain cleaning agent is a water-based cleaning agent, so that the water solubility is better. The cationic cleaning agent has high cleaning speed and higher efficiency, can achieve better cleaning effect in the case of organic matter particles containing negative charges, and can have wider application range in the case of increasingly complex oil stain and oil dirt environments, so that the water-based oil stain cleaning agent is an excellent oil stain cleaning agent and has good development prospect.

The specific implementation mode is as follows:

the invention relates to a preparation method of a cationic oil stain cleaning agent, which has the following structural general formula:

the preparation method comprises the following steps:

the method comprises the steps of firstly, putting quantitative tert-butyl phenol and a catalyst into a high-temperature high-pressure reaction kettle for sealing, replacing air in the kettle in a nitrogen purging mode, vacuumizing by using a vacuum pump until the reading of a pressure gauge is-0.09 MPa, heating to 120 ℃, opening a feed valve of the high-temperature high-pressure reaction kettle, and slowly introducing ethylene oxide, wherein the mass ratio of the p-tert-butyl phenol to the ethylene oxide is 1: 69-159, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing the feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 1;

and step two, opening the feeding valve of the high-temperature high-pressure reaction kettle, and slowly introducing propylene oxide into the reaction kettle, wherein the mass ratio of the total reaction materials to the propylene oxide is 1: 2, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing the feeding valve when the addition of the propylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, finishing the reaction, and obtaining an intermediate product 2

And step three, opening a feed valve of the high-temperature high-pressure reaction kettle, and slowly introducing ethylene oxide into the reaction kettle, wherein the mass ratio of the total reaction materials to the ethylene oxide is 3: 1, controlling the reaction temperature to be 135-145 ℃, enabling the pressure of the reaction kettle to be 0.24-0.26 MPa, and closing a feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting in the kettle for 30-60 min until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and obtaining block polyether A;

and fourthly, putting the block polyether A obtained quantitatively in the third step into a three-way bottle, continuously stirring and heating in a water bath until the temperature is 50-60 ℃, adding a catalyst into the three-way bottle, wherein the mass of the catalyst is 1.3-1.5% of that of the polyether A, heating in the water bath until the temperature is 65-70 ℃, slowly dropwise adding an aqueous solution of 3-chloro-2 hydroxypropyl trimethyl ammonium chloride with the concentration of 30% into the three-way bottle, wherein the mass of the 3-chloro-2 hydroxypropyl trimethyl ammonium chloride is 4% of the mass of the total reaction materials, heating to 75-85 ℃ after dropwise adding, fully reacting for 9-10 hours, after the first-stage reaction is finished, cooling the temperature in the bottle to room temperature, continuing to react for 0.5-1.5 hours, discharging, diluting with water to prepare a 50% aqueous solution of the oil stain cleaning agent, and preparing the cationic oil stain cleaning agent.

The above are the basic steps of the preparation method of the present invention. The following are preferred embodiments of the present invention:

in the first step, the mass ratio of p-tert-butylphenol to ethylene oxide is 1: 69-159, specifically 1: 69. 1: 99. 1: 159;

in the first step, the used catalyst is potassium hydroxide, and the dosage of the catalyst is 0.1-0.2 percent of the total mass of the ethylene oxide and the propylene oxide in the first step, the second step and the third step, and is specifically 0.2 percent;

in the second step, the mass ratio of the total materials in the high-temperature high-pressure reaction kettle to the propylene oxide is 1: 2;

in the third step, the mass ratio of the total materials in the high-temperature high-pressure reaction kettle to the ethylene oxide is 3: 1;

in the first step, the second step and the third step, the pressure of the high-temperature high-pressure reaction kettle is between 0.24MPa and 0.26MPa during reaction, and the reaction is continued for 30 to 60min, specifically 45min after the pressure in the reaction kettle falls back;

in the fourth step, the reaction catalyst is potassium hydroxide, and the mass of the catalyst is 1.3-1.5% of that of the polyether A, specifically 1.5%. (ii) a

In the fourth step, the reaction is heated to 50-60 ℃ in a water bath for the first time; heating in a water bath for the second time to 65-70 ℃; heating in a water bath for the third time to 75-85 ℃, and keeping the temperature for 9-10 hours, specifically 10 hours; when the temperature is recovered to the room temperature, the continuous reaction time is 0.5 h-1.5 h, in particular 1 h;

in the fourth step, the mass of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in the reaction accounts for 4% of the mass of the total reaction materials, and water is added into the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to prepare a 30% aqueous solution; the dropping time of the aqueous solution of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 4-6 hours, specifically 5 hours;

in the fourth step, after the reaction is finished, the obtained oil stain cleaning agent is supplemented with a solvent to prepare a 50% solution, wherein the added solvent is water.

The chemical reaction equation related to the preparation method is as follows:

wherein:

specific examples are set forth below to provide those skilled in the art with a better understanding of the present invention and to enable its practice. The application range of the present invention is not affected by the embodiment, and the specific implementation manner can be determined according to the technical scheme and the application specific situation of the present invention.

Example 1

Firstly, putting 2g of tert-butyl phenol and 1.12g of potassium hydroxide into a high-temperature high-pressure reaction kettle for sealing, replacing air in the kettle in a nitrogen purging mode, vacuumizing by using a vacuum pump until the reading of a pressure gauge is-0.09 MPa, heating to 120 ℃, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 138g of ethylene oxide, controlling the reaction temperature to be 140 ℃, keeping the pressure of the reaction kettle at 0.25MPa, and closing the feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting for 45min in the kettle until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 1;

and step two, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 280g of propylene oxide into the reaction kettle, controlling the reaction temperature to be 140 ℃ and the pressure of the reaction kettle to be 0.25MP, and closing the feed valve when the propylene oxide is added. After the pressure of the reaction kettle falls back, the reaction is continued in the kettle for 45min until the reading of a pressure gauge of the reaction kettle is reduced to-0.09 MPa, the reaction is finished, and an intermediate product 2 is obtained

And step three, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 140g of ethylene oxide into the reaction kettle, controlling the reaction temperature to be 140 ℃ and the pressure of the reaction kettle to be 0.25MP, and closing the feed valve when the addition of the propylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting for 45min in the kettle until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and obtaining block polyether A;

and fourthly, placing 27.6g of the block polyether A obtained in the third step into a trisection bottle, continuously stirring and heating in a water bath until the temperature is 50 ℃, adding 0.414g of potassium hydroxide into the trisection bottle, heating the water bath to 70 ℃, slowly dropwise adding 3.74g of 30% aqueous solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the trisection bottle, dropwise adding for 5 hours, heating to 80 ℃ after dropwise adding, fully reacting for 10 hours, cooling the temperature in the bottle to room temperature after the first-stage reaction is finished, continuously reacting for 1 hour, discharging, diluting with 26.07g of water, and preparing the oil stain cleaning agent into 50% aqueous solution to obtain an experimental sample 1.

Example 2

Firstly, putting 2g of tert-butyl phenol and 1.6g of potassium hydroxide into a high-temperature high-pressure reaction kettle for sealing, replacing air in the kettle in a nitrogen purging mode, vacuumizing by using a vacuum pump until the reading of a pressure gauge is-0.09 MPa, heating to 120 ℃, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 198g of ethylene oxide, controlling the reaction temperature to be 140 ℃, keeping the pressure of the reaction kettle at 0.25MPa, and closing the feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting for 45min in the kettle until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 1;

and step two, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 400g of propylene oxide into the reaction kettle, controlling the reaction temperature to be 140 ℃ and the pressure of the reaction kettle to be 0.25MP, and closing the feed valve when the propylene oxide is added. After the pressure of the reaction kettle falls back, the reaction is continued in the kettle for 45min until the reading of a pressure gauge of the reaction kettle is reduced to-0.09 MPa, the reaction is finished, and an intermediate product 2 is obtained

And step three, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 200g of ethylene oxide into the reaction kettle, controlling the reaction temperature to be 140 ℃ and the pressure of the reaction kettle to be 0.25MP, and closing the feed valve when the addition of the propylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting for 45min in the kettle until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and obtaining block polyether A;

and fourthly, placing 27.6g of the block polyether A obtained in the third step into a trisection bottle, continuously stirring and heating in a water bath until the temperature is 50 ℃, adding 0.414g of potassium hydroxide into the trisection bottle, heating the water bath to 70 ℃, slowly dropwise adding 3.74g of 30% aqueous solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the trisection bottle, dropwise adding for 5 hours, heating to 80 ℃ after dropwise adding, fully reacting for 10 hours, cooling the temperature in the bottle to room temperature after the first-stage reaction is finished, continuously reacting for 1 hour, discharging, diluting with 26.07g of water, and preparing the oil stain cleaning agent into 50% aqueous solution to obtain an experimental sample 2.

Example 3

Firstly, putting 2g of tert-butyl phenol and 2.56g of potassium hydroxide into a high-temperature high-pressure reaction kettle for sealing, replacing air in the kettle in a nitrogen purging mode, vacuumizing by using a vacuum pump until the reading of a pressure gauge is-0.09 MPa, heating to 120 ℃, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 318g of ethylene oxide, controlling the reaction temperature to be 140 ℃, keeping the pressure of the reaction kettle at 0.25MPa, and closing the feed valve when the addition of the ethylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting for 45min in the kettle until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and finishing the reaction to obtain an intermediate product 1;

and step two, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 640g of propylene oxide into the reaction kettle, controlling the reaction temperature to be 140 ℃ and the pressure of the reaction kettle to be 0.25MP, and closing the feed valve when the propylene oxide is added. After the pressure of the reaction kettle falls back, the reaction is continued in the kettle for 45min until the reading of a pressure gauge of the reaction kettle is reduced to-0.09 MPa, the reaction is finished, and an intermediate product 2 is obtained

And step three, opening a feed valve of the high-temperature high-pressure reaction kettle, slowly introducing 320g of ethylene oxide into the reaction kettle, controlling the reaction temperature to be 140 ℃ and the pressure of the reaction kettle to be 0.25MP, and closing the feed valve when the addition of the propylene oxide is finished. After the pressure of the reaction kettle falls back, continuously reacting for 45min in the kettle until the reading of a pressure meter of the reaction kettle is reduced to-0.09 MPa, and obtaining block polyether A;

and fourthly, placing 27.6g of the block polyether A obtained in the third step into a trisection bottle, continuously stirring and heating in a water bath until the temperature is 50 ℃, adding 0.414g of potassium hydroxide into the trisection bottle, heating the water bath to 70 ℃, slowly dropwise adding 3.74g of 30% aqueous solution of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the trisection bottle, dropwise adding for 5 hours, heating to 80 ℃ after dropwise adding, fully reacting for 10 hours, cooling the temperature in the bottle to room temperature after the first-stage reaction is finished, continuously reacting for 1 hour, discharging, diluting with 26.07g of water, and preparing the oil stain cleaning agent into 50% aqueous solution to obtain an experimental sample 2.

Example 4 evaluation of cleaning Effect of cationic oil stain cleaning agent

And taking GB/T35759-. Wherein, the experimental sample 1, the experimental sample 2 and the experimental sample 3 respectively correspond to a mass ratio of p-tert-butylphenol to ethylene oxide of 1: 69. 1: 99. 1: 159, respectively.

1. A preparation stage:

(1) types of metal test pieces: a) steel No. 45; b) z30 primary cast iron; c) h62 brass; d) LY12-BC2 duralumin; e) 1Crl8Ni9Ti stainless steel.

(2) The test piece pretreatment method comprises the following steps: the test piece was polished to shine with No. 240 abrasive cloth. The polished test piece is wiped by absorbent gauze or absorbent cotton, hung on an S-shaped hook, immersed in absolute ethyl alcohol and then scrubbed by using tweezers to clamp the absorbent gauze or the absorbent cotton. Then the test piece is moved to acetone or petroleum ether at 30-60 ℃ for rinsing, and is dried by hot air, and the clean test piece is hung on a test piece rack for standby by connecting an S-shaped hook.

(3) Preparing a water-based oil stain cleaning agent: the test solution for the detergency and the foam performance is prepared by using 250mg/kg of hard water (containing 0.1658/L of anhydrous calcium chloride and 0.247g/L of magnesium sulfate heptahydrate) according to the concentration of 3 percent; the test solution for corrosion, rinsing and rust prevention is prepared into a 3% solution by using distilled water. The surface of the test piece for corrosion and rust prevention test is graded according to the following standards: A) steel and cast iron: grade 0, no surface rust and no obvious change; grade 1, no rust on the surface, slight discoloration or loss of gloss; grade 2, light rust or uneven color change on the surface; grade 3, large area of surface is rusted. B) Copper and aluminum: level 0, no apparent change in surface; level 1, slight uniform discoloration or loss of gloss of the surface; 2-level, uneven color change and light loss on the surface, and spots on the part; grade 3, severe discoloration or corrosion of the surface.

2. Evaluation of detergency:

(1) preparing artificial oil stain: 8% of barium petroleum sulfonate; lanolin magnesium soap, 3.5%; lanolin, 2%; 30% of industrial vaseline; no. 20 machine oil, 34.5%; mechanical oil No. 30, 12%; 2% of calcium-based lubricating grease; 8 percent of alumina.

(2) The evaluation method comprises the following steps: the beaker containing 3% of the oil stain cleaning agent is placed in a water bath kettle at the temperature of 60 +/-2 ℃. And clamping the oil-smeared test piece on a swinging frame of a swinging washing machine. Soaking in cleaning agent solution for 3min, and then starting a swing washing machine for swing washing for 3 min. And after the swinging and washing are finished, taking out the test piece together with the hook, swinging and washing in distilled water at 60 +/-2 ℃ for 30s, hanging on a test piece rack, drying in a constant-temperature drying box at 40 +/-2 ℃ for 2h, cooling to room temperature in a dryer, weighing, and calculating the cleaning power.

3. Defoaming performance evaluation: the test solution is placed in a constant temperature water bath at 40 ℃ for aging for 30 min. When the test solution is aged, a water pump is started to enable circulating water to pass through a graduated tube jacket, and the water temperature is controlled to be 40 +/-0.5 ℃. During the test, the inner wall of the graduated tube is washed by distilled water, then the inner wall of the graduated tube is washed by test solution completely, and no foam is left on the inner wall. Injecting the test solution from the bottom of the graduated tube to a level above 50mL, closing the stopcock of the graduated tube, standing for 5min, and adjusting the stopcock to ensure that the liquid level is just at 50mL mark. The dropping tube is filled with 200mL of test solution by a suction method and is placed on the upper opening of the graduated tube by 90cm according to requirements. The stopwatch was started immediately and the initial foam height (average height of foam edge and apex) was read when the solution in the drip tube was run off, and a second reading was taken at the end of 5 min.

4. And (3) corrosion evaluation: the medicine jar containing 400mL of test solution is placed in a constant-temperature water bath kettle, and the water temperature is 80 +/-2 ℃. Then the weighed test piece is hung on a cross beam transversely placed on the opening of the medicine cylinder, and the test piece is completely immersed in the test solution. After 2h, the test piece was taken out, rinsed with freshly boiled and cooled distilled water (10 times of rinsing), dehydrated with absolute ethanol and dried with hot air. After the appearance is checked, the test piece is dried in an oven at the temperature of 40 +/-2 ℃ for 30min, cooled and weighed.

5. Evaluation of rust prevention: the medicine jar containing 400mL of the test solution is placed into a constant temperature water bath kettle, and the test solution is kept at a constant temperature of 80 +/-2 ℃. And immersing the test piece in the test solution for 30s and taking out. Sucking off the liquid at the lower end and hole of the test piece by using filter paper, and drying the test piece in an oven at 35 +/-2 ℃ for 15 min. Then, the test piece is transferred into a hygrothermograph which is placed in an oven with the constant temperature of 35 +/-2 ℃ and the relative humidity of 90 percent in advance, and is placed for 24 hours, and the temperature of the oven is kept at 35 +/-2 ℃ all the time. After completion, the test piece was checked for appearance.

6. Evaluation of rinsing Performance: the beaker containing 400mL of the test solution was placed in a thermostatic water bath. The sample solution was kept at a constant temperature of 60. + -. 2 ℃. Soaking the prepared test piece in the test solution for 5min, taking out, immediately sucking off the liquid at the lower end and holes of the test piece by using filter paper, and drying in an oven at 40 + -2 deg.C for 30 min. The test piece was taken out and shaken back and forth 10 times (once for each round trip) in 400mL of distilled water at a temperature of 60. + -. 2 ℃ for a time not exceeding 10 s. Then, the test piece is dried by hot air, the appearance of the test piece is checked, and the surface of the test piece is visually checked to see whether cleaning agent residues exist.

7. Evaluation of high and low temperature stability: high-temperature stability: taking about 50mL of a sample into a 100mL colorless wide-mouth glass bottle with a plug, placing the bottle in a thermostat at 60 +/-2 ℃ after plugging, taking out the bottle after 6 hours, and immediately observing the appearance; low-temperature stability: about 50mL of the sample is put into a 100mL colorless wide-mouth glass bottle with a plug, the wide-mouth glass bottle with the plug is placed in a refrigerator at minus 5 +/-2 ℃ after the plug is added, the wide-mouth glass bottle is taken out after 24 hours, and the appearance is observed after the room temperature is restored.

The results of the above property evaluations are shown in the following table.

TABLE 1 comparison of detergency ratios for different detergents

TABLE 2 comparison of defoaming Properties of different detergents

	Defoaming Property/mm
		Experimental sample 1	2.9
Experimental sample 2	2.2
		Experimental sample 3	1.5
Commercially available cleaning agent	2.0

TABLE 3 comparison of corrosion behavior of different detergents

TABLE 4 comparison of rust and rinsing performances of different detergents

TABLE 5 comparison of high and Low temperature stability of different detergents

	High temperature stability	Stability at Low temperature
			Experimental sample 1	Without demixing and precipitation	Without demixing and precipitation
Experimental sample 2	Without demixing and precipitation	Without demixing and precipitation
			Experimental sample 3	Without demixing and precipitation	Without demixing and precipitation
Commercially available cleaning agent	Without demixing and precipitation	Without demixing and precipitation

From the above experiments, it can be seen that the ratio of p-tert-butylphenol to ethylene oxide is 1: 159, test sample 3 performed best and the cleaning effect was best.