A modified acrylic emulsion and its application

Abstract

The present invention relates to the field of textile sizing agents, and specifically relates to a modified acrylic emulsion and its application, which are used to solve the problems that traditional textile sizing agents have poor water resistance, are prone to mildew, and have low abrasion resistance, and are difficult to meet the requirements of modern textile industry; adding multifunctional modified monomers to the modified acrylic emulsion can greatly improve its antibacterial property and hydrophobic property, adding modified silica can greatly improve its abrasion resistance, hydrophobic property and ultraviolet resistance, and both the multifunctional modified monomers and the modified silica are polymerized in the modified acrylic emulsion in the form of chemical bonds, which can make the two evenly distributed in the modified acrylic emulsion and effectively enhance the properties of the modified acrylic emulsion. After the textile is treated with the modified acrylic emulsion, the antibacterial property, water resistance and abrasion resistance of the textile can be effectively improved, mildew of the textile is effectively prevented, and the service life of the textile is prolonged.

Description

Technical Field

[0001] The present invention relates to the field of textile sizing agents, and particularly relates to a modified acrylic emulsion and its application. Background Art

[0002] Textile sizing agents are important auxiliary materials indispensable in the textile industry, and their properties directly affect the quality of textiles. With the rapid development of the textile industry, the requirements for textile sizing agents are also getting higher and higher.

[0003] Traditional textile sizing agents usually use starch, polyvinyl alcohol, etc. as the main raw materials, but these materials have certain limitations, such as poor water resistance, easy mildew, low abrasion resistance, etc. With the development of the textile industry, the performance requirements for sizing agents are getting higher and higher, and the current textile sizing agents are difficult to meet the needs of modern textile industry. Therefore, developing a modified acrylic emulsion and its application has important practical value. Summary of the Invention

[0004] In order to overcome the above technical problems, the purpose of the present invention is to provide a modified acrylic emulsion and its application: by ultrasonically dispersing styrene, methyl methacrylate, acrylic acid, multifunctional modified monomer, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate and deionized water, and then carrying out stirring reaction, after the reaction is completed, the reaction product is cooled, and then sieved to obtain the modified acrylic emulsion, which solves the problems that traditional textile sizing agents have poor water resistance, easy mildew, low abrasion resistance, and are difficult to meet the needs of modern textile industry.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A modified acrylic emulsion, comprising the following components in parts by weight:

[0007] 50 - 60 parts of styrene, 11 - 17 parts of methyl methacrylate, 28 - 42 parts of acrylic acid, 13 - 29 parts of multifunctional modified monomer, 6 - 12 parts of modified silica, 0.08 - 0.16 parts of sodium dodecylbenzenesulfonate, 1.5 - 2.5 parts of potassium persulfate and 150 - 170 parts of deionized water.

[0008] As a further scheme of the present invention: the multifunctional modified monomer is prepared by the following steps:

[0009] Step a1: Add 6-(trifluoromethyl)-3-pyridinemethanol, anhydrous potassium carbonate, potassium iodide, and anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 15 - 20 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then, while stirring, gradually add ethyl chloroacetate dropwise, controlling the dropping rate at 1 - 2 drops / s. After the addition is complete, raise the temperature to 55 - 60 °C and continue to stir and react for 2 - 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it for 1 - 1.5 h under the condition of a temperature of 60 - 65 °C to obtain Intermediate 1;

[0010] Step a2: Add Intermediate 1, sodium hydroxide, deionized water, and anhydrous methanol into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 - 20 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then, raise the temperature to 40 - 45 °C and continue to stir and react for 2 - 3 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 4 - 5 with hydrochloric acid solution, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it for 2 - 3 h under the condition of a temperature of 60 - 65 °C to obtain Intermediate 2;

[0011] Step a3: Add Intermediate 2, allylamine, triethylamine, and anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 15 - 20 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then, while stirring, gradually add phosphorus oxychloride dropwise, controlling the dropping rate at 1 - 2 drops / s. After the addition is complete, raise the temperature to 80 - 85 °C and continue to stir and react for 4 - 5 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Wash the filter cake with sodium bicarbonate solution 3 - 5 times, and then place it in a vacuum drying oven and dry it for 2 - 3 h under the condition of a temperature of 60 - 65 °C to obtain Intermediate 3;

[0012] Step a4: Add Intermediate 3, 1-bromodecane, and anhydrous ethanol into a three-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser. Introduce nitrogen gas for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then, raise the temperature to reflux and continue to stir and react for 4 - 5 h. After the reaction is completed, cool the reaction product to room temperature, and then rotate the evaporator to remove the solvent to obtain the multifunctional modified monomer.

[0013] As a further solution of the present invention: the dosage ratio of 6-trifluoromethyl-3-pyridinemethanol, anhydrous potassium carbonate, potassium iodide, anhydrous acetonitrile and ethyl chloroacetate in step a1 is 10 mmol: 12 - 15 mmol: 2 - 3 mmol: 35 - 45 mL: 11 - 13 mmol.

[0014] As a further solution of the present invention: the dosage ratio of intermediate 1, sodium hydroxide, deionized water and anhydrous methanol in step a2 is 10 mmol: 12 - 15 mmol: 10 - 15 mL: 20 - 25 mL; the mass fraction of the hydrochloric acid solution is 20 - 25%.

[0015] As a further solution of the present invention: the dosage ratio of intermediate 2, allylamine, triethylamine, anhydrous acetonitrile and phosphorus oxychloride in step a3 is 10 mmol: 10 mmol: 10 mmol: 40 - 50 mL: 8 - 10 mmol; the mass fraction of the sodium bicarbonate solution is 10 - 12%.

[0016] As a further solution of the present invention: the dosage ratio of intermediate 3, 1-bromodecane and anhydrous ethanol in step a4 is 10 mmol: 12 - 14 mmol: 40 - 50 mL.

[0017] As a further solution of the present invention: the modified silica is prepared by the following steps:

[0018] Add nano-silica powder and deionized water into a three-necked flask equipped with a stirrer and a thermometer, ultrasonically disperse for 25 - 30 min under the conditions of a temperature of 25 - 30 °C and an ultrasonic frequency of 40 - 50 kHz, then add vinyltrimethoxysilane and continue ultrasonically dispersing for 3 - 5 min, then adjust to pH 10 - 11 with ammonia water, then stir and react for 10 - 15 h under the conditions of a temperature of 80 - 85 °C and a stirring rate of 300 - 400 r / min. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, place the precipitate in a vacuum drying oven, and dry at a temperature of 60 - 65 °C for 3 - 4 h to obtain the modified silica.

[0019] As a further solution of the present invention: the dosage ratio of the nano-silica powder, deionized water and vinyltrimethoxysilane is 1 g: 30 - 35 mL: 0.3 - 0.9 g; the mass fraction of the ammonia water is 15 - 20%.

[0020] As a further solution of the present invention: the modified acrylic emulsion is prepared by the following steps:

[0021] Step 1: Weigh 50 - 60 parts by weight of styrene, 11 - 17 parts of methyl methacrylate, 28 - 42 parts of acrylic acid, 13 - 29 parts of multifunctional modified monomer, 6 - 12 parts of modified silica, 0.08 - 0.16 parts of sodium dodecylbenzenesulfonate, 1.5 - 2.5 parts of potassium persulfate, and 150 - 170 parts of deionized water, and set aside;

[0022] Step 2: Add styrene, methyl methacrylate, acrylic acid, multifunctional modified monomer, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three - necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. Introduce nitrogen for protection, and perform ultrasonic dispersion for 1 - 1.5 h under the conditions of a temperature of 25 - 30 °C and an ultrasonic frequency of 40 - 50 kHz. Then, carry out a stirring reaction for 6 - 8 h under the conditions of a temperature of 65 - 75 °C and a stirring rate of 300 - 400 r / min. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 150 - 200 - mesh sieve to obtain a modified acrylic emulsion.

[0023] As a further solution of the present invention: the application of the modified acrylic emulsion in the field of textile sizing agents.

[0024] The beneficial effects of the present invention:

[0025] A modified acrylic emulsion and its application of the present invention are as follows. By performing ultrasonic dispersion on styrene, methyl methacrylate, acrylic acid, multifunctional modified monomer, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water, then carrying out a stirring reaction, cooling the reaction product after the reaction is completed, and then passing it through a sieve, a modified acrylic emulsion is obtained. Adding a multifunctional modified monomer to this modified acrylic emulsion can greatly improve its antibacterial and hydrophobic properties. Adding modified silica can greatly improve its wear resistance, hydrophobicity, and ultraviolet resistance. Moreover, both the multifunctional modified monomer and modified silica are polymerized in the modified acrylic emulsion in the form of chemical bonds, which can make the two evenly distributed in the modified acrylic emulsion, effectively enhancing the performance of the modified acrylic emulsion. Therefore, after the textile is treated with the modified acrylic emulsion of the present application, the antibacterial property, water resistance, and wear resistance of the textile can be effectively improved, enabling the textile to maintain stable performance in a humid environment, effectively preventing the textile from mildewing, and extending the service life of the textile;

[0026] In the process of preparing the modified acrylic emulsion, a multifunctional modified monomer was first prepared. First, 6-(trifluoromethyl)pyridine-3-methanol and ethyl chloroacetate were reacted. The hydroxyl group on 6-(trifluoromethyl)pyridine-3-methanol underwent a nucleophilic substitution reaction with the chlorine atom on ethyl chloroacetate to introduce an ester group, obtaining intermediate 1. Then, intermediate 1 was hydrolyzed under alkaline conditions and then acidified, and the ester group was converted into a carboxyl group to obtain intermediate 2. Then, intermediate 2 was reacted with allylamine, and the carboxyl group on intermediate 2 reacted with the amino group on allylamine to introduce an alkenyl group, obtaining intermediate 3. Finally, intermediate 3 was reacted with 1-bromodecane, and the tertiary amine group on the pyridine ring in intermediate 3 reacted with the bromine atom on 1-bromodecane to form a quaternary ammonium group, obtaining the multifunctional modified monomer; the molecular structure of this multifunctional modified monomer contains a large number of C-F bonds, which can endow it with excellent hydrophobic and water-repellent properties, and its water resistance is greatly improved. The quaternary ammonium group endows it with excellent antibacterial and bacteriostatic properties, and the presence of the alkenyl group enables it to undergo a polymerization reaction as a reaction monomer. Therefore, the presence of the multifunctional modified monomer can endow the modified acrylic emulsion with excellent water resistance and antibacterial properties;

[0027] In the process of preparing the modified acrylic emulsion, a modified silica was also prepared. The nano-silica powder was treated with vinyltrimethoxysilane. The siloxane groups on vinyltrimethoxysilane hydrolyzed to form silanols, which could undergo dehydration condensation with the hydroxyl groups on the surface of the nano-silica powder particles, thereby grafting onto the surface of the nano-silica powder and introducing an alkenyl group at the same time, obtaining the modified silica; silica has excellent mechanical properties, making the emulsion have excellent wear resistance, capable of resisting the action of external frictional forces, and also endowing it with excellent hydrophobicity and anti-ultraviolet properties. Moreover, after the silica is modified, its dispersibility is greatly improved, avoiding its agglomeration, and through the polymerization reaction of the alkenyl group, it can be evenly distributed in the modified acrylic emulsion, greatly improving the performance of the modified acrylic emulsion. Specific embodiments

[0028] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0029] Example 1:

[0030] This example is a preparation method of a modified acrylic emulsion, including the following steps:

[0031] Step S1: Add 10 mmol of 6-(trifluoromethyl)-3-pyridinemethanol, 12 mmol of anhydrous potassium carbonate, 2 mmol of potassium iodide, and 35 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 15 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 11 mmol of ethyl chloroacetate dropwise, controlling the dropping rate at 1 drop / s. After the addition is complete, continue to stir and react at 55 °C for 2 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at 60 °C for 1 h to obtain Intermediate 1;

[0032] Step S2: Add 10 mmol of Intermediate 1, 12 mmol of sodium hydroxide, 10 mL of deionized water, and 20 mL of anhydrous methanol into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react at 40 °C for 2 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 4 with a 20% hydrochloric acid solution by mass, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at 60 °C for 2 h to obtain Intermediate 2;

[0033] Step S3: Add 10 mmol of Intermediate 2, 10 mmol of allylamine, 10 mmol of triethylamine, and 40 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 15 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 8 mmol of phosphorus oxychloride dropwise, controlling the dropping rate at 1 drop / s. After the addition is complete, continue to stir and react at 80 °C for 4 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Wash the filter cake three times with a 10% sodium bicarbonate solution by mass, and then place it in a vacuum drying oven and dry it at 60 °C for 2 h to obtain Intermediate 3;

[0034] Step S4: Add 10 mmol of Intermediate 3, 12 mmol of 1-bromodecane, and 40 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser. Introduce nitrogen gas for protection. Stir and react for 20 min at a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react under reflux conditions for 4 h. After the reaction is completed, cool the reaction product to room temperature, and then remove the solvent by rotary evaporation to obtain the multifunctional modified monomer;

[0035] Step S5: Add 1 g of nano-silica powder and 30 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Under the conditions of a temperature of 25°C and an ultrasonic frequency of 40 kHz, ultrasonically disperse for 25 min. Then add 0.3 g of vinyltrimethoxysilane and continue ultrasonically dispersing for 3 min. Then adjust the pH to 10 with 15% ammonia water by mass fraction. Then, under the conditions of a temperature of 80°C and a stirring rate of 300 r / min, stir and react for 10 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, place the precipitate in a vacuum drying oven, and dry it at a temperature of 60°C for 3 h to obtain modified silica;

[0036] Step S6: Weigh 50 parts of styrene, 11 parts of methyl methacrylate, 28 parts of acrylic acid, 13 parts of multifunctional modified monomer, 6 parts of modified silica, 0.08 part of sodium dodecylbenzenesulfonate, 1.5 parts of potassium persulfate, and 150 parts of deionized water by weight, and set aside;

[0037] Step S7: Add styrene, methyl methacrylate, acrylic acid, multifunctional modified monomer, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. Introduce nitrogen gas for protection. Under the conditions of a temperature of 25°C and an ultrasonic frequency of 40 kHz, ultrasonically disperse for 1 h. Then, under the conditions of a temperature of 65°C and a stirring rate of 300 r / min, stir and react for 6 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 150-mesh sieve to obtain a modified acrylic emulsion.

[0038] Example 2:

[0039] This example is a preparation method of a modified acrylic emulsion, which includes the following steps:

[0040] Step S1: Add 10 mmol of 6-trifluoromethyl-3-pyridinemethanol, 14 mmol of anhydrous potassium carbonate, 2.5 mmol of potassium iodide, and 40 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant pressure dropping funnel. Under the conditions of a temperature of 28°C and a stirring rate of 350 r / min, stir and react for 18 min. Then, while stirring, gradually add 12 mmol of ethyl chloroacetate dropwise, control the dropping rate at 1 drop / s. After the dropping is completed, raise the temperature to 58°C and continue stirring and reacting for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at a temperature of 62°C for 1.2 h to obtain intermediate 1;

[0041] Step S2: Add 10 mmol of intermediate 1, 14 mmol of sodium hydroxide, 13 mL of deionized water, and 22 mL of anhydrous methanol into a three-necked flask equipped with a stirrer and a thermometer. Stir and react at a temperature of 28 °C and a stirring rate of 350 r / min for 18 min, then raise the temperature to 42 °C and continue to stir and react for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 4.5 with a hydrochloric acid solution with a mass fraction of 22%. Then perform vacuum filtration, place the filter cake in a vacuum drying oven, and dry it at a temperature of 62 °C for 2.5 h to obtain intermediate 2;

[0042] Step S3: Add 10 mmol of intermediate 2, 10 mmol of allylamine, 10 mmol of triethylamine, and 45 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant pressure dropping funnel. Stir and react at a temperature of 28 °C and a stirring rate of 350 r / min for 18 min, then gradually add 9 mmol of phosphorus oxychloride dropwise while stirring, control the dropping rate to be 1 drop / s. After the dropping is completed, raise the temperature to 82 °C and continue to stir and react for 4.5 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, then perform vacuum filtration, wash the filter cake 4 times with a sodium bicarbonate solution with a mass fraction of 11%, and then place it in a vacuum drying oven and dry it at a temperature of 62 °C for 2.5 h to obtain intermediate 3;

[0043] Step S4: Add 10 mmol of intermediate 3, 13 mmol of 1-bromodecane, and 45 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet pipe, and a reflux condenser. Introduce nitrogen gas for protection, stir and react at a temperature of 28 °C and a stirring rate of 350 r / min for 25 min, then raise the temperature to reflux and continue to stir and react for 4.5 h. After the reaction is completed, cool the reaction product to room temperature, then rotary evaporate to remove the solvent to obtain a multifunctional modified monomer;

[0044] Step S5: Add 1 g of nano-silica powder and 32 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse at a temperature of 28 °C and an ultrasonic frequency of 45 kHz for 28 min, then add 0.6 g of vinyltrimethoxysilane and continue to ultrasonically disperse for 4 min, then adjust to pH 10.5 with ammonia water with a mass fraction of 18%. Then stir and react at a temperature of 82 °C and a stirring rate of 350 r / min for 12 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, place the precipitate in a vacuum drying oven, and dry it at a temperature of 62 °C for 3.5 h to obtain modified silica;

[0045] Step S6: Weigh 55 parts by weight of styrene, 14 parts of methyl methacrylate, 35 parts of acrylic acid, 21 parts of multifunctional modified monomer, 9 parts of modified silica, 0.12 part of sodium dodecylbenzenesulfonate, 2.0 parts of potassium persulfate, and 160 parts of deionized water, and set aside.

[0046] Step S7: Add styrene, methyl methacrylate, acrylic acid, multifunctional modified monomer, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. Introduce nitrogen for protection, and ultrasonically disperse for 1.2 h under the conditions of a temperature of 28 °C and an ultrasonic frequency of 45 kHz. Then, stir and react for 7 h under the conditions of a temperature of 70 °C and a stirring rate of 350 r / min. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 180-mesh sieve to obtain the modified acrylic emulsion.

[0047] Example 3:

[0048] This example is a preparation method of a modified acrylic emulsion, which includes the following steps:

[0049] Step S1: Add 10 mmol of 6-trifluoromethyl-3-pyridinemethanol, 15 mmol of anhydrous potassium carbonate, 3 mmol of potassium iodide, and 45 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, dropwise add 13 mmol of ethyl chloroacetate drop by drop while stirring, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react at 60 °C for 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at 65 °C for 1.5 h to obtain Intermediate 1.

[0050] Step S2: Add 10 mmol of Intermediate 1, 15 mmol of sodium hydroxide, 15 mL of deionized water, and 25 mL of anhydrous methanol into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, continue to stir and react at 45 °C for 3 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 5 with a 25% hydrochloric acid solution, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at 65 °C for 3 h to obtain Intermediate 2.

[0051] Step S3: Add 10 mmol of intermediate 2, 10 mmol of allylamine, 10 mmol of triethylamine, and 50 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, while stirring, gradually add 10 mmol of phosphorus oxychloride dropwise, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react at 85 °C for 5 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Wash the filter cake 5 times with a 12% sodium bicarbonate solution by mass fraction, and then place it in a vacuum drying oven and dry it at 65 °C for 3 h to obtain intermediate 3;

[0052] Step S4: Add 10 mmol of intermediate 3, 14 mmol of 1-bromodecane, and 50 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser. Introduce nitrogen gas for protection and stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, continue to stir and react under reflux conditions for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then rotate the evaporator to remove the solvent to obtain a multifunctional modified monomer;

[0053] Step S6: Weigh 60 parts of styrene, 17 parts of methyl methacrylate, 42 parts of acrylic acid, 29 parts of multifunctional modified monomer, 12 parts of modified silica, 0.16 part of sodium dodecylbenzenesulfonate, 2.5 parts of potassium persulfate, and 170 parts of deionized water by weight, and set aside;

[0054] Step S5: Add 1 g of nano-silica powder and 35 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 30 min under the conditions of a temperature of 30 °C and an ultrasonic frequency of 50 kHz. Then, add 0.9 g of vinyltrimethoxysilane and continue to ultrasonically disperse for 5 min. Then, adjust the pH to 11 with 20% ammonia water by mass fraction. Then, stir and react at 85 °C and a stirring rate of 400 r / min for 15 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Place the precipitate in a vacuum drying oven and dry it at 65 °C for 4 h to obtain modified silica;

[0055] Step S7: Add styrene, methyl methacrylate, acrylic acid, multifunctional modifying monomer, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. Introduce nitrogen for protection. Under the conditions of a temperature of 30 °C and an ultrasonic frequency of 50 kHz, ultrasonically disperse for 1.5 h. Then, under the conditions of a temperature of 75 °C and a stirring rate of 400 r / min, stir and react for 8 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 200-mesh sieve to obtain the modified acrylic emulsion.

[0056] Comparative Example 1:

[0057] This comparative example is a preparation method of a modified acrylic emulsion, including the following steps:

[0058] Step S1: Weigh 60 parts by weight of styrene, 17 parts of methyl methacrylate, 42 parts of acrylic acid, 12 parts of silica, 0.16 part of sodium dodecylbenzenesulfonate, 2.5 parts of potassium persulfate, and 170 parts of deionized water, and set aside;

[0059] Step S2: Add styrene, methyl methacrylate, acrylic acid, silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. Introduce nitrogen for protection. Under the conditions of a temperature of 30 °C and an ultrasonic frequency of 50 kHz, ultrasonically disperse for 1.5 h. Then, under the conditions of a temperature of 75 °C and a stirring rate of 400 r / min, stir and react for 8 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 200-mesh sieve to obtain the modified acrylic emulsion.

[0060] Comparative Example 2:

[0061] This comparative example is a preparation method of a modified acrylic emulsion, including the following steps:

[0062] Step S1: Add 1 g of nano-silica powder and 35 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Under the conditions of a temperature of 30 °C and an ultrasonic frequency of 50 kHz, ultrasonically disperse for 30 min. Then add 0.9 g of vinyltrimethoxysilane and continue to ultrasonically disperse for 5 min. Then adjust the pH to 11 with 20% ammonia water by mass fraction. Then, under the conditions of a temperature of 85 °C and a stirring rate of 400 r / min, stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Place the precipitate in a vacuum drying oven and dry at a temperature of 65 °C for 4 h to obtain the modified silica;

[0063] Step S2: Weigh 60 parts by weight of styrene, 17 parts of methyl methacrylate, 42 parts of acrylic acid, 12 parts of modified silica, 0.16 part of sodium dodecylbenzenesulfonate, 2.5 parts of potassium persulfate, and 170 parts of deionized water, and set aside;

[0064] Step S3: Add styrene, methyl methacrylate, acrylic acid, modified silica, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube. Introduce nitrogen for protection, and ultrasonically disperse for 1.5 h under the conditions of a temperature of 30 °C and an ultrasonic frequency of 50 kHz. Then, stir and react for 8 h under the conditions of a temperature of 75 °C and a stirring rate of 400 r / min. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 200-mesh sieve to obtain a modified acrylic emulsion.

[0065] Comparative Example 3:

[0066] This comparative example is a preparation method of a modified acrylic emulsion, including the following steps:

[0067] Step S1: Add 10 mmol of 6-trifluoromethyl-3-pyridinemethanol, 15 mmol of anhydrous potassium carbonate, 3 mmol of potassium iodide, and 45 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, while stirring, gradually dropwise add 13 mmol of ethyl chloroacetate, control the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react at 60 °C for 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at 65 °C for 1.5 h to obtain Intermediate 1;

[0068] Step S2: Add 10 mmol of Intermediate 1, 15 mmol of sodium hydroxide, 15 mL of deionized water, and 25 mL of anhydrous methanol into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, continue to stir and react at 45 °C for 3 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 5 with a 25% hydrochloric acid solution by mass, and then perform vacuum filtration. Place the filter cake in a vacuum drying oven and dry it at 65 °C for 3 h to obtain Intermediate 2;

[0069] Step S3: Add 10 mmol of intermediate 2, 10 mmol of allylamine, 10 mmol of triethylamine, and 50 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, while stirring, gradually add 10 mmol of phosphorus oxychloride dropwise, control the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 5 h under the condition of heating to 85 °C. After the reaction is completed, cool the reaction product to room temperature, then pour it into deionized water, and then perform vacuum filtration. Wash the filter cake 5 times with a 12% sodium bicarbonate solution by mass fraction, and then place it in a vacuum drying oven and dry it for 3 h at a temperature of 65 °C to obtain intermediate 3;

[0070] Step S4: Add 10 mmol of intermediate 3, 14 mmol of 1-bromodecane, and 50 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet pipe, and a reflux condenser. Introduce nitrogen gas for protection. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, continue to stir and react for 5 h under the condition of heating to reflux. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a multifunctional modified monomer;

[0071] Step S5: Weigh 60 parts of styrene, 17 parts of methyl methacrylate, 42 parts of acrylic acid, 29 parts of the multifunctional modified monomer, 0.16 part of sodium dodecylbenzenesulfonate, 2.5 parts of potassium persulfate, and 170 parts of deionized water by weight, and set aside;

[0072] Step S6: Add styrene, methyl methacrylate, acrylic acid, the multifunctional modified monomer, sodium dodecylbenzenesulfonate, potassium persulfate, and deionized water into a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet pipe. Introduce nitrogen gas for protection. Ultrasonically disperse for 1.5 h under the conditions of a temperature of 30 °C and an ultrasonic frequency of 50 kHz. Then, stir and react for 8 h under the conditions of a temperature of 75 °C and a stirring rate of 400 r / min. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 200-mesh sieve to obtain a modified acrylic emulsion.

[0073] Performance detection:

[0074] Immerse 200 mm×200 mm non-woven fabric specimens in the modified acrylic emulsions of Examples 1-3 and Comparative Examples 1-3, respectively, in an amount of 100 g. After 30 min, take them out, then roll them 5 times under a rolling pressure of 10 kg, then take them out, place them in a tray and dry them for 5 min at a temperature of 130 °C, and then cool them to obtain test samples. Perform performance detection on the test samples, and the detection results are shown in the following table:

[0075]

[0076] Referring to the data in the above table, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be known that adding multifunctional modified monomers and modified silica can effectively improve the antibacterial performance and water resistance of the modified acrylic emulsion, and the best effect is achieved under the synergistic action of the two.

[0077] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0078] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar methods for substitution, as long as they do not deviate from the invention or exceed the scope defined by this claims, they should all fall within the protection scope of the present invention.

Claims

1. A modified acrylic emulsion, characterized in that: It includes the following components by weight: 50-60 parts of styrene, 11-17 parts of methyl methacrylate, 28-42 parts of acrylic acid, 13-29 parts of multifunctional modified monomer, 6-12 parts of modified silicon dioxide, 0.08-0.16 parts of sodium dodecylbenzene sulfonate, 1.5-2.5 parts of potassium persulfate and 150-170 parts of deionized water; Wherein, the multifunctional modified monomer is prepared by the following steps: Step a1: 6-trifluoromethyl-3-pyridinemethanol, anhydrous potassium carbonate, potassium iodide and anhydrous acetonitrile are stirred for reaction, and then ethyl chloroacetate is added dropwise while stirring. After the addition is completed, the stirring reaction is continued. After the reaction is completed, the reaction product is cooled and then poured into deionized water, and then vacuum filtered and the filter cake is dried to obtain intermediate 1; Step a2: stirring the intermediate 1, sodium hydroxide, deionized water and anhydrous methanol for reaction, cooling the reaction product after the reaction is completed, adjusting the pH with a hydrochloric acid solution, vacuum filtering, and drying the filter cake to obtain the intermediate 2; Step a3: stirring the intermediate 2, allylamine, triethylamine and anhydrous acetonitrile for reaction, then adding phosphorus oxychloride dropwise while stirring, and continuing to stir the reaction after the addition is complete. After the reaction is completed, the reaction product is cooled, then poured into deionized water, and then vacuum filtered, and the filter cake is washed and dried to obtain the intermediate 3; Step a4: stirring the intermediate 3, 1-bromodecane and anhydrous ethanol for reaction, cooling the reaction product after the reaction is completed, and then rotary evaporating to obtain a multifunctional modified monomer; Wherein, the modified silicon dioxide is prepared by the following steps: Nano-silica powder and deionized water are added to a three-necked flask for ultrasonic dispersion, and then vinyltrimethoxysilane is added for continued ultrasonic dispersion. Then, the pH is adjusted with ammonia water, and then stirred for reaction. After the reaction is completed, the reaction product is cooled, centrifuged, and the precipitate is dried to obtain modified silica.

2. A modified acrylic emulsion according to claim 1, characterized in that: The usage ratio of the 6-trifluoromethyl-3-pyridinemethanol, anhydrous potassium carbonate, potassium iodide, anhydrous acetonitrile and ethyl chloroacetate in step a1 is 10 mmol: 12-15 mmol: 2-3 mmol: 35-45 mL: 11-13 mmol.

3. A modified acrylic emulsion according to claim 1, characterized in that: The usage ratio of the intermediate 1, sodium hydroxide, deionized water and anhydrous methanol in step a2 is 10mmol:12-15mmol:10-15mL:20-25mL; the mass fraction of the hydrochloric acid solution is 20-25%.

4. A modified acrylic emulsion according to claim 1, characterized in that: The usage ratio of the intermediate 2, allylamine, triethylamine, anhydrous acetonitrile and phosphorus oxychloride in step a3 is 10mmol:10mmol:10mmol:40-50mL:8-10mmol.

5. A modified acrylic emulsion according to claim 1, characterized in that: The usage ratio of the intermediate 3, 1-bromodecane and anhydrous ethanol in step a4 is 10 mmol: 12-14 mmol: 40-50 mL.

6. A modified acrylic emulsion according to claim 1, characterized in that: The dosage ratio of the nano silicon dioxide powder, deionized water and vinyl trimethoxysilane is 1g:30-35mL:0.3-0.9g; the mass fraction of the ammonia water is 15-20%.

7. A modified acrylic emulsion according to claim 1, characterized in that: The modified acrylic emulsion is prepared by the following steps: Step 1: weigh 50-60 parts of styrene, 11-17 parts of methyl methacrylate, 28-42 parts of acrylic acid, 13-29 parts of multifunctional modified monomer, 6-12 parts of modified silicon dioxide, 0.08-0.16 parts of sodium dodecylbenzene sulfonate, 1.5-2.5 parts of potassium persulfate and 150-170 parts of deionized water according to weight parts, and set aside; Step 2: Ultrasonic dispersion of styrene, methyl methacrylate, acrylic acid, multifunctional modified monomer, modified silica, sodium dodecylbenzene sulfonate, potassium persulfate and deionized water, followed by stirring for reaction, and after the reaction is completed, the reaction product is cooled and then sieved to obtain a modified acrylic emulsion.

8. Use of the modified acrylic emulsion according to any one of claims 1 to 7 in the field of textile slurry.

Images