A phenylpropanol resin coated silicone elastomer SA@SE and a preparation method and application thereof

Abstract

The present application relates to the technical field of functional resin, aiming at the problem that the existing polyorganosiloxane and PC resin are prone to phase separation, and the mechanical properties of the toughened modified PC resin material are obviously reduced, the present application discloses a kind of phenylpropene resin coated organic silicon elastomer SA@SE and its preparation method and application, the SA@SE has shell-core structure, the shell of the SA@SE is linear structure or slightly crosslinked phenylpropene resin, the core of the SA@SE is the polyorganosiloxane elastomer formed by hydrogen-containing polysiloxane, ethylene polysiloxane and third functional component through silicon hydrogenation addition reaction, and the third functional component is selected from styrene, allyl phenyl ether, allyl benzyl ether, cyclohexyl vinyl ether and the like.The SA@SE of the present application is a copolymer grafted and bonded between the inner and outer core-shell through covalent bond, which can realize the mutual solubility with bisphenol A type PC resin and the like, avoid phase separation and delamination, and improve the toughening and impact resistance of the modified PC resin.

Description

Technical Field

[0001] This invention relates to the field of functional resin technology, and more specifically, to a styrene-acrylic resin-coated silicone elastomer SA@SE, its preparation method, and its application. Background Technology

[0002] Bisphenol A polycarbonate (PC resin) is a high-molecular-weight thermoplastic polymer formed by the chemical reaction of bisphenol A and phosgene. It is not only transparent but also possesses excellent heat stability, electrical insulation, and impact resistance, making it one of the most popular engineering plastics in recent years for applications such as functional films, electronic products, and new materials. However, due to its high rigidity, poor flexibility, aging resistance, and low-temperature impact resistance, as well as its poor resistance to hydrolysis and susceptibility to stress cracking during application, performance modification with toughening functional components can meet broader market demands.

[0003] As is well known, polysiloxane segments are flexible, hydrophobic, and exhibit excellent resistance to high and low temperatures and aging. Furthermore, silicone rubber made from these segments possesses outstanding low-temperature elasticity. Therefore, the industry generally considers it theoretically feasible to use silicone elastomers to toughen and modify PC resin. For example, patent CN118221941A provides a silicone-containing acrylate-styrene-acrylonitrile core-shell graft copolymer and its preparation method. This patent constructs a core-shell structure using silicon-containing structural units, acrylate structural units, and vinyl structural units. The silicon-containing structural units are converted from vinyl amino silicone oil. The core material is acrylate rubber made from acrylate monomers, grafting agents, and crosslinking agents. A shell polymer formed from vinyl aromatic monomers and vinyl nitrile monomers is then grafted onto the core, resulting in a final acrylate-styrene-acrylonitrile copolymer resin with good weather resistance and low-temperature impact resistance.

[0004] However, in existing core-shell structures, the organosilicon core is mostly prepared by ring-opening polymerization of small-molecule siloxane rings or hydrolytic condensation of small-molecule alkoxysilanes. Secondly, existing organosilicon-grafted acrylic acid copolymers and their application in PC resin toughening and other modification treatments are still affected by factors such as the organosilicon chain segment and elastomer structure, surface energy, etc., resulting in poor miscibility between organosilicon-grafted acrylate copolymers and PC resin, easily leading to separation and delamination, which seriously affects the mechanical properties of the modified PC resin. Furthermore, whether a core-shell structure styrene-acrylic resin-coated organosilicon toughening agent can be prepared by hydrosilylation addition reaction of hydrogen-containing polysiloxane macromolecules and vinyl polysiloxane macromolecules to form a silicone elastomer core, and then chemically bonded to styrene-acrylic resin to prepare a core-shell structure styrene-acrylic resin-coated organosilicon toughening agent, thus improving the miscibility and mechanical properties of the toughening agent and PC resin, is rarely reported in the literature. Summary of the Invention

[0005] The purpose of this invention is to solve the problem that existing polyorganosiloxanes easily undergo phase separation when they come into contact with PC resin, leading to a significant decrease in the mechanical properties of toughened and modified PC resin materials.

[0006] This invention is achieved through the following technical solution:

[0007] This invention provides a styrene-acrylic resin-coated silicone elastomer SA@SE with a core-shell structure. The shell of SA@SE is a linear or slightly cross-linked styrene-acrylic resin, and the core of SA@SE is a polyorganosiloxane elastomer ViSE formed by the hydrosilylation addition reaction of hydrogen-containing polysiloxane, ethylene polysiloxane, and a third functional component, with reactive vinyl groups remaining in the structure. The third functional component is selected from styrene, allyl phenyl ether, allyl benzyl ether, cyclohexyl vinyl ether, and α-C 8-18 One or more mixtures of olefins, 1,6-hexadiene, 1,9-decadiene, (poly)ethylene glycol dielyl ether, (poly)propylene glycol dielyl ether, p-styrene, etc.

[0008] Preferably, the ethylene polysiloxane has vinyl groups and / or side chains connected to it, and the main chain contains dimethylsiloxane, or / and diethylsiloxane, or / and methylphenylsiloxane, or / and diphenylsiloxane, or / and methylC 2-18 Siloxane copolymers containing one or more copolymer segments, such as alkylsiloxanes, have a vinyl content of approximately 0.1 wt%-3 wt% and a viscosity of approximately 100-60000 mPa·s. Here, the vinyl content of the ethylene polysiloxane refers to the mass percentage of reactive vinyl groups.

[0009] Vinyl polysiloxane (VPS) can be selected from vinyl-terminated polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, poly(dimethylsiloxane-diethylsiloxane), poly(dimethylsiloxane-methylphenylsiloxane), poly(dimethylsiloxane-diphenylsiloxane), and poly(dimethylsiloxane-methylC) 2-18 Alkylsiloxanes), or poly(methylvinylsiloxane-dimethylsiloxane), poly(methylvinylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-methylphenylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-diphenylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-methylC) with vinyl groups attached to the side chain. 2-18Alkylsiloxanes), or vinyl-dimethylsiloxanes with vinyl groups and side chains both connected to vinyl groups, including poly(methylvinylsiloxane-dimethylsiloxane), poly(methylvinylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-methylphenylsiloxane), poly(methylvinylsiloxane-diphenylsiloxane), and poly(methylvinylsiloxane-methylC... 2-18 Alkylsiloxanes), poly(methylvinylsiloxane-dimethylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-methylphenylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-diphenylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-methylC 2-18 One or more of alkylsiloxanes, etc., are ordered, purchased or commissioned for processing from Shanghai Jiancheng Organosilicon Co., Ltd., Jiangxi Huarunzhi New Materials Co., Ltd., Tangshan Sanyou Silicon Industry Co., Ltd., Shenzhen Jiefengchuan Chemical Technology Co., Ltd., Wuhan Kangqiong Biomedical Technology Co., Ltd., etc.

[0010] Preferably, the hydrogen-containing polysiloxane has Si-H bonds in its end groups and / or side chains, and its main chain contains dimethylsiloxane, or / and diethylsiloxane, or / and methylphenylsiloxane, or / and diphenylsiloxane, or / and methylC 2-18 The siloxane copolymers are composed of one or more copolymer segments, such as alkylsiloxanes. The Si-H bond content of the hydrogen-containing polysiloxane is approximately 0.05%-1.6%, and the viscosity is approximately 20-1000 mPa·s. Here, the Si-H bond content of the hydrogen-containing polysiloxane refers to the molar content or the content of reactive hydrogen. According to conventional practice in the art, the key component, reactive hydrogen, is defined by the molar content of Si-H bonds.

[0011] Hydrogen-containing polysiloxanes (HPS) can be selected from Si-H end-capped polydimethylsiloxanes, polydiethylsiloxanes, poly(dimethylsiloxane-diethylsiloxane), poly(dimethylsiloxane-methylphenylsiloxane), poly(dimethylsiloxane-diphenylsiloxane), and poly(dimethylsiloxane-methylC) 2-18 Alkylsiloxanes), or poly(methylhydrosiloxane-dimethylsiloxane), poly(methylhydrosiloxane-diethylsiloxane), poly(methylhydrosiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-diphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane), or poly(methylhydrosiloxane-dimethylsiloxane-methylC) with Si-H bond-terminated trimethylsilyl groups on the side chain. 2-18Alkylsiloxanes), or dimethylhydrosilane-terminated poly(methylhydrosiloxane-dimethylsiloxane), dimethylhydrosilane-terminated poly(methylhydrosiloxane-diethylsiloxane), dimethylhydrosilane-terminated poly(methylhydrosiloxane-diphenylsiloxane), dimethylhydrosilane-terminated poly(methylhydrosiloxane-methylphenylsiloxane), or dimethylhydrosilane-terminated poly(methylhydrosiloxane-methylC) 2-18 Alkylsiloxanes), poly(methylhydrosiloxane-dimethylsiloxane-diethylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-diphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylC) 2-18 Alkylsiloxane), or hydrogen-containing methyl silicone resin, hydrogen-containing phenyl silicone resin, hydrogen-containing C 2-18 One or more of silicone resins are ordered or commissioned for processing from companies such as Jiangxi Huarunzhi New Materials Co., Ltd., Wuhan Huaxiang Kejie Biotechnology Co., Ltd., Zhejiang Hengyecheng Organosilicon Co., Ltd., Zhejiang Hanbang New Materials Co., Ltd., and Lanxing Group.

[0012] This invention also discloses a method for preparing the above-mentioned styrene-acrylic resin-coated silicone elastomer SA@SE, which specifically includes the following steps:

[0013] S1 Preparation of polyorganosiloxane elastomers:

[0014] With a Si-H bond to alkenyl group molar ratio less than 1, hydrogen-containing polysiloxane, ethylene polysiloxane, and a third functional component were mixed, a platinum catalyst was added, the mixture was stirred, heated to 80-120℃, reacted for 30-120 min, cooled, and pulverized to obtain a polyorganosiloxane elastomer ViSE with residual reactive vinyl groups in its structure. The residual vinyl group in ViSE was 0.05wt%-1.0wt% of the total mass of the polyorganosiloxane elastomer ViSE.

[0015] S2 Preparation of pre-emulsified suspension:

[0016] Take acrylate, phenylenyl compound, and / or acrylonitrile, and / or crosslinking agent, stir and mix well to obtain styrene-acrylic monomer mixture A; then add molecular weight regulator, polyorganosiloxane elastomer ViSE obtained in step S1 and oil-soluble initiator, disperse evenly to obtain monomer mixture B containing oil-soluble initiator; separately take surfactant, dissolve it in water, and then add monomer mixture B to perform pre-emulsification to obtain pre-emulsified suspension;

[0017] Preparation and post-demulsification treatment of S3 styrene-acrylic resin-coated silicone elastomer SA@SE:

[0018] First, divide the pre-emulsified suspension into two portions. Take one portion of the pre-emulsified suspension, stir, heat to 75-85℃ and react for 10-30 minutes. Then, add the other portion of the pre-emulsified suspension and a water-soluble initiator and keep it at the temperature for reaction. Then, cool to room temperature, add a demulsifier to demulsify, filter out the mud-like solid, wash and dry to obtain styrene-acrylic resin-coated silicone elastomer SA@SE with a core-shell structure.

[0019] Preferably, the acrylate is selected from those containing C1- 12 Alkyl acrylates, C1- 12 One or more of the following: alkyl methacrylates, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc.

[0020] Preferably, the phenylenyl compound is selected from one or more of styrene, 4-chlorostyrene, allyl phenyl ether, 4-vinyl biphenyl, etc.

[0021] Preferably, the crosslinking agent is selected from one or more of the following: 1,4-divinylbenzene, divinylbenzene, 4,4'-divinylbiphenyl, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and methylenebis-propionamide.

[0022] Preferably, in step S2, the styrene-acrylic monomer mixture A comprises, by mass parts, 40-70 parts acrylate, 17-60 parts phenylene compound, 0-10 parts acrylonitrile and 0-3 parts crosslinking agent.

[0023] Based on the total mass of styrene-acrylic monomer mixture A, the amount of molecular weight regulator added is 0.1wt%-1wt%, the amount of polyorganosiloxane elastomer ViSE added is 10wt%-50wt%, and the amount of oil-soluble initiator added is 1wt%-3wt%; based on the total mass of monomer mixture B, the amount of surfactant added is 5wt%-15wt%.

[0024] Preferably, in step S3, the portion of pre-emulsified suspension that is first stirred and heated accounts for 1 / 10 to 1 / 3 of the total mass of the pre-emulsified suspension; then another portion of pre-emulsified suspension and water-soluble initiator are added dropwise at a uniform rate for 2-3 hours, and the reaction time is kept warm for 1-4 hours.

[0025] The application of the styrene-acrylic resin-coated silicone elastomer SA@SE disclosed in this invention in resin material processing can be used as a toughening functional component, etc.

[0026] The technical solution of the present invention has the following beneficial effects:

[0027] This invention uses hydrogen-containing polysiloxane (HPS), ethylene polysiloxane (VPS), and a third functional component (VF) as core raw material components. Through hydrosilylation addition reaction, a polyorganosiloxane elastomer ViSE with a certain amount of reactive vinyl groups in its structure is first synthesized. This ViSE is then used as a reactive monomer for organosilicon macromolecules. Under the combined action of anionic / nonionic surfactants and high-shear emulsification, the polyorganosiloxane elastomer ViSE is pre-emulsified with styrene-acrylic monomers and then subjected to seed emulsion suspension copolymerization. This results in a styrene-acrylic resin-coated organosilicon elastomer SA@SE copolymer with a shell and core structure, consisting of styrene-acrylic resin as the shell material, VF-modified polyorganosiloxane elastomer as the core material, and covalent grafting between the inner and outer layers. Through improvements to the shell material and core, and structural design, this invention achieves high miscibility of the core-shell structure styrene-acrylic resin-coated silicone elastomer SA@SE in PC resin, solving the problems of phase separation and delamination that easily occur when polysiloxanes encounter PC resin due to immiscibility. In addition, the styrene-acrylic resin-coated silicone elastomer SA@SE of this invention can be used to modify PC resin, which can also effectively improve the toughness and low-temperature impact resistance of the modified PC resin. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, they are performed according to conventional conditions or conditions recommended by the manufacturer; where the manufacturers of the instruments, equipment, reagents, or raw materials used are not specified, they are all conventional products that can be purchased commercially.

[0029] This invention provides a styrene-acrylic resin-coated silicone elastomer SA@SE with a core-shell structure. The shell of SA@SE is a linear or lightly cross-linked styrene-acrylic resin, specifically a copolymer of a phenyl alkenyl compound and acrylate (AE), and / or acrylonitrile, and / or a crosslinking agent (CA). The core of SA@SE is a polyorganosiloxane elastomer ViSE with residual vinyl groups formed by hydrosilylation addition reaction of hydrogen-containing polysiloxane (HPS), ethylene polysiloxane (VPS), and a third functional component (VF).

[0030] Phenyl alkenyl compounds are unsaturated compounds whose molecular structure contains both reactive alkenyl and phenyl groups, and can be selected from one or more of styrene (ST), 4-chlorostyrene (CST), allyl phenyl ether (APE), 4-vinyl biphenyl, etc.

[0031] Acrylates (AE) are those containing C in their structure. 1-12 Alkyl acrylates or methacrylates, such as C1-12 Alkyl acrylates, C 1-12 Alkyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc., specifically selected from one or more of methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate (IBOMA), etc.

[0032] The crosslinking agent (CA) is an ester, aromatic hydrocarbon, or amide containing two reactive alkenyl groups in its molecular structure. Specifically, it can be selected from one or more of the following: 1,4-divinylbenzene, 4,4'-divinylbiphenyl (DVBP), ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and methylenebis-propionamide.

[0033] Hydrogen-containing polysiloxanes (HPS) are those with Si-H bonds in their end groups and / or side chains, and whose main chain contains dimethylsiloxane, or / and diethylsiloxane, or / and methylphenylsiloxane, or / and diphenylsiloxane, or / and methylC. 2-18 Siloxane copolymers of one or more copolymer segments, such as alkylsiloxanes. In hydrogen-containing polysiloxanes (HPS), the Si-H bond content is approximately 0.05%-1.6%, and the viscosity is approximately 20-1000 mPa·s.

[0034] VPS is a polyvinyl siloxane (VPS) with vinyl groups and / or side chains, and a main chain containing dimethylsiloxane, or / and diethylsiloxane, or / and methylphenylsiloxane, or / and diphenylsiloxane, or / and methylC. 2-18 Siloxane copolymers of one or more copolymer segments, such as alkylsiloxanes; in ethylene polysiloxane (VPS), the vinyl (Vi) content is about 0.1wt%-3wt%, and the viscosity is about 100-60000mPa.s.

[0035] The third functional component (VF) is a substance containing 1-2 alkenyl groups in its structure, capable of undergoing hydrosilylation addition reaction, and increasing the miscibility between the polyorganosiloxane elastomer ViSE and the shell layer. Specifically, it can be selected from styrene, allyl phenyl ether (APE), allyl benzyl ether (ABE), cyclohexyl vinyl ether (CHVE), α-C 8-18One or more mixtures of olefins, 1,6-hexadiene, 1,9-decadiene, (poly)ethylene glycol dielyl ether, (poly)propylene glycol dielyl ether, p-styrene, etc.

[0036] In this invention, when preparing the core, the three main components (i.e., hydrogen-containing polysiloxane HPS, ethylene polysiloxane VPS, and the third functional component VF) can be directly mixed and reacted in one pot. Alternatively, the hydrogen-containing polysiloxane HPS and the third functional component VF can be mixed and reacted first, and then the ethylene polysiloxane VPS can be added for reaction. The reaction temperature is 80-120℃ and the reaction time is 30-120min. The polyorganosiloxane elastomer ViSE obtained after the reaction has a residual vinyl (Vi) content of about 0.05wt%-1.0wt% of the total mass of the polyorganosiloxane elastomer ViSE.

[0037] The preparation method of the styrene-acrylic resin-coated silicone elastomer SA@SE of the present invention specifically includes the following steps:

[0038] (1) Preparation of polyorganosiloxane elastomer ViSE

[0039] Weigh out hydrogen-containing polysiloxane (HPS), ethylene polysiloxane (VPS), and a third functional component (VF) according to a Si-H bond to alkenyl group molar ratio of less than 1. The amount of the aforementioned chemical bonds and groups is limited so that after the hydrosilylation addition reaction, the residual vinyl (Vi) content in the system is approximately 0.05wt%-1.0wt% (based on the mass fraction of Vi remaining in every 100 grams of polyorganosiloxane elastomer ViSE). Take the above three components, add a measured amount of platinum catalyst, stir and mix well, then heat to 80-120℃ to carry out the hydrosilylation addition reaction for 30-120 min. After cooling to room temperature, pulverize and ball-mill to obtain a white, uniform nano-micron elastic powder with an average particle size φ of approximately 30nm-50μm. This is the polyorganosiloxane elastomer ViSE with residual reactive vinyl groups in its structure, containing approximately 0.05wt%-1.0wt% vinyl groups, for later use.

[0040] The platinum catalyst can be selected from an alcoholic solution of chloroplatinic acid and / or a complexed platinum catalyst. The alcohol in the alcoholic solution is one of ethanol, isopropanol, n-propanol, tert-butanol, etc., and the amount of chloroplatinic acid used is approximately 10-200 ppm of the total mass of HPS, VPS, and VF. The complexed platinum catalyst is usually a homogeneous complex formed by the coordination complexation of a vinyl-containing silane or polysiloxane with platinum. It can be a caster catalyst (such as the caster catalyst KP-22 available from Shanghai Neutron Star Chemical Co., Ltd., which is a 1,3-diethylene-1,1,3,3-tetramethyldisiloxane complexed platinum) or a vinyl polysiloxane complexed platinum with a platinum content of approximately 1000-30000 ppm (available from Shenzhen Kejunchi Technology Co., Ltd.). The amount of the complexed platinum catalyst used is approximately 0.1 wt%-0.5 wt% of the total mass of HPS, VPS, and VF.

[0041] (2) Preparation of pre-emulsified suspension

[0042] By mass, take 40-70 parts of acrylate (AE), 17-60 parts of phenylene compound, 0-10 parts of acrylonitrile and 0-3 parts of crosslinking agent, stir and mix well to obtain styrene-acrylic monomer mixture A; then, by mass of styrene-acrylic monomer mixture A, add 0.1wt%-1wt% of molecular weight regulator, 10wt%-50wt% of polyorganosiloxane elastomer ViSE and 1wt%-3wt% of oil-soluble initiator, stir and mix well to obtain monomer mixture B containing oil-soluble initiator. Additionally, based on the total mass of monomer mixture B, weigh 5wt%-15wt% of surfactant (SA), dissolve it in water to form a transparent aqueous solution, then add it to mixture B, and pre-emulsify it using a high-shear emulsifier for 5-10 minutes. Adjust the viscosity of the system to 10-100 mPa·s with a thickener to obtain a pre-emulsified suspension. The effective component content (the percentage of the sum of the masses of styrene-acrylic monomer mixture A and surfactant SA to the total mass of the pre-emulsified suspension) is 25wt%-35wt%.

[0043] The molecular weight regulator is a substance that can terminate the copolymerization reaction of alkenylphenyl compounds with monomers such as acrylates or regulate the rate of the copolymerization reaction. Specifically, it can be selected from one or more of the following: dodecyl mercaptoethanol, mercaptopropanol, 1,3-propanedithiol, mercaptoformic acid, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, mercaptobenzoic acid, mercaptophenol, and 2,6-dimethylmercaptophenol. The thiols and thiophenols can be used directly or after being fully diluted with solvents such as esters (e.g., butyl acetate) and alcohols (e.g., isopropanol).

[0044] Oil-soluble initiators are substances that can dissolve in oil-phase monomers and decompose upon heating to generate free radicals, effectively initiating the free radical copolymerization reaction of styrene-propane monomers. Specifically, they can be selected from one or more of benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), percarbonate, tert-butyl peroxide, etc.

[0045] Surfactants (SA) are mixtures of anionic and nonionic surfactants, with a mass ratio of anionic to nonionic surfactant of 1:0.5-3. The anionic surfactant can be selected from one or more of the following: sodium fatty alcohol polyoxyethylene ether sulfate (AES), ammonium fatty alcohol polyoxyethylene ether sulfate, sodium dodecylbenzene sulfonate (DBSA-Na), potassium dodecylbenzene sulfonate (DBSA-K), sodium secondary alkyl sulfonate (AOS), sodium dodecyl sulfate (SDS), potassium dodecyl sulfate (K12), and sodium salts of carboxyethylated fatty alcohol polyoxyethylene ethers (AEC, such as AEC-9, AEC-10). The nonionic surfactant can be selected from fatty alcohol polyoxyethylene ethers with an EO number of 3-20 (such as AEO-3, AEO-9, etc.). The following are some of the following: Pingjia O-15, Pingpingjia O-20), nonylphenol polyoxyethylene ether OP (such as OP-4, OP-7, OP-10, OP-15), octylphenol polyoxyethylene ether Tx (such as Tx-4, Tx-7, Tx-10), fatty acid polyoxyethylene ether ester SG (such as SG-10, SG-15), isomeric decayl alcohol polyoxyethylene ether (such as 1350, 1370, 1390, 13120, etc.), isomeric decayl alcohol polyoxyethylene ether XP or XL (such as XP-30, XP-60, XP-90, XL-40, XL-70, XL-90), etc.

[0046] The thickener is a water-soluble thickener, meaning it is a substance that can significantly change the viscosity of an aqueous system when dissolved in water. Specific options include carbomer, acrylic resin thickeners, and thickeners with an average molecular weight Mn of approximately (3-10)×10⁻⁶. 4 One of the following: hydroxyethyl cellulose, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, polyurethane thickener 8W, thickener 638, polyethylene glycol, etc.

[0047] (3) Preparation and post-demulsification treatment of styrene-acrylic resin-coated silicone elastomer SA@SE

[0048] Take the pre-emulsified suspension, first take 1 / 10-1 / 3 of it by mass, stir and heat to 75-85℃, and carry out seed suspension emulsion polymerization reaction for 10-30 minutes. Then add the remaining pre-emulsified suspension and water-soluble initiator dropwise at a uniform rate, controlling the total dropwise addition time to 2-3 hours. Then keep the reaction at the temperature for 1-4 hours to obtain a suspension with a large number of fine elastic solids.

[0049] Cool the suspension to room temperature, remove the small amount of gel adhering to the bottle wall, stir, add a demulsifier to demulsify the system into a mud-like solid, filter out the solid, wash with deionized water 2-3 times, rinse with a small amount of ethanol, and dry at 50-70℃ for 1-2 hours. Note that during the drying process, stir or shake intermittently to prevent the powder particles from sticking together, and obtain a white elastic powder. Depending on the application requirements, it can be selectively pulverized to obtain styrene-acrylic resin-coated silicone elastomer SA@SE.

[0050] The water-soluble initiator can be selected from ammonium persulfate (APS) or potassium persulfate (KPS), and the amount of water-soluble initiator added is 0.1wt%-1.0wt% of the total mass of the pre-emulsified suspension.

[0051] The demulsifier is an infinite salt or a small molecule organic alcohol. The infinite salt can be selected from one or more of sodium chloride, sodium bromide, potassium chloride, potassium bromide, magnesium chloride, magnesium bromide, zinc chloride, zinc bromide, sodium sulfate, magnesium sulfate, zinc sulfate, etc., and the small molecule organic alcohol can be selected from ethanol and / or isopropanol.

[0052] During filtration, atmospheric pressure filtration or vacuum filtration can be used with filter paper, 60-200 mesh copper mesh, 120-200 mesh nylon mesh, industrial filter cloth, or filter bags.

[0053] The styrene-acrylic resin-coated silicone elastomer SA@SE disclosed in this invention can be used in the fields of PC resin, PC alloy resin processing, thermosetting epoxy resin and coating as a toughening and modifying material. It can effectively achieve miscibility with bisphenol A polycarbonate, epoxy resin, etc., avoid phase separation or delamination, and obtain significant toughening and impact resistance effects.

[0054] Example 1

[0055] Step 1: Take 20.0g of poly(methylhydrosiloxane-dimethylsiloxane) (denoted as HPS-1) with a silicon-hydrogen bond content of approximately 0.5% and 6.71g of... Allyl phenyl ether (APE) and 54.0g of vinyl-terminated vinyl dimethylsilyl-terminated poly(dimethylsiloxane-diphenylsiloxane) (commonly known as vinyl phenyl silicone oil, denoted as VPS-1) with a vinyl content of approximately 3wt% were mixed. Then, 0.40g of complexed platinum catalyst KP-22 (Shanghai Neutron Star Chemical Co., Ltd.) was added and stirred until well mixed. The mixture was then heated to 120℃ and reacted for 30min to obtain an elastomer preliminary product with a total mass of approximately 80.71g. After cooling to room temperature, the elastomer was pulverized into coarse particles with an average particle size of approximately 1.83mm using a molecular crusher. Then, it was ball-milled for 4h using an M-3SP2 planetary ball mill with zirconia beads to obtain a white, uniform elastic powder with an average particle size of approximately 30.23nm. This is the polyorganosiloxane elastomer with residual vinyl in its structure, denoted as ViSE-1. The vinyl content in ViSE-1 (calculated as the mass fraction of vinyl contained in 100g of ViSE-1) is approximately 0.33wt%.

[0056] Step 2: Weigh 25.0g of methyl methacrylate (MMA), 15.0g of butyl acrylate (BA), and 60.0g of styrene (ST), mix them thoroughly to obtain approximately 100.0g of styrene-acrylic monomer mixture A-1. Then add approximately 0.2g of dodecanethiol, approximately 50.0g of ViSE-1, and approximately 2.0g of benzoyl peroxide (BPO), disperse and mix thoroughly to obtain a total of approximately 152.2g of monomer mixture B-1. Separately, take 7.61g of anionic surfactant DBSA-Na and 15.22g of nonionic surfactant 1390, mix them thoroughly to obtain surfactant SA-1; then add approximately 401.70g of deionized water, stir to dissolve into a clear aqueous solution, then add monomer mixture B-1, emulsify for 5 minutes using an IKA high-shear emulsifier with a speed of approximately 10000r / min, and then use Mn approximately 3×10 4 The viscosity of the system was adjusted to approximately 15.20 mPa·s by hydroxyethyl cellulose, resulting in a total of approximately 577.0 g of pre-emulsified suspension, of which A-1, ViSE-1, and SA-1 were used as active components, accounting for approximately 30 wt% of the total mass of the pre-emulsified suspension.

[0057] Step 3: In a three-necked flask equipped with a thermometer, an electric stirrer, and a reflux condenser, add 57.7g of pre-emulsified suspension, stir, heat to 75℃ and react for 30 minutes, then continue heating to 80℃. Then, add the remaining pre-emulsified suspension and a water-soluble initiator solution prepared with approximately 2.89g of ammonium persulfate (APS) and 25.96g of H2O dropwise at a uniform rate, controlling the addition of both to be completed in about 3 hours. Then, keep the reaction at 85℃ for 1 hour to obtain a white suspension containing a large number of fine elastic solid particles. The white suspension was cooled to room temperature, and 28.85g of sodium chloride (NaCl) was added while stirring to break the emulsion and form a fine mud-like solid. The solid was then filtered through a 200-mesh nylon mesh. The filtered solid was washed three times with an equal mass of deionized water and then rinsed once with ethanol. It was then dried at 70°C for 1 hour to obtain approximately 146.35g of white elastomer powder, namely styrene-acrylic resin-coated silicone elastomer, denoted as SA@SE-1.

[0058] Example 2

[0059] Step 1: Take 20.0g of a side-linked trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane) (HPS-2) with a silane-hydrogen bond content of approximately 0.36%, 4.54g of cyclohexyl vinyl ether (CHVE), and 111.78g of a vinyl-terminated vinyl dimethylsilyl-terminated poly(dimethylsiloxane-methylphenylsiloxane) (commonly known as vinylphenyl silicone oil, denoted as VPS-2) with a vinyl content of approximately 1wt%. Mix them thoroughly, then add 0.34g of a platinum complex catalyst (from Shenzhen Kejunchi Technology Co., Ltd.) with a platinum content of 30000ppm, and stir until homogeneous. The mixture was then heated to 90°C and reacted for 120 minutes to obtain a preliminary elastomer product with a total mass of approximately 136.32 g. After cooling to room temperature, the elastomer was crushed into coarse particles with an average particle size of approximately 2.05 mm using a molecular crusher. Then, it was ball-milled for 5 hours using an M-3SP2 planetary ball mill with zirconia beads to obtain a white, uniform elastic powder with an average particle size of approximately 181.59 nm. This powder is a polyorganosiloxane elastomer with residual vinyl groups in its structure, denoted as ViSE-2. The vinyl content in ViSE-2 (calculated as the mass fraction of vinyl groups contained in every 100 grams of ViSE-2) is approximately 0.11 wt%.

[0060] Step 2: Weigh out 45.0g of methyl methacrylate (MMA), 15.0g of isobornyl methacrylate (IBOMA), 20.0g of styrene (ST), 18.0g of allyl phenyl ether (APE), and 2.0g of 4,4'-divinylbiphenyl (DVBP), mix them well, and obtain approximately 100.0g of styrene-propyl monomer mixture A-2; then add approximately 0.15g of mercaptoethanol, approximately 30g of ViSE-2, and approximately 1.5g of azobisisobutyronitrile (AIBN), stir well, and obtain a total of approximately 131.65g of monomer mixture B-2 containing oil-soluble initiator.

[0061] Separately, 1.63g of anionic surfactant SDS and 4.88g of nonionic surfactant XP-90 were mixed to obtain surfactant SA-2. Then, about 408.48g of deionized water was added and stirred to dissolve it into a transparent aqueous solution. Then, monomer mixture B-2 was added and emulsified for 10min using an IKA high-shear emulsifier with a speed of about 10000r / min. Then, carbomer was added to adjust the viscosity of the system to about 45.7mPa.s, resulting in a total of about 546.64g of pre-emulsified suspension, in which A-2, ViSE-2, and SA-2 were used as effective components, with the effective components accounting for about 25wt% of the total mass of the pre-emulsified suspension.

[0062] Step 3: In a three-necked flask equipped with a thermometer, an electric stirrer, and a reflux condenser, add 110.59g of pre-emulsified suspension, stir, heat to 82℃ and react for 15 minutes. Then, add the remaining pre-emulsified suspension and a water-soluble initiator solution prepared with approximately 1.64g of potassium persulfate (KPS) and 14.76g of H2O dropwise at a uniform rate, controlling the addition to be completed in about 2 hours. Then, keep the reaction at 82℃ for 2 hours to obtain a white suspension containing a large number of fine elastic solid particles.

[0063] The white suspension was cooled to room temperature, and 28.0 g of potassium chloride (KCl) was added while stirring to break the emulsion and form a fine mud-like solid. The solid was then filtered through a 200-mesh nylon mesh. The filtered solid was washed three times with an equal mass of deionized water and then rinsed once with ethanol. It was then dried at 65°C for 1.5 h to obtain approximately 119.26 g of white elastomer powder, namely styrene-acrylic resin-coated silicone elastomer, denoted as SA@SE-2.

[0064] Example 3

[0065] Step 1: Take 10.0g of trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methyldodecylsiloxane) (denoted as HPS-3) with a silane-hydrogen bond content of approximately 0.75%, 4.45g of allyl benzyl ether ABE, 6.06g of polyethylene glycol dielyl ether DAPEG with an EO number of 3, and 125.0g of vinyl dimethylsilyl-terminated poly(methylvinylsiloxane-dimethylsiloxane-diphenylsiloxane) (denoted as VPS-3) with vinyl groups attached to both ends, with a vinyl content of approximately 0.5wt%, mix well, and then add 0.15g of platinum complex catalyst KP-22 (from Shanghai Neutron Star Chemical Co., Ltd.). The mixture was stirred evenly and then heated to 85°C for 60 minutes to obtain a preliminary elastomer product with a total mass of 145.51g. After cooling to room temperature, the elastomer was crushed into coarse particles with an average particle size of about 2.61mm using a molecular crusher. Then, it was ball-milled for 4.5 hours using an M-3SP2 planetary ball mill with zirconia beads to obtain a white, uniform elastic powder with an average particle size of about 215.37nm. This is a polyorganosiloxane elastomer with residual vinyl groups in its structure, denoted as ViSE-3. The vinyl content in ViSE-3 (calculated as the mass fraction of vinyl groups contained in 100g of ViSE-3) is about 0.15wt%.

[0066] Step 2: Weigh out 40.0g of methyl methacrylate (MMA), 13.5g of butyl acrylate (BA), 20.0g of styrene (ST), 25.0g of 4-vinylbiphenyl (VBP), and 1.5g of propylene glycol diacrylate (PGDA), mix them well, and obtain approximately 100.0g of styrene-acrylic monomer mixture A-3; then add approximately 0.12g of mercaptopropionic acid, approximately 25.0g of ViSE-3, and approximately 1.25g of azobisisobutyronitrile (AIBN), stir well, and obtain a total of approximately 126.37g of monomer mixture B-3 containing oil-soluble initiator.

[0067] Separately, 3.12g of anionic surfactant K12 and 6.26g of nonionic surfactant XL-70 were mixed to obtain surfactant SA-3. Then, about 248.54g of deionized water was added and stirred to dissolve into a transparent aqueous solution. Then, monomer mixture B-3 was added, and emulsification was carried out for 6 minutes using an IKA high-shear emulsifier with a speed of about 10000r / min. Then, 8W of thickener was added to adjust the viscosity of the system to about 35.10mPa.s, resulting in a total of about 384.28g of pre-emulsified suspension, in which A-3, ViSE-3, and SA-3 were used as effective components, with the effective components accounting for about 35wt% of the total mass of the pre-emulsified suspension.

[0068] Step 3: In a three-necked flask equipped with a thermometer, an electric stirrer, and a reflux condenser, add 76.86g of pre-emulsified suspension, stir, heat to 80℃ and react for 15 minutes. Then, add the remaining pre-emulsified suspension and a water-soluble initiator solution prepared with approximately 0.96g of potassium persulfate and 8.64g of H2O dropwise at a uniform rate, controlling the addition of both to be completed in about 2 hours. Then, keep the mixture at 80℃ and react for 1 hour to obtain a white suspension containing a large number of fine elastic solid particles.

[0069] The white suspension was cooled to room temperature, and 19.08 g of sodium sulfate (Na2SO4) was added while stirring to demulsify the suspension, forming a fine mud-like solid. The solid was then filtered through a 200-mesh nylon screen. The filtered solid was washed three times with an equal mass of deionized water, then rinsed once with ethanol, and finally dried at 70°C for 1.5 h to obtain approximately 113.87 g of white elastomer powder, namely styrene-acrylic resin-coated silicone elastomer, denoted as SA@SE-3.

[0070] Comparative Example 1

[0071] The difference between this comparative example and Example 1 is that the raw materials and amounts used in step 1 are different, and multiple sets of experiments were conducted, as detailed below:

[0072] Experiment 1: 20.0 g of HPS-1, 6.71 g of phenyl allyl ether (APE), and 100.0 g of VPS-1 were mixed thoroughly, and then 0.40 g of complexed platinum catalyst KP-22 was added. The mixture was stirred until homogeneous, and then heated to 120 °C for 30 min. After the reaction, an organosilicon elastomer with a vinyl residue of approximately 1.3 wt% was obtained. However, the surface of this organosilicon elastomer was soft and sticky, making it impossible to prepare a core material with a suitable particle size through crushing or other methods.

[0073] Experiment 2: 10.0g HPS-1, 6.71g phenyl allyl ether (APE), and 150.0g VPS-1 were mixed thoroughly, and then 0.40g of complexed platinum catalyst KP-22 was added. The mixture was stirred until homogeneous, and then heated to 120℃ for 30 minutes. After the reaction, an organosilicon elastomer with a vinyl residue of approximately 1.78wt% was obtained. However, the surface of this organosilicon elastomer was soft and sticky, and it could not be processed into a core material with a suitable particle size by means of crushing or other methods.

[0074] Experiment 3: The soft silicone elastomer obtained in Experiment 2 was swollen with the styrene-acrylic monomer in Example 1, and then reacted with the method in step 3 of Example 1 to prepare the target product styrene-acrylic resin-coated silicone elastomer. The results showed that during the drop addition of the pre-emulsified suspension, a large amount of gel or coagulation into large clumps of gel appeared in the system, and the preparation of the target product styrene-acrylic resin-coated silicone elastomer failed.

[0075] Through the preparation process of this comparative example, it can be seen that when preparing polyorganosiloxane elastomer ViSE, the amount of raw materials and other conditions are key factors affecting whether the product can be successfully prepared. When the amount exceeds the range defined by this invention, it is impossible to successfully prepare the intermediate product of polyorganosiloxane elastomer ViSE with the specific structure and morphology conceived in this invention and the target product of styrene-acrylic resin-coated organosilicon elastomer SA@SE.

[0076] Comparative Example 2

[0077] The difference between this comparative example and Example 2 is that the amount of crosslinking agent DVBP in step 2 was increased to 10.0 g, while the amounts of other raw materials and preparation conditions remained unchanged. The results showed that during the dropwise addition of the pre-emulsified suspension, the system gelled due to the excessive crosslinking density of the styrene-acrylic resin in the shell, preventing further reaction; thus, the preparation of the target product, styrene-acrylic resin-coated silicone elastomer, failed.

[0078] Through the preparation process of this comparative example, it can be seen that the amount of each component raw material used in the preparation of the pre-emulsified suspension is also a key factor affecting whether the subsequent steps can successfully synthesize the styrene-acrylic resin-coated silicone elastomer SA@SE. When the amount of raw materials and usage exceeds the range specified in this invention, the styrene-acrylic resin-coated silicone elastomer SA@SE product with the specific structure and morphology conceived in this invention cannot be successfully obtained.

[0079] Comparative Example 3

[0080] The difference between this comparative example and Example 1 is that it does not contain a third functional monomer and the molecular structure of VPS does not contain diphenylsiloxane units, as detailed below:

[0081] With a Si-H to -CH=CH2 molar ratio of 1:1.1, 20.0g of commercially available HPS-1 (Zhejiang Hengyecheng Organosilicon Co., Ltd.) with a silicon-hydrogen bond content of approximately 0.5wt% was mixed with 99.0g of commercially available vinyl dimethylsilyl-terminated polydimethylsiloxane (denoted as VPS-6, Jiangxi Huarunzhi New Materials Co., Ltd.) with a vinyl content of approximately 3wt%. Then, 0.40g of complexed platinum catalyst KP-22 was added, and the mixture was stirred until homogeneous. The mixture was then heated to 120℃ and reacted for 30min. After crushing and ball milling, a polydimethylsiloxane elastomer ViSE-6 with an average particle size of 31.53nm and a vinyl content of approximately 0.23wt% was obtained. ViSE-6 was then used instead of ViSE-1 in Example 1 for subsequent preparations to obtain a styrene-acrylic resin-coated organosilicon elastomer, denoted as SA@SE-6.

[0082] Test case

[0083] The styrene-acrylic resin-coated silicone elastomers SA@SE-1, SA@SE-2, SA@SE-3, and SA@SE-6 prepared in Examples 1-3 and Comparative Example 3 were taken as samples, and SA@SE toughened modified PC resins were prepared accordingly. The PC resin used was PC-1100 from Lotte, South Korea.

[0084] The preparation process of SA@SE toughened modified PC resin is as follows: SA@SE and PC resin are mixed at a mass ratio of 1:24, and antioxidant-225 (0.1 wt% of PC resin mass) is added. The mixture is then melt-mixed for 5 minutes at 250℃ and approximately 120 rpm using an XSS-300 torque rheometer (Shanghai Kechuang Rubber & Plastic Equipment Co., Ltd.). The torque and energy consumption are recorded. The melt-mixed sample is then placed in a mold and pressed into a sheet using a flat vulcanizing apparatus to obtain a 2 mm thick sample sheet. Simultaneously, the toughening agent, PC resin masterbatch, and antioxidant-225 are mixed at the above mass ratio and melt-extruded and granulated using a twin-screw extruder at 250℃. The granules are then injection molded into notched impact and mechanical property test strips.

[0085] The different SA@SE toughened modified PC resins prepared were denoted as ASPC. Unmodified blank PC resin was taken as the blank group, and the polyorganosiloxane elastomer ViSE-1 from Example 1 was physically composited with PC resin at a mass ratio of 1:24 as the reference group. Application performance tests were conducted according to relevant standard injection molding samples, as detailed below:

[0086] (1) Referring to GB / T 2410-2008 "Determination of transmittance and haze of transparent plastic", samples pressed by a flat vulcanizing apparatus were taken and the haze (H) of different ASPCs was determined by a TH-100 haze meter (Hangzhou Caipu Technology Co., Ltd.).

[0087] (2) In accordance with GB / T528-1998 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber", notched specimens were prepared and then frozen in a -40℃ freezer for 4 hours. After taking them out, the notched impact strength of different ASPCs was determined within 3 minutes using a Shimadzu AGS-X electronic universal testing machine.

[0088] (3) Samples were prepared in accordance with GB / T1040-2006.9 "Determination of tensile properties of plastics" and the tensile strength of different ASPCs was determined using a Shimadzu AGS-X electronic universal testing machine.

[0089] The results of the above performance tests are summarized in Table 1 below:

[0090] Table 1. Material property test results of different samples

[0091]

[0092] The above experimental and performance test results show that, compared with Comparative Example 3, the blank group, and Reference-1 group, the styrene-acrylic resin-coated silicone elastomer SA@SE and its preparation method proposed in Examples 1 to 3 exhibit significantly higher torque and energy consumption. This indicates that the styrene-acrylic resin of the present invention does indeed chemically coat the surface of the silicone elastomer. Furthermore, the modified PC resin prepared using the styrene-acrylic resin-coated silicone elastomer SA@SE from Examples 1 to 3 has lower light transmittance, and its haze, impact resistance, and tensile strength are significantly higher than those of the PC resin samples in Comparative Example 3 (blank group) and Reference-1 group. This demonstrates that the styrene-acrylic resin-coated silicone elastomer SA@SE and its preparation method proposed in the present invention can improve the low-temperature impact performance of modified PC resins by enhancing its miscibility with PC resins, etc.

[0093] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A styrene-acrylic resin-coated silicone elastomer SA@SE, characterized in that, The SA@SE has a core-shell structure. The shell layer is a linear or slightly cross-linked styrene-acrylic resin. The core layer is a polyorganosiloxane elastomer ViSE formed by the hydrosilylation addition reaction of hydrogen-containing polysiloxane, ethylene polysiloxane, and a third functional component. The ViSE contains residual vinyl groups, with a vinyl residue amounting to 0.05 wt%-1.0 wt% of the total mass of the ViSE. The third functional component is selected from styrene, allyl phenyl ether, allyl benzyl ether, cyclohexyl vinyl ether, and α-C... 8-18 One or more mixtures of olefins, 1,6-hexadiene, 1,9-decadiene, ethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, and polypropylene glycol diallyl ether; the vinyl content of the ethylene polysiloxane is 0.1wt%-3wt%; the molar ratio of the Si-H bonds in the hydrogen-containing polysiloxane to the sum of the alkenyl groups in the ethylene polysiloxane and the third functional component is less than 1; the ethylene polysiloxane contains diphenylsiloxane repeating units; the raw materials of the styrene-acrylic resin, by mass parts, include 40-70 parts acrylate, 17-60 parts phenyl alkenyl compound, 0-10 parts acrylonitrile, and 0-3 parts crosslinking agent.

2. The styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 1, characterized in that, The ethylene polysiloxane has vinyl groups and / or side chains connected to it, and its main chain contains dimethylsiloxane, diethylsiloxane, methylphenylsiloxane, diphenylsiloxane, or methylC. 2-18 A siloxane copolymer of at least two copolymer units in an alkylsiloxane.

3. The styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 1, characterized in that, The hydrogen-containing polysiloxane has Si-H bonds in its end groups and / or side chains, and its main chain contains dimethylsiloxane, diethylsiloxane, methylphenylsiloxane, diphenylsiloxane, or methylC. 2-18 A siloxane copolymer of at least two copolymer units in an alkylsiloxane.

4. A method for preparing the styrene-acrylic resin-coated silicone elastomer SA@SE according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1 Preparation of polyorganosiloxane elastomers: With a Si-H bond to alkenyl group molar ratio of less than 1, hydrogen-containing polysiloxane, ethylene polysiloxane, and a third functional component were mixed, a platinum catalyst was added, and the mixture was stirred until homogeneous. The mixture was then heated to 80-120℃ and reacted for 30-120 min. After cooling, the mixture was pulverized to obtain a polyorganosiloxane elastomer ViSE with residual vinyl groups in its structure. The residual vinyl group content was 0.05wt%-1.0wt% of the total mass of the polyorganosiloxane elastomer ViSE. S2 Preparation of pre-emulsified suspension: Take acrylate, phenylenyl compound, and / or acrylonitrile, and / or crosslinking agent, stir and mix well to obtain styrene-acrylic monomer mixture A; then add molecular weight regulator, polyorganosiloxane elastomer ViSE obtained in step S1 and oil-soluble initiator, disperse evenly to obtain monomer mixture B containing oil-soluble initiator; separately take surfactant, dissolve it in water, and then add monomer mixture B to perform pre-emulsification to obtain pre-emulsified suspension; Preparation and post-demulsification treatment of S3 styrene-acrylic resin-coated silicone elastomer SA@SE: First, divide the pre-emulsified suspension into two portions. Take one portion of the pre-emulsified suspension, stir and heat it to 75-85℃ for 10-30 minutes. Then, add the other portion of the pre-emulsified suspension and a water-soluble initiator and keep it at the temperature for reaction. Then, cool it to room temperature, add a demulsifier to demulsify, filter out the solid, wash and dry it to obtain styrene-acrylic resin-coated silicone elastomer SA@SE.

5. The method for preparing styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 4, characterized in that, The acrylate is selected from those containing C1- 12 Alkyl acrylates, C1- 12 One or more of the following: alkyl methacrylates, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, and isobornyl methacrylate.

6. The method for preparing styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 4, characterized in that, The phenylenyl compound is selected from one or more of styrene, 4-chlorostyrene, allyl phenyl ether, and 4-vinyl biphenyl.

7. The method for preparing styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 4, characterized in that, The crosslinking agent is selected from one or more of the following: 1,4-divinylbenzene, 4,4'-divinylbiphenyl, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and methylenebisacrylamide.

8. The method for preparing styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 4, characterized in that, In step S2, Based on the total mass of mixture A, the amount of molecular weight regulator added is 0.1wt%-1wt%, the amount of polyorganosiloxane elastomer added is 10wt%-50wt%, and the amount of oil-soluble initiator added is 1wt%-3wt%. The amount of surfactant added is 5wt%-15wt% based on the total mass of mixture B.

9. The method for preparing styrene-acrylic resin-coated silicone elastomer SA@SE according to claim 4, characterized in that, In step S3, the portion of pre-emulsified suspension that is first stirred and heated accounts for 1 / 10 to 1 / 3 of the total mass of the pre-emulsified suspension; then another portion of pre-emulsified suspension and water-soluble initiator are added dropwise at a uniform rate over a period of 2-3 hours, and the reaction is kept at a temperature for 1-4 hours.

10. The application of the styrene-acrylic resin-coated silicone elastomer SA@SE according to any one of claims 1 to 3, or the styrene-acrylic resin-coated silicone elastomer SA@SE prepared by the preparation method according to any one of claims 4 to 9, in resin material processing.

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