CN104892817A - Preparation method of organosilicon styrene-acrylate fine emulsion - Google Patents

Abstract

The invention discloses a preparation method of a silicone styrene-acrylic microemulsion, which comprises mixing styrene, an acrylic ester monomer, a silicone monomer and a stabilizer, and stirring until completely dissolved to obtain an oil phase mixture; mixing the emulsifier Dissolved with water, stirred evenly to obtain a water phase mixture; organosilicon monomers include non-functional organosilicon monomers and functional organosilicon monomers, wherein the non-functional organosilicon monomers are methyltrimethyl(ethyl)oxy At least one of silane, propyltrimethyl(ethyl)oxysilane or phenyltrimethyl(ethyl)oxysilane; the oil phase mixture is added to the water phase mixture, and after hydrolysis-emulsification reaction, ultrasonic fine emulsification is carried out, The mixed solution is subjected to mini-emulsion polymerization under an oxygen-free condition of 60-100°C to obtain a silicone styrene-acrylic emulsion. Both the silicon content and the solid content of the organosilicon styrene-acrylic miniemulsion prepared by the invention are relatively high, and the aggregation rate can be reduced to less than 1%.

Description

A kind of preparation method of organosilicon styrene-acrylic microemulsion

technical field

The invention relates to the technical field of emulsion preparation, in particular to a method for preparing an organosilicon styrene-acrylic miniemulsion.

Background technique

Styrene-acrylic emulsion (styrene-acrylate emulsion) is a system that has been studied more in emulsion polymerization, and it is also one of the top ten non-crosslinked emulsions with important industrial application value in the world today. As an important intermediate chemical product, styrene-acrylic emulsion has a very wide range of uses. It is mainly used as architectural coatings, metal surface latex coatings, floor coatings, paper adhesives, adhesives, plastic processing additives, etc. Although styrene-acrylic emulsion is cheap, its weather resistance is average, and its outdoor application is still limited.

Silicone-modified styrene-acrylic emulsion is referred to as silicone-styrene-acrylic emulsion. Silicone has excellent properties such as anti-contamination, high and low temperature resistance, UV and infrared radiation resistance, and oxidative degradation resistance. Modification of styrene-acrylic emulsion with silicone can significantly improve its weather resistance, gloss retention, elasticity and durability etc. At present, the method of silicone modified styrene-acrylic emulsion is mainly divided into two categories: physical modification method and chemical modification method. The physical modification method is relatively simple to operate, but due to the poor compatibility between silicone and the matrix, the modification effect is not outstanding. The method of chemical connection can effectively improve the compatibility of silicone with styrene and acrylate, and the modification effect is more significant.

Miniemulsion polymerization is a new type of emulsion polymerization. Different from the micelle nucleation mechanism of traditional emulsion polymerization, miniemulsion polymerization is mainly based on droplet nucleation. By adding water-insoluble low-molecular-weight stabilizers and effective emulsifiers, the monomers can reach a stable dispersion state in the water phase and form 50-500nm monomer droplets, whose surface area is equivalent to that of micelles. The monomer droplets are small and numerous, which makes it easier to capture free radicals to initiate nucleation. Therefore, in the miniemulsion polymerization, the monomers are directly polymerized in it without migration through the water phase diffusion, especially suitable for the polymerization of relatively hydrophobic monomers into stable emulsions, in the preparation of silicone modified polyacrylate emulsions showed a greater advantage. Marcu, I. etc. found by studying the copolymer emulsion preparation technology of vinyltriethoxysilane (VTES) and n-butyl acrylate (BA), in traditional emulsion polymerization, coagulation rate can be as high as 32.7%, and in miniemulsion The highest in the polymerization is only 5.5%, which proves that the miniemulsion polymerization is more suitable for the preparation of silicone-modified polyacrylate emulsion. However, the coagulation rate of 5.5% is still relatively high in practical applications, and the preparation process of the silicone styrene-acrylic microemulsion needs to be improved.

In the preparation of silicone styrene-acrylic microemulsion, commonly used silicone monomers are: (1) Cyclosiloxane, such as octamethylcyclotetrasiloxane (D ₄ ), vinyl cyclosiloxane (D _4vi ) , generally need to carry out ring-opening under acid or alkali catalysis and then polymerize with acrylate, the process is more complicated; (2) organic siloxane monomer containing polymerization activity, such as 3-(methacryloyloxy)propyl trimethoxy 3-(methacryloyloxy)propyltriethoxysilane, vinyltriisopropoxysilane, vinyltriethoxysilane, can be directly copolymerized with acrylate monomer, but the price It is more expensive, which restricts the increase of the silicone content in the silicone styrene-acrylic microemulsion from the cost, and limits the improvement of the comprehensive performance of the silicone styrene-acrylic emulsion.

Contents of the invention

The present invention innovatively uses cheap non-functional silicone monomers as the main silicone component, and combines functional silicone monomers containing polymerization activity with cheap styrene monomers and acrylate soft monomers The monomer system is subjected to miniemulsion polymerization, and the silicone styrene-acrylic miniemulsion prepared has high silicon content and solid content, and the coagulation rate can be reduced to 0%.

A preparation method of organosilicon styrene-acrylic microemulsion, comprising the steps of:

1) Mix styrene monomer, acrylate soft monomer, silicone monomer and stabilizer, and stir until completely dissolved to obtain an oil phase mixture; dissolve the emulsifier with water, and obtain a water phase mixture after stirring evenly ;

The organosilicon monomers include non-functional organosilicon monomers and functional organosilicon monomers;

The non-functional organosilicon monomer is selected from methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane, benzene At least one of triethoxysilane;

2) adding the oil phase mixture into the water phase mixture, after hydrolysis-emulsification reaction, and then supersonic fine emulsification to obtain the mixed liquid;

3) The mixed solution is subjected to miniemulsion polymerization under an oxygen-free condition of 60-100° C. to obtain the silicone styrene-acrylic emulsion.

The monomer component in the present invention is composed of styrene hard monomer, acrylate soft monomer, non-functional silicone monomer and a small amount of functional silicone monomer, wherein the styrene hard monomer ensures that the emulsion has a certain hardness It can be used as architectural coatings, acrylate soft monomers with lower glass transition temperatures can reduce the film-forming temperature of emulsions and improve their flexibility; When the content of silicone monomer in the acrylic emulsion is low, the preparation cost can be maintained low, and the added small amount of functional silicone monomer with unsaturated double bonds can be hydrolyzed and condensed with non-functional silicone monomer, and It can carry out free radical polymerization with styrene and acrylate monomers to play a coupling role and improve the compatibility between silicone and other components, so as to prepare a stable silicone styrene-acrylic microemulsion with high silicon content.

In the preparation process, due to the fast hydrolysis rate of non-functional silicone monomers, if a large number of hydrolysis and condensation reactions occur in the siloxane group during the emulsion radical polymerization process, the two reactions will easily lead to instability of the emulsion state, so , the present invention chooses to prolong the time in the pre-emulsification stage, so that the organosilicon monomer is dispersed in styrene and acrylic ester monomer for hydrolysis and condensation reaction, and then the miniemulsion polymerization is carried out when the reversible hydrolysis reaction reaches a certain balance.

Preferably, in step 1), the organosilicon monomer accounts for 20-45 wt.% of the total monomer mass.

The total mass of monomers mentioned in this aspect refers to the total mass of styrene monomers, acrylate soft monomers and silicone monomers, the same below.

Preferably, in step 1), the mass of the non-functional organosilicon monomer is 5.0 to 8.0 times the mass of the functional organosilicon monomer;

The functional organosilicon monomers are 3-(methacryloxy)propyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, vinyltriisopropoxysilane , vinyltrimethoxysilane, vinyltriethoxysilane at least one. As preferably, in step 1), the acrylate soft monomer is at least one of n-butyl acrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, ethyl acrylate, and isooctyl methacrylate A sort of;

The mass ratio of the styrene monomer to the acrylate soft monomer is 0.5-5.0.

In order to improve the stability of miniemulsion polymerization under high silicon content and high solid content, as a preference, in step 1), the stabilizer is selected from fatty alcohol stabilizers with 12 to 18 carbons, and At least one of 12-20 long-chain alkane stabilizers and styrene-acrylate-siloxane copolymer stabilizers is used in an amount of 0.5-2wt.% of the total mass of the monomers. Further preferably, the stabilizer is a mixture of hexadecane and styrene-n-butyl acrylate-siloxane random copolymer. More preferably, hexadecane and styrene-n-butyl acrylate-siloxane random copolymer are added by mass, and the total amount of stabilizers is 2wt.% of the total mass of the monomers.

The preparation method of described styrene-acrylate-siloxane copolymer stabilizer is as follows:

a. Place a certain proportion of copper bromide (CuBr ₂ ) and N, N, N′, N″, N″-pentamethyldivinyltriamine (PMDETA), and an appropriate amount of solvent in a round-bottomed flask. Nitrogen fully removes water and oxygen;

b. Dissolve the initiator in the mixture of styrene, acrylic ester monomer and polymerization-active organosiloxane monomer, pour it into the polymerization bottle, and fully remove water and oxygen;

c. mixing the mixed solution in step b with the mixture in step a, and reacting for several hours at a certain temperature and in an anhydrous oxygen environment;

d. Ice water cooling to terminate the reaction, neutral Al ₂ O ₃ or silica gel filled column filtration to remove the catalyst to obtain a clear liquid;

e. The polymer was purified by multiple precipitations using a non-polar solvent, and the precipitate was vacuum-dried.

The above-mentioned acrylate monomers include one or more of n-butyl acrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, ethyl acrylate, and isooctyl methacrylate. The organosiloxane monomers containing polymerization activity include the functional organosilicon monomers as 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethyl One or more of oxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane. The initiator is selected from traditional radical polymerization initiators such as azobisisobutyronitrile, and the solvent is preferably toluene. The molar ratio of _CuBr2 to PMDETA is 1:0.5~1:5, the molar ratio of catalyst to initiator is 1:10~10:1, the molar ratio of monomer to initiator is 2:1~100:1, and the polymerization temperature is 60~100 ℃.

Preferably, in step 1), the emulsifier is a composite emulsifier system composed of sodium lauryl sulfate and OP-10, the mass ratio of sodium lauryl sulfate to OP-10 is 0.25 to 4, emulsifying The weight of the agent accounts for 3-4 wt% of the total weight of the monomers. More preferably, the mass ratio of sodium lauryl sulfate to OP-10 is 0.67-1.5, and the total mass of the emulsifier accounts for 3.5 wt% of the total mass of the monomers.

Preferably, in step 1), the ratio of total monomer mass to water mass is 1:3-3:1, and the solid content is between 30%-50%. More preferably, the ratio of the total mass of monomers to the mass of water is 1:2-1:1.

Preferably, in step 2), the hydrolysis-emulsification time is 1-5 hours; more preferably 2-4 hours.

As preferably, in step 2), the process of described ultrasonic microemulsification is:

Ultrasound for 2-4s, stop for 1-2s, control the total ultrasonic time to 30-90min, and control the temperature of the reaction system not higher than 35°C during the ultrasonication process;

The ultrasonic power is 300-550W, and the ultrasonic frequency is 15-35KHZ.

As preferably, step 3) in, the initiator of described miniemulsion polymerization is made up of potassium persulfate and sodium bisulfite, and the mass ratio of potassium persulfate and sodium bisulfite is 3: 1, and total amount of initiator is 0.6-1.5wt.%; more preferably 1wt.%.

Compared with prior art, the present invention has following advantage:

(1) The organosilicon component mainly adopts cheap non-functional organosilicon monomers, which can maintain a low preparation cost while increasing the organosilicon content of the organosilicon styrene-acrylic microemulsion, and add a small amount of functional organosilicon monomers The body can make the organic silicon component and the styrene and acrylate components produce chemical bonds, improve the compatibility between the components, and the silicone component can reach 30-45wt.% of the total mass of the monomer, high 10-20wt.% of the general literature reports;

(2) The polymerization method adopts the miniemulsion polymerization method, and the monomers are directly polymerized in the droplets, which can improve the stability of the silicone-modified styrene-acrylic emulsion, reduce the coagulation rate, and make the prepared emulsion particle size smaller, The film-forming material is finer and denser, and the aggregation rate of the miniemulsion polymerization in the present invention can be reduced to 0% through optimization of the preparation process;

(3) In order to improve the stability of the miniemulsion and reduce the organic volatility of the final product, a special styrene-acrylate-siloxane copolymer is used as a stabilizer, which can partially replace the traditional organic volatility stabilizer , and better overcome the Ostwald aging effect, reduce the particle size and particle size distribution of the emulsion, and can still be prepared under the conditions of higher silicon content (>30wt.%) and higher solid content (>40wt.%) A silicone styrene-acrylic microemulsion with small particle size, narrow particle size distribution, and good storage stability, thermal stability, mechanical stability and dilution stability can be obtained.

Detailed ways

Further description will be made below in conjunction with specific examples, but the present invention is not limited to the following examples.

Example 1

(1) Styrene, n-butyl acrylate, methyltrimethoxysilane and 3-(methacryloyloxy)propyltrimethoxysilane are used in a molar ratio of 2:1:0.92:0.08 and 2wt.% (mass The fractions are based on the total mass of the monomers, the same below) Hexadecane is added together into a single-necked flask equipped with magnetic stirring, and stirred for more than 1 hour to completely dissolve the stabilizer and become an oil phase mixture;

(2) Add 2.1wt.% sodium dodecyl sulfate (SDS) and 1.4wt.% OP-10 together with deionized water whose mass is 1.5 times the total mass of monomers into a four-necked flask equipped with magnetic stirring , stirred for more than 1 hour to become an aqueous phase mixture;

(3) The oil phase mixture is gradually added dropwise to the water phase mixture, and the hydrolysis reaction of the organic silicon and the emulsification process of the whole mixture are carried out simultaneously at 30° C., and the hydrolysis and emulsification time is 3 hours;

(4) Ultrasonic finely emulsify the milky white mixture, use alcohol refrigeration cycle to prevent the mixture from heating up during the ultrasonic process, the total ultrasonic time is 15min, the ultrasonic power is 440W, and the ultrasonic frequency is 25KHZ;

(5) Transfer the finely emulsified mixture back to a four-necked flask equipped with magnetic stirring, a thermometer, and a condenser tube, pass nitrogen to remove oxygen for more than 30 minutes, and after the oil bath is heated to 85°C, add 0.75wt.% oxidant potassium persulfate (KPS) and 0.25wt.% reducing agent sodium bisulfite (SHS) were added to the system to initiate the polymerization reaction, and the reaction time was 3h.

The particle size (Dz) of the organosilicon styrene-acrylic microemulsion prepared in this embodiment is 99.35, and the particle size distribution (PDI) is 0.143. to a solid content of 3%, after standing for 72 hours, the volume of the supernatant and the lower layer of sediment are less than 5%), mechanical stability (the diameter of the stirring plate is 40mm, 2500r/min, stirring for 0.5h, no demulsification and no obvious flocs), etc. Stability test.

Example 2

(1) Styrene, butyl acrylate, methyltrimethoxysilane and 3-(methacryloyloxy)propyltrimethoxysilane are mixed according to the molar ratio of 2:1:0.92:0.08 and 1wt.% hexadecane With 1wt.% methyl methacrylate-n-butyl acrylate-siloxane random copolymer (Mn=4600g/mol, PDI=1.17PS:BA(mol)=2:1,3-(methacryloyl Oxygen) propyltrimethoxysilane content is 20mol%) is added together in the one-necked flask equipped with magnetic stirring, stirs more than 1 hour, makes stabilizer dissolve completely, becomes oily phase mixture;

(2) Add 2.1wt.% sodium dodecyl sulfate (SDS) and 1.4wt.% OP-10 together with deionized water whose mass is 1.2 times the total mass of monomers into a four-necked flask equipped with magnetic stirring , stirred for more than 1 hour to become an aqueous phase mixture;

(3) The oil phase mixture is gradually added dropwise to the water phase mixture, and the hydrolysis reaction of the organic silicon and the emulsification process of the whole mixture are carried out simultaneously at 30° C., and the hydrolysis and emulsification time is 3 hours;

(4) Ultrasonic finely emulsify the milky white mixture, use alcohol refrigeration cycle to prevent the mixture from heating up during the ultrasonic process, the total ultrasonic time is 15min, the ultrasonic power is 440W, and the ultrasonic frequency is 25KHZ;

(5) Transfer the finely emulsified mixture back to a four-necked flask equipped with magnetic stirring, a thermometer, and a condenser tube, pass nitrogen to remove oxygen for more than 30 minutes, and after the oil bath is heated to 85°C, add 0.75wt.% oxidant potassium persulfate (KPS) and 0.25wt.% reducing agent sodium bisulfite (SHS) were added to the system to initiate the polymerization reaction, and the reaction time was 3h.

The particle size (Dz) of the organosilicon styrene-acrylic microemulsion prepared in this embodiment is 60.67, and the particle size distribution (PDI) is 0.078. to a solid content of 3%, after standing for 72 hours, the volume of the supernatant and the lower layer of sediment are less than 5%), mechanical stability (the diameter of the stirring plate is 40mm, 2500r/min, stirring for 0.5h, no demulsification and no obvious flocs), etc. Stability testing.

Example 3

(1) Styrene, n-butyl acrylate, methyltriethoxysilane and 3-(methacryloyloxy)propyltrimethoxysilane are mixed according to the molar ratio of 2:1:0.71:0.08 and 1wt.% ten Hexane and 1wt.% methyl methacrylate-n-butyl acrylate-siloxane random copolymer (Mn=4600g/mol, PDI=1.17, PS:BA(mol)=2:1,3-(form Acryloyloxy) propyltrimethoxysilane content is 20mol%) together into a single-necked flask equipped with a magnetic stirrer, stirred for more than 1 hour, so that the stabilizer is completely dissolved to become an oil phase mixture;

(2) Add 2.1wt.% sodium dodecyl sulfate (SDS) and 1.4wt.% OP-10 together with deionized water whose mass is 1.2 times the total mass of monomers into a four-necked flask equipped with magnetic stirring , stirred for more than 1 hour to become an aqueous phase mixture;

(3) The oil phase mixture is gradually added dropwise to the water phase mixture, and the hydrolysis reaction of the organosilicon and the emulsification process of the whole mixture are carried out simultaneously at 30° C., and the hydrolysis and emulsification time is 4 hours;

(4) Ultrasonic finely emulsify the milky white mixture, use alcohol refrigeration cycle to prevent the mixture from heating up during the ultrasonic process, the total ultrasonic time is 15min, the ultrasonic power is 440W, and the ultrasonic frequency is 25KHZ;

(5) Transfer the finely emulsified mixture back to a four-necked flask equipped with magnetic stirring, a thermometer, and a condenser tube, pass nitrogen to remove oxygen for more than 30 minutes, and after the oil bath is heated to 85°C, add 0.75wt.% oxidant potassium persulfate (KPS) and 0.25wt.% reducing agent sodium bisulfite (SHS) were added to the system to initiate the polymerization reaction, and the reaction time was 3h.

The organosilicon styrene-acrylic microemulsion particle size (Dz) prepared by the present embodiment is 55.22., and the particle size distribution (PDI) is 0.091. It is still stable after being placed for more than 60 days, and has passed GB/T 11175-2002 dilution stability ( Diluted to a solid content of 3%, after standing for 72 hours, the volume of the supernatant and the lower sediment are less than 5%), mechanical stability (the diameter of the stirring plate is 40mm, 2500r/min, stirring for 0.5h, no demulsification and no obvious flocs) and other stability tests.

Comparative example 1

Styrene, n-butyl acrylate, methyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane (MEMO) with a molar ratio of 2:1:0.92:0.08, and 2.1wt. % sodium dodecyl sulfate (SDS), 1.4wt.% OP-10, and deionized water with a mass of 1.5 times the total mass of the monomers were added together to a four-necked flask equipped with magnetic stirring, a thermometer, and a condenser. Synchronously carry out the hydrolysis reaction of organic silicon and the emulsification process of the whole mixture at 30°C, the hydrolysis and emulsification time is 3 hours, and then pass nitrogen to remove oxygen for more than 30 minutes, after the oil bath is heated to 85°C, 0.75wt.% oxidant potassium persulfate ( KPS) and 0.25wt.% reducing agent sodium bisulfite (SHS) were added to the system to initiate a polymerization reaction, a large amount of coagulation was produced during the reaction, and after a reaction time of 3 hours, the whole gelled.

Comparative example 2

(1) Styrene, n-butyl acrylate, 3-(methacryloyloxy)propyltrimethoxysilane are added together with 2wt.% hexadecane in a molar ratio of 2:1:1 to a magnetic stirring tank In a single-necked flask, stir for more than 1 hour to completely dissolve the stabilizer and form an oil phase mixture;

(2) Add 2.1wt.% sodium dodecyl sulfate (SDS) and 1.4wt.% OP-10 together with deionized water whose mass is 1.5 times the total mass of monomers into a four-necked flask equipped with magnetic stirring , stirred for more than 1 hour to become an aqueous phase mixture;

(3) The oil phase mixture is gradually added dropwise to the water phase mixture, and the hydrolysis reaction of the organic silicon and the emulsification process of the whole mixture are carried out simultaneously at 30° C., and the hydrolysis and emulsification time is 3 hours;

(4) Ultrasonic finely emulsify the milky white mixture, use alcohol refrigeration cycle to prevent the mixture from heating up during the ultrasonic process, the total ultrasonic time is 15min, the ultrasonic power is 440W, and the ultrasonic frequency is 25KHZ;

(5) Transfer the finely emulsified mixture back to a four-necked flask equipped with magnetic stirring, a thermometer, and a condenser tube, pass nitrogen to remove oxygen for more than 30 minutes, and after the oil bath is heated to 85°C, add 0.75wt.% oxidant potassium persulfate (KPS) and 0.25wt.% reducing agent sodium bisulfite (SHS) were added to the system to initiate the polymerization reaction, and the reaction time was 3h.

The particle size (Dz) of the silicone styrene-acrylic microemulsion prepared in this example was 118.66, the particle size distribution (PDI) was 0.189, and it lost its stability after being left for 28 days.

Claims (10)

1. a preparation method of organosilicon styrene-acrylic microemulsion, is characterized in that, comprises the steps: 1) Mix styrene monomer, acrylate soft monomer, silicone monomer and stabilizer, and stir until completely dissolved to obtain an oil phase mixture; dissolve the emulsifier in water, and obtain a water phase mixture after stirring evenly ; The organosilicon monomers include non-functional organosilicon monomers and functional organosilicon monomers; The non-functional organosilicon monomer is selected from methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane, benzene At least one of triethoxysilane; 2) adding the oil phase mixture into the water phase mixture, after hydrolysis-emulsification reaction, and then supersonic fine emulsification to obtain the mixed liquid; 3) The mixed solution is subjected to miniemulsion polymerization under an oxygen-free condition of 60-100° C. to obtain the silicone styrene-acrylic emulsion. 2. The preparation method of the silicone styrene-acrylic microemulsion according to claim 1, characterized in that, in step 1), the silicone-based monomer accounts for 20-45wt.% of the total monomer mass. 3. the preparation method of organosilicon styrene-acrylic microemulsion according to claim 1, is characterized in that, in step 1), the quality of described non-functional organosilicon monomer is 5.0～ 8.0 times; The functional organosilicon monomers are 3-(methacryloxy)propyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, vinyltriisopropoxysilane , vinyltrimethoxysilane, vinyltriethoxysilane at least one. 4. the preparation method of organosilicon styrene-acrylic microemulsion according to claim 1 is characterized in that, in step 1), described acrylic acid ester soft monomer is n-butyl acrylate, hydroxyethyl methacrylate, At least one of hydroxyethyl methacrylate, ethyl acrylate, and isooctyl methacrylate; The mass ratio of the styrene monomer to the acrylate soft monomer is 0.5-5.0. 5. the preparation method of organosilicon styrene-acrylic microemulsion according to claim 1 is characterized in that, in step 1), described stabilizer is selected from the fatty alcohol stabilizer that carbon number is 12～18, carbon number At least one of long-chain alkane stabilizers and acrylate-siloxane copolymer stabilizers of 12-20, and the dosage is 0.5-2wt.% of the total mass of the monomers. 6. the preparation method of organosilicon styrene-acrylic microemulsion according to claim 1 is characterized in that, in step 1), described emulsifier is the compound emulsifier system that sodium lauryl sulfate and OP-10 form , the mass ratio of sodium lauryl sulfate to OP-10 is 0.25-4, and the mass of the emulsifier accounts for 3-4 wt.% of the total mass of the monomer. 7. The preparation method of the organosilicon styrene-acrylic microemulsion according to claim 1, characterized in that, in step 1), the ratio of the total mass of monomers to the mass of water is 1:3 to 3:1. 8. The preparation method of silicone styrene-acrylic emulsion according to claim 1, characterized in that, in step 2), the time for hydrolysis-emulsification is 1 to 5 hours. 9. the preparation method of organosilicon styrene-acrylic microemulsion according to claim 1, is characterized in that, in step 2), the process of described supersonic microemulsification is: Intermittent ultrasound was used, each ultrasound was 2 to 4 s, and the interval was 1 to 2 s. The total time of ultrasound was 30 to 90 minutes. During the ultrasonic process, the temperature of the reaction system should not be higher than 35°C; The ultrasonic power is 300-550W, and the ultrasonic frequency is 15-35KHz. 10. the preparation method of organosilicon styrene-acrylic miniemulsion according to claim 1, is characterized in that, step 3) in, the initiator of described miniemulsion polymerization is made up of potassium persulfate and sodium bisulfite, over The mass ratio of potassium sulfate to sodium bisulfite is 3:1, and the total amount of initiator used is 0.6-1.5wt.% of the total mass of all monomers.