An acrylic resin coated silicone elastomer (PA@SE) prepared by aqueous phase suspension emulsion polymerization and a preparation method and application thereof

Abstract

The application relates to the technical field of functional resin, and particularly discloses an acrylic resin coated silicone elastomer PA@SE prepared through aqueous phase suspension emulsion polymerization as well as a preparation method and application thereof. The PA@SE has a core-shell structure, the shell layer is linear acrylic resin or slightly crosslinked acrylic resin, the inner core of the PA@SE is polyorganosiloxane elastomer ViSE formed through a silicon-hydrogenation addition reaction of hydrogen-containing polysiloxane, ethylene polysiloxane and a third functional component, and the third functional component includes vinyl acetate, allyl acetate, allyl phenyl ether, allyl benzyl ether, cyclohexyl vinyl ether, alpha-C 8‑18 Olefins, 1,6-hexadiene, 1,9-decadiene, (poly)ethylene glycol diallyl ether, (poly)propylene glycol diallyl ether, or a mixture of one or more thereof. The acrylic resin coated silicone elastomer PA@SE provided by the application can not only be mutually soluble with PC resin and the like, but also can realize toughening and reinforcing effects in PC resin and the like.

Description

Technical Field

[0001] This invention relates to the field of functional resin technology, and more specifically, to an acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization, its preparation method, and its application. Background Technology

[0002] PC resin is a high-molecular-weight thermoplastic polymer synthesized from bisphenol A and phosgene through a chemical reaction. This material not only boasts a transparent appearance but also exhibits excellent heat resistance, electrical insulation, and impact strength, making it a highly favored engineering plastic in recent years for applications such as functional films, electronic device manufacturing, and new material research and development. However, polycarbonate resin itself has inherent drawbacks: it is relatively rigid but lacks flexibility, exhibits poor aging resistance and low-temperature impact resistance, and is susceptible to hydrolysis, leading to stress cracking during processing and molding. To broaden its application scenarios and meet wider market demands, related research proposes modifying its properties by adding toughening components to compensate for these performance shortcomings.

[0003] Polysiloxane segments are flexible, exhibit excellent hydrophobic properties, and possess superior resistance to high and low temperatures and aging. Therefore, it is theoretically feasible to use flexible organosilicon 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. The silicone-containing acrylate-styrene-acrylonitrile core-shell graft copolymer of this patent includes silicone structural units, acrylate structural units, and vinyl structural units. By introducing monomeric silicone oil containing vinyl and amino functional groups during the preparation of large-particle-size silicone acrylate latex, an amino-functionalized silicone-polyacrylate is prepared. Then, a shell polymer formed by vinyl aromatic monomers and vinyl nitrile monomers is grafted onto it, so that the final acrylate-styrene-acrylonitrile copolymer resin has good weather resistance and low-temperature impact resistance.

[0004] However, existing core-shell structured organosilicon-grafted acrylic acid copolymers and their application in PC resin toughening and other modification treatments have problems such as poor miscibility between organosilicon-grafted acrylic acid copolymers and PC resins, and the tendency for separation and delamination to occur over time, which affects the mechanical properties of the modified PC resin. 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 an acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization, having a core-shell structure. The shell of the PA@SE is a linear or lightly cross-linked acrylic resin, and the core of the PA@SE is a polyorganosiloxane elastomer ViSE formed by hydrosilylation addition reaction of hydrogen-containing polysiloxane, ethylene polysiloxane, and a third functional component. The third functional component includes vinyl acetate, allyl acetate, allyl phenyl ether, allyl benzyl ether, cyclohexyl vinyl ether (CHVE), and α-C 8-18 One or more mixtures of olefins, 1,6-hexadiene, 1,9-decadiene, (poly)ethylene glycol dielyl ether, and (poly)propylene glycol dielyl ether.

[0008] Preferably, the hydrogen-containing polysiloxane (HPS) 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 A siloxane copolymer of one or more copolymer segments, such as alkylsiloxanes. The Si-H bond content in hydrogen-containing polysiloxanes (in terms of the number of moles of Si-H bonds per 100g of hydrogen-containing polysiloxane) is approximately 0.05%-1.6%, and the viscosity is approximately 20-1000 mPa·s.

[0009] 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), poly(methylhydrosiloxane-dimethylsiloxane-diphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylC) with Si-H bond-terminated trimethylsilyl groups. 2-18 Alkylsiloxanes), or dimethylsiloxane-terminated poly(methylhydrosiloxane-dimethylsiloxane), or dimethylsiloxane-terminated poly(methylhydrosiloxane-diethylsiloxane), poly(methylhydrosiloxane-diphenylsiloxane), poly(methylhydrosiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-methylC) 2-18Alkylsiloxanes), 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 alkyl silicone resins are ordered, purchased, or commissioned for processing from companies such as Jiangxi Huarunzhi New Material Co., Ltd., Wuhan Huaxiang Kejie Biotechnology Co., Ltd., Zhejiang Hengyecheng Organosilicon Co., Ltd., Zhejiang Hanbang New Material Co., Ltd., and Lanxing Group.

[0010] Preferably, the ethylene polysiloxane (VPS) has vinyl groups and / or side chains attached to it, and the 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. The vinyl Vi content (by mass of vinyl groups per 100g of polysiloxane) in ethylene polysiloxanes is approximately 0.1wt%-3wt%, and the viscosity is approximately 100-60000mPa.s.

[0011] 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 chains. 2-18 Alkylsiloxanes), or vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-dimethylsiloxane), vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-diethylsiloxane), vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-methylphenylsiloxane), vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-diphenylsiloxane), vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-methylC) 2-18Alkylsiloxanes), vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-dimethylsiloxane-diethylsiloxane), vinyl dimethylsiloxane-terminated poly(methylvinylsiloxane-dimethylsiloxane-methylphenylsiloxane), or vinyl dimethylsiloxane-terminated 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.

[0012] Preferably, the acrylic resin is a copolymer of methyl methacrylate and other acrylates, and / or a crosslinking agent, wherein the other acrylates contain C in their structure. 2-12 Alkyl or C 5-12 Cycloalkyl acrylates or methacrylates.

[0013] In this invention, the shell of PA@SE is preferably an acrylate copolymer, specifically selected from methyl methacrylate (MMA)-co-C 2-12 Alkyl (meth)acrylates, MMA-co-cyclohexyl (meth)acrylate, MMA-co-isobornyl (meth)acrylate, MMA-co-C 2-12 Alkyl (meth)acrylate-co-(meth)acrylate cyclohexyl ester, MMA-co-C 2-12 One or more of alkyl (meth)acrylates, co-(meth)acrylate isobornyl ester, etc. Further, mildly cross-linked acrylate copolymers, such as MMA-co-C, can be selected. 2-12 Alkyl (meth)acrylate-co-ethylene glycol di(meth)acrylate, MMA-co-C 2-12 Alkyl (meth)acrylate - co-diethylene glycol di(meth)acrylate, MMA-co-C 2-12 Alkyl (meth)acrylate-co-diethylene glycol di(meth)acrylate, MMA-co-C 2-12 Alkyl (meth)acrylate-co-propylene glycol di(meth)acrylate, MMA-co-C 2-12 Alkyl (meth)acrylate - co-dipropylene glycol di(meth)acrylate, MMA-co-C 2-12Alkyl (meth)acrylate-co-dipropylene glycol di(meth)acrylate, MMA-co-cyclohexyl (meth)acrylate-co-ethylene glycol di(meth)acrylate, MMA-co-cyclohexyl (meth)acrylate-co-propylene glycol di(meth)acrylate, MMA-co-cyclopentyl (meth)acrylate-co-ethylene glycol di(meth)acrylate, MMA-co-cyclopentyl (meth)acrylate-co-propylene glycol di(meth)acrylate, MMA-co-isoborneol (meth)acrylate-co-ethylene glycol di(meth)acrylate, MMA-co-isoborneol (meth)acrylate-co-propylene glycol di(meth)acrylate, etc.

[0014] This invention also provides a method for preparing the above-mentioned acrylic resin-coated silicone elastomer PA@SE by aqueous suspension emulsion polymerization, comprising the following steps:

[0015] S1 Preparation of polyorganosiloxane elastomers:

[0016] With a Si-H bond to vinyl molar ratio of less than 1, hydrogen-containing polysiloxane, ethylene polysiloxane, and the third functional component were mixed, a platinum catalyst was added, and the mixture was stirred until homogeneous. The mixture was heated to 75-120℃ and reacted for 30-120 min. After cooling, the mixture was pulverized to obtain a polyorganosiloxane elastomer ViSE with residual vinyl in its structure. The residual vinyl content was 0.01wt%-0.8wt% of the total mass of the polyorganosiloxane elastomer ViSE.

[0017] S2 Preparation of pre-emulsified suspension:

[0018] Take 40-70 parts of methyl methacrylate, 27-60 parts of other acrylates, and 0-3 parts of crosslinking agent, stir and mix well to obtain acrylic monomer mixture A; based on the total mass of acrylic monomer mixture A, add 1wt%-2wt% of molecular weight regulator, 10wt%-50wt% of polyorganosiloxane elastomer ViSE obtained in step S1, and 1wt%-3wt% of oil-soluble initiator to obtain monomer mixture B containing oil-soluble initiator; separately, based on the total mass of monomer mixture B, take 5wt%-10wt% of surfactant, dissolve it in water, and then add it to monomer mixture B for pre-emulsification treatment to obtain a pre-emulsified suspension;

[0019] S3 Preparation of acrylic resin-coated silicone elastomer PA@SE and post-demulsification treatment:

[0020] First, divide the pre-emulsified suspension into two portions. Take one portion of the pre-emulsified suspension, stir it, heat it 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 it to room temperature, add a demulsifier to demulsify it, filter out the solid, wash and dry it to obtain acrylic resin-coated silicone elastomer PA@SE.

[0021] Preferably, in step S1, the average particle size of the polyorganosiloxane elastomer is 30 nm-50 μm.

[0022] Preferably, in step S2, the other acrylates (AE) contain C in their structure. 2-12 Alkyl or C 5-12 The cycloalkyl acrylate or methacrylate may be selected from one or more of the following: 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, etc.

[0023] The crosslinking agent may be selected from one or more of the following: 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, methylenebisacrylamide, N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, etc.

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

[0026] This invention first synthesizes a novel polyorganosiloxane elastomer ViSE by hydrosilylation addition reaction of hydrogen-containing polysiloxane (HPS), vinyl polysiloxane (VPS), and a third-class alkenyl functional monomer component (VF). The ViSE is then pulverized and ball-milled to obtain a polyorganosiloxane elastomer ViSE with a certain amount of reactive alkenyl groups remaining in its structure. Using this elastic powder as the core monomer of the reactive organosilicon macromolecule, the ViSE is pre-emulsified with an oil-phase acrylate monomer under the combined action of anionic and nonionic surfactants and a high-shear emulsifier. Seed suspension emulsion copolymerization is then performed to obtain a core-shell copolymer PA@SE, with an acrylate resin outer shell, a polyorganosiloxane elastomer core, and the inner and outer shell layers chemically bonded together by covalent bonds. By designing the shell PA resin structure and controlling the particle size and structure of the core organosilicon elastic powder, this invention not only enables the shell-core structure PA@SE material to be miscible with conventional PC resins, solving the common industrial technical problems of immiscibility and easy phase separation between existing polyorganosiloxanes and PC resins, but also enables PA@SE to be used in the processing of PC and PC / ABS alloy resins or composite materials, achieving significant toughening and strengthening effects without reducing mechanical properties. Detailed Implementation

[0027] 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.

[0028] This invention provides an acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization. The PA@SE has a core-shell structure. The shell of the PA@SE is a linear or lightly cross-linked acrylic resin, specifically a copolymer of methyl methacrylate (MMA) and other acrylates (AE), and / or a cross-linking agent. The core of the PA@SE is a polyorganosiloxane elastomer ViSE formed by hydrosilylation addition reaction of hydrogen-containing polysiloxane (HPS), ethylene polysiloxane (VPS), and a third functional component (VF).

[0029] Other acrylates (AEs) contain C in their structure. 2-12 Alkyl or C 5-12The cycloalkyl acrylate or methacrylate may be selected from one or more of the following: ethyl methacrylate, propyl methacrylate, n-butyl methacrylate (MBA), isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate (CHMA), and isobornyl methacrylate (IBOMA).

[0030] The crosslinking agent may be selected from one or more of the following: ethylene glycol dimethacrylate, propylene glycol dimethacrylate (PDMA), butanediol dimethacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate (DPGDA), triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, methylenebisacrylamide, N-hydroxymethylacrylamide, and N-hydroxyethylacrylamide.

[0031] 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 A siloxane copolymer of one or more copolymer segments, such as alkylsiloxanes. The Si-H bond content in hydrogen-containing polysiloxanes (HPS) is approximately 0.05%-1.6%, and the viscosity is approximately 20-1000 mPa·s.

[0032] 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. The vinyl (Vi) content in ethylene polysiloxane (VPS) is approximately 0.1wt%-3wt%, and the viscosity is approximately 100-60000 mPa·s.

[0033] The third functional component (VF) is a substance containing one or two alkenyl groups in its structure, capable of undergoing hydrosilylation addition reaction with Si-H bonds, and increasing the miscibility of the polyorganosiloxane elastomer ViSE with acrylate resins. Specifically, it can be selected from vinyl acetate (VA), allyl acetate (AA), allyl phenyl ether, allyl benzyl ether (ABE), cyclohexyl vinyl ether, α-C... 8-18 One or more of the following: olefins, 1,6-hexadiene, 1,9-decadiene, (poly)ethylene glycol dielyl ether, (poly)propylene glycol dielyl ether.

[0034] In this invention, when preparing the core material, 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 75-120℃, and the reaction time is 30-120min. The residual vinyl (Vi) content in the polyorganosiloxane elastomer ViSE after the reaction is about 0.01wt%-0.8wt% of the total mass of the polyorganosiloxane elastomer ViSE.

[0035] The method for preparing acrylic resin-coated silicone elastomer PA@SE of the present invention includes the following steps:

[0036] (1) Preparation of polyorganosiloxane elastomer ViSE

[0037] 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, so that the residual vinyl (Vi) content in the system after hydrosilylation addition reaction is about 0.01wt%-0.8wt% (based on the mass fraction of Vi remaining per 100g of polysiloxane elastomer). Take the above three components, add platinum catalyst according to the stoichiometric ratio, stir and mix well, and then heat to 75-120℃ to carry out hydrosilylation addition reaction for 30-120min. After cooling to room temperature, pulverize to obtain white uniform nano-micro elastic powder with an average particle size φ of about 30nm-50μm, which is the polyorganosiloxane elastomer ViSE with reactive vinyl residue on the surface, wherein the vinyl residue content is about 0.01wt%-0.8wt%, and store for later use.

[0038] 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 or more 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 typically 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 0.05wt%-0.5wt% of the total mass of HPS, VPS, and VF.

[0039] (2) Preparation of pre-emulsified suspension

[0040] Take 40-70 parts by weight of methyl methacrylate (MMA), 27-60 parts of other acrylates (AE), and 0-3 parts of crosslinking agent, mix them well to obtain acrylic monomer mixture A; then add 1wt%-2wt% of molecular weight regulator, 10wt%-50wt% of polyorganosiloxane elastomer ViSE and 1wt%-3wt% of oil-soluble initiator according to the total mass of acrylic monomer mixture A, mix them well to obtain monomer mixture B.

[0041] Take another surfactant (SA), the amount of which is 5wt%-10wt% of the mass of monomer mixture B, add it to deionized water, stir to dissolve, prepare a transparent aqueous solution, then add monomer 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.

[0042] The molecular weight regulator is a substance that can terminate or regulate the polymerization rate of acrylate monomers. 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, mercaptophenol, 2,6-dimethylmercaptophenol, mercaptobenzoic acid, etc. Among them, thiols and thiophenols can be used directly or after being fully diluted with ester solvents before use.

[0043] Oil-soluble initiators are substances that can dissolve in oil-phase acrylate monomers, decompose upon heating to generate free radicals, and effectively initiate the polymerization reaction of monomers such as acrylates. They can be selected from one or more of benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), percarbonate, tert-butyl peroxide, etc.

[0044] Surfactants (SA) are mixtures of anionic and nonionic surfactants, with a mass ratio of anionic to nonionic surfactant of 1:0.5-5. The anionic surfactant can be selected from one or more of the following: sodium fatty alcohol polyoxyethylene ether sulfate (AES), sodium dodecylbenzene sulfonate (DBSA-Na), sodium secondary alkyl sulfonate (AOS), sodium dodecyl sulfate (SDS), potassium dodecyl sulfate (K12), and sodium salts of carboxylated fatty alcohol polyoxyethylene ethers, such as AEC-9 and AEC-10. The nonionic surfactant can be selected from fatty alcohol polyoxyethylene ethers with EO numbers of 3-20 (such as AEO-3, AEO-9, and O-15 and O-20). One or more of the following: O-25, nonylphenol polyoxyethylene ether OP (such as OP-4, OP-7, OP-10, OP-15, etc.), octylphenol polyoxyethylene ether Tx (such as Tx-4, Tx-7, Tx-10), fatty acid polyoxyethylene ether ester (SG), isomeric decayl alcohol polyoxyethylene ether (such as 1350, 1370, 1390, 13120, etc.), and isomeric decayl alcohol polyoxyethylene ether XP or XL (such as XP-30, XP-70, XP-90 or XL-40, XL-70, XL-90, etc.).

[0045] Thickeners are water-soluble substances that can dissolve in water and significantly alter the viscosity of the aqueous phase. Specific options include carbomer and acrylic resin thickeners with an average molecular weight (Mn) of approximately (3-10) × 10⁻⁶. 4 One of the following: hydroxyethyl cellulose or hydroxypropyl cellulose, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol (such as 1788 or 1799), polyethylene glycol, etc.

[0046] (3) Preparation of acrylic resin-coated silicone elastomer PA@SE and post-demulsification treatment

[0047] 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 min. 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 h, and then keep the reaction at the temperature for 1-4 h. Then add a demulsifier to demulsify, filter out the solid, wash with deionized water and ethanol respectively, and dry at 50-70℃ for 1-2 h. After pulverization, an acrylic resin-coated silicone elastomer with a shell and core structure of acrylic resin as the shell and addition-type polyorganosiloxane elastomer ViSE is obtained, denoted as PA@SE, with an average particle size of 20-300 μm.

[0048] The water-soluble initiator can be selected from ammonium persulfate (APS) or potassium persulfate (KPS). The amount of water-soluble initiator added is 0.1wt%-1.0wt% of the total mass of the pre-emulsified suspension. It can be prepared into a solution of a certain concentration with water before use.

[0049] 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.

[0050] During filtration, atmospheric pressure filtration or vacuum filtration can be used with filter paper, 60-200 mesh copper mesh, 120-200 mesh nylon mesh, 60-200 mesh industrial filter cloth or filter bag.

[0051] The acrylic resin-coated silicone elastomer PA@SE proposed in this invention, through the control of the shell resin structure, core elastomer structure, and particle size, not only achieves high miscibility with organic resins such as acrylic resins, PC resins, and epoxy resins, but also, when used for the modification and processing of PC resins, can achieve significant toughening and impact resistance effects. It can be applied in the fields of PC resin, PC alloy processing, thermosetting epoxy resins and coatings, etc., and can be used as a toughening agent for thermoplastic PC resins, thermosetting epoxy resins and coatings, and acrylic resins and coatings. Moreover, it does not exhibit separation or delamination during use, and has the effect of increasing the flexibility and impact resistance of the cured resin coating.

[0052] Example 1

[0053] Step 1: Take 20.0g of poly(methylhydrosiloxane-dimethylsiloxane) (denoted as HPS-1) with a silane-hydrogen bond molar content of approximately 0.5%, 5.01g of allyl acetate AA, and 54.0g of poly(dimethylsiloxane-diphenylsiloxane) (denoted as VPS-1) with an end-group vinyl dimethylsilyl capping of approximately 3wt% and mix them. Then add 0.39g of platinum complex catalyst KP-22 (Shanghai Neutron Star Chemical Co., Ltd.), stir evenly, and then... The mixture was then heated to 95°C and reacted for 30 minutes to obtain a preliminary elastomer product with a total mass of approximately 79.01 g. After cooling to room temperature, the elastomer was crushed into coarse particles with an average particle size of approximately 1.92 mm using a molecular crusher. Then, it was ball-milled for 4 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 33.24 nm, which is the polyorganosiloxane elastomer, denoted as ViSE-1. The vinyl content in ViSE-1 (the mass fraction of vinyl contained in 100 g of ViSE-1) is approximately 0.34 wt%.

[0054] Step 2: Weigh 70.0g of methyl methacrylate (MMA), 20.0g of butyl acrylate (BA), and 10.0g of cyclohexyl methacrylate (CHMA) separately, mix well, and obtain approximately 100.0g of acrylic monomer mixture A-1; then add approximately 2.0g of dodecanethiol, approximately 50g of ViSE-1, and approximately 2.0g of benzoyl peroxide (BPO), disperse and mix well, and obtain a total of approximately 154.0g of monomer mixture B-1. Take 7.70g of anionic surfactant DBSA-Na and 7.70g of nonionic surfactant isotridecyl alcohol polyoxyethylene ether 1390, mix, and obtain surfactant SA-1; then add approximately 382.60g of deionized water, stir to dissolve until a clear aqueous solution is obtained, then add monomer mixture B-1, and emulsify for 5 minutes using an IKA high-shear emulsifier with a speed of approximately 10000r / min, then add approximately 3×10 Mn. 4 Hydroxyethyl cellulose was used to adjust the viscosity of the system to approximately 10.80 mPa·s, resulting in a total of approximately 552.0 g of pre-emulsified suspension. A-1, ViSE-1, and SA-1 were used as effective components, with the effective components accounting for approximately 30 wt% of the total mass of the pre-emulsified suspension.

[0055] Step 3: In a three-necked flask equipped with a thermometer, electric stirrer, and reflux condenser, add 55.2g 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 10.0g of 10% APS aqueous solution dropwise at a uniform rate, controlling the addition to be completed in approximately 2 hours. Maintain the reaction at 80℃ for 1 hour to obtain a white suspension containing a large number of fine elastic solid particles. Cool the white suspension to room temperature and transfer it to a beaker. While stirring, add 27.60g of sodium chloride (NaCl) to break the emulsion and form a fine mud-like solid. Filter the solid through a 200-mesh nylon mesh. Wash the filtered solid three times with an equal mass of deionized water, then rinse once with ethanol. Dry at 70℃ for 1 hour to obtain approximately 128.30g of white elastomer powder, i.e., acrylic resin-coated silicone elastomer, denoted as PA@SE-1.

[0056] Example 2

[0057] Step 1: Take 20.0g of a side-linked trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane) (denoted as HPS-2) with a silane-hydrogen bond molar 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) (denoted as VPS-2) with a vinyl content of approximately 1wt%. Mix them together, then add 0.34g of platinum complex catalyst KP-22 (Shanghai Neutron Star Chemical Co., Ltd.), stir evenly, and then heat to [temperature missing]. The reaction was carried out at 90℃ 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 6 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, which is the polyorganosiloxane elastomer, denoted as ViSE-2. The vinyl content in ViSE-2 (the mass fraction of vinyl contained in 100 g of ViSE-2) is approximately 0.11 wt%.

[0058] Step 2: Weigh out 55.0g of methyl methacrylate (MMA), 29.4g of butyl acrylate (BA), 15.0g of isobornyl methacrylate (IBOMA), and 1.0g of propylene glycol dimethacrylate (PDMA), mix them well, and obtain approximately 100.0g of acrylic monomer mixture A-2; then add approximately 1.0g of mercaptoethanol, approximately 30g of ViSE-2, and approximately 1.5g of azobisisobutyronitrile (AIBN), disperse and mix well, and obtain a total of approximately 132.5g of monomer mixture B-2. Take 3.27g of anionic surfactant SDS and 3.28g of nonionic surfactant isomeric deca-ol polyoxyethylene ether XP-90, mix them to obtain surfactant SA-2; then add about 411.15g of deionized water, stir to dissolve until a clear aqueous solution is obtained, then add monomer mixture B-2, and emulsify for 6min using an IKA high-shear emulsifier with a speed of about 10000r / min. Then add carbomer and adjust the viscosity of the system to about 95.6mPa.s to obtain a total of about 550.2g of pre-emulsified suspension, in which A-2, ViSE-2, and SA-2 are the effective components, and the proportion of effective components is about 25wt% of the total mass of the pre-emulsified suspension.

[0059] Step 3: In a three-necked flask equipped with a thermometer, electric stirrer, and reflux condenser, add 137.55g of pre-emulsified suspension, stir, heat to 80℃, and react for 15 minutes. Then, add the remaining pre-emulsified suspension and 8.0g of 10% KPS aqueous solution dropwise at a uniform rate, controlling the addition to be completed in about 2 hours. Then, maintain the reaction at 80℃ for 1.5 hours to obtain a white suspension containing a large number of fine elastic solid particles. Cool the white suspension to room temperature and transfer it to a beaker. While stirring, add 28.02g of potassium chloride (KCl) to break the emulsion and form a fine mud-like solid. Filter the solid through a 200-mesh nylon mesh. Wash the filtered solid three times with an equal mass of deionized water, then rinse once with ethanol. Dry at 65℃ for 2 hours to obtain approximately 111.36g of white elastomer powder, namely acrylic resin-coated silicone elastomer, denoted as PA@SE-2.

[0060] Example 3

[0061] Step 1: Take 10.0g of trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methyldodecylsiloxane) (denoted as HPS-3) with a silane-hydrogen bond molar 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 approximately 3, and 125.0g of vinyl-dimethylsilyl-terminated poly(vinylsiloxane-dimethylsiloxane-diphenylsiloxane) (denoted as VPS-3) with a vinyl content of approximately 0.5wt% and vinyl groups attached to both ends. Mix them together, and then add 0.15g of platinum complex catalyst KP-22 (Shanghai). 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 approximately 145.51 g. After cooling to room temperature, the elastomer was crushed into coarse particles with an average particle size of approximately 2.61 mm 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 approximately 215.37 nm, which is the polyorganosiloxane elastomer, denoted as ViSE-3. The vinyl content in ViSE-3 (the mass fraction of vinyl contained in 100 g of ViSE-3) is approximately 0.15 wt%.

[0062] Step 2: Weigh out 60.0g of methyl methacrylate (MMA), 23.2g of n-butyl methacrylate (MBA), 15.0g of cyclohexyl methacrylate (CHMA), and 1.8g of dipropylene glycol dimethacrylate (DPGDA), mix them well, and obtain approximately 100.0g of acrylic monomer mixture A-3; then add approximately 1.0g of mercaptoacetic acid, 25.0g of ViSE-3, and approximately 1.25g of azobisisobutyronitrile (AIBN), disperse and mix well, and obtain a total of approximately 127.25g of monomer mixture B-3. Take 3.02g of sodium dodecyl sulfate and 4.54g of nonionic surfactant isomeric decayl alcohol polyoxyethylene ether XL-70, mix them to obtain surfactant SA-3; then add about 246.79g of deionized water, stir to dissolve until a clear aqueous solution is obtained, then add monomer mixture B-3, and emulsify for 6min using an IKA high shear emulsifier with a speed of about 10000r / min. Then add thickener 8W to adjust the viscosity of the system to about 87.90mPa.s, and a total of about 381.60g of pre-emulsified suspension is obtained, in which A-3, ViSE-3, and SA-3 are the effective components, and the proportion of effective components is about 25wt% of the total mass of the pre-emulsified suspension.

[0063] Step 3: In a three-necked flask equipped with a thermometer, electric stirrer, and reflux condenser, add 76.32g of pre-emulsified suspension, stir, heat to 80℃, and react for 15 minutes. Then, add the remaining pre-emulsified suspension and 10.0g of 10% KPS aqueous solution dropwise at a uniform rate, controlling the addition to be completed in about 2 hours. Then, keep the reaction at 85℃ for 1 hour to obtain a white suspension containing a large number of fine elastic solid particles. Cool the white suspension to room temperature and transfer it to a beaker. While stirring, add 20.08g of sodium bromide (NaBr) to break the emulsion and form a fine mud-like solid. Filter the solid through a 200-mesh nylon mesh. Wash the filtered solid three times with an equal mass of deionized water, then rinse once with ethanol. Dry at 70℃ for 1.5 hours to obtain approximately 107.1g of white elastomer powder, namely acrylic resin-coated silicone elastomer, denoted as PA@SE-3.

[0064] Comparative Example 1

[0065] 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:

[0066] Experiment 1: 20.0g HPS-1, 5.01g allyl acetate, and 100.0g VPS-1 were mixed, and then 0.40g of complexed platinum catalyst KP-22 was added. The mixture was stirred evenly in one pot, and then heated to 95℃ for 30 minutes. After the reaction, an organosilicon elastomer with a vinyl residue of 1.32wt% 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.

[0067] Experiment 2: 20.0g HPS-1, 5.01g allyl acetate, and 150.0g VPS-1 were mixed thoroughly, and then 0.40g of platinum complex catalyst KP-22 was added. The mixture was stirred until homogeneous, and then heated to 95℃ for 30 minutes. After the reaction, an organosilicon elastomer with a vinyl residue of 1.77wt% 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.

[0068] Experiment 3: The silicone elastomer obtained in Experiment 2 was swollen with the acrylate monomer in Example 1, and then reacted with the method in step 3 of Example 1 to prepare the target product acrylic resin coated silicone elastomer. The results showed that during the drop addition of the pre-emulsified suspension, a large amount of gel appeared in the system or directly coagulated into a soft elastomer, that is, the preparation of the target product acrylic resin coated silicone elastomer failed.

[0069] Through the preparation process of this comparative example, it can be seen that the amount of raw materials used and other conditions are key factors affecting whether the product can be successfully prepared when preparing polyorganosiloxane elastomer ViSE. When the amount used exceeds the range specified in 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 final product of acrylic resin-coated silicone elastomer PA@SE.

[0070] Comparative Example 2

[0071] The difference between this comparative example and Example 2 is that the amount of crosslinking agent PDMA in step 2 was increased to 10.0 g, while the rest of the preparation process remained unchanged. The results showed that the system gelled during the dropwise addition of the pre-emulsified suspension, preventing further reaction. In other words, the preparation of the target product, acrylic resin-coated silicone elastomer, failed.

[0072] 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 acrylic resin-coated silicone elastomer PA@SE. When the amount of raw materials and usage exceeds the range defined by this invention, the acrylic resin-coated silicone elastomer PA@SE product with the specific structure and morphology conceived in this invention cannot be successfully obtained.

[0073] Comparative Example 3

[0074] The difference between this comparative example and Example 1 is that allyl acetate is not introduced and the VPS structure does not contain diphenylsiloxane units. The specific differences are as follows:

[0075] In step 1, 20.0g of HPS-1 with a silane-hydrogen bond molar content of approximately 0.5% and 99.0g of commercially available vinyl dimethylsilyl-terminated polydimethylsiloxane (VPS-6, Jiangxi Huarunzhi New Material Co., Ltd.) with a vinyl content of approximately 3wt% were taken and mixed. Then, 0.39g of complexed platinum catalyst KP-22 was added and stirred evenly. The mixture was then heated to 95℃ and reacted for 30min to obtain a preliminary elastomer product with a total mass of approximately 79.01g. After cooling to room temperature, the elastomer was pulverized using a molecular crusher and then 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 31.53nm, which is the polyorganosiloxane elastomer, denoted as ViSE-6. The vinyl content in 100g of ViSE-6 is approximately 0.23wt%. Subsequent steps and process conditions were the same as in Example 1 to prepare an acrylic resin-coated organosilicon elastomer, denoted as PA@SE-6.

[0076] Test case

[0077] The styrene-acrylic resin-coated silicone elastomers prepared in Examples 1-3 and Comparative Example 3 were respectively designated as PA@SE-1, PA@SE-2, PA@SE-3, and PA@SE-6 as samples, and PA@SE toughened modified PC resins were prepared accordingly.

[0078] The preparation process of PA@SE toughened modified PC resin is as follows: PC resin (PC-1100 from Lotte, South Korea) and PA@SE are mixed at a mass ratio of 1:24. Antioxidant-225, accounting for 0.1 wt% of the mass of PC resin, is added and mixed evenly. 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 by the instrument. The melt-mixed sample is then placed in a mold and pressed into a sheet using a flat vulcanizing apparatus to obtain a sample sheet with a thickness of 2 mm. Alternatively, the toughening agent, PC resin masterbatch, and antioxidant-225 are mixed evenly at the above mass ratio and then melt-mixed at 250℃ using a twin-screw extruder. The mixture is then extruded and granulated, and injection molded into notched impact and mechanical property test strips using an injection molding machine.

[0079] Then, the different PA@SE toughened modified PC resins prepared were designated as MPC, and unmodified blank PC resin was taken as the blank group. The polyorganosiloxane elastomer ViSE-1 in Example 1 was physically compounded with PC resin at a mass ratio of 1:24 as the reference group. The application performance was tested according to the relevant standard injection molding test strips, as follows:

[0080] (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 MPCs was determined by a TH-100 haze meter (Hangzhou Caipu Technology Co., Ltd.).

[0081] (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 MPCs was determined within 3 minutes using a Shimadzu AGS-X electronic universal testing machine.

[0082] (3) Samples were prepared in accordance with GB / T1040-2006.9 "Determination of tensile properties of plastics" and the tensile strength of different MPCs was determined using a Shimadzu AGS-X electronic universal testing machine.

[0083] The results of the above performance tests are summarized in Table 1 below:

[0084] Table 1. Material property test results of different samples

[0085]

[0086] The above experimental and performance test results show that, compared with Comparative Example 3 and the blank group, the acrylic resin-coated silicone elastomer PA@SE and its preparation method proposed in Examples 1 to 3 exhibit significantly higher torque and energy consumption. Furthermore, the modified PC resin prepared using the acrylic resin-coated silicone elastomer PA@SE from Examples 1 to 3 has lower light transmittance, and its haze, low-temperature impact resistance, and tensile strength are significantly higher than those of the silicone elastomer-modified PC resin in Comparative Example 3 and the blank PC resin in the blank group. This demonstrates that the acrylic resin-coated silicone elastomer PA@SE and its preparation method proposed in this invention can indeed improve the mechanical properties of modified PC resins, such as impact resistance and tensile strength, by enhancing the miscibility of PA@SE with PC resins.

[0087] 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. An acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization, characterized in that, Having a core-shell structure, the shell of the PA@SE is a linear structure or a slightly cross-linked acrylic resin, and the core of the PA@SE is a polyorganosiloxane elastomer ViSE formed by hydrosilylation addition reaction of hydrogen-containing polysiloxane, ethylene polysiloxane and a third functional component. The polyorganosiloxane elastomer ViSE contains residual vinyl groups, with the residual vinyl group amounting to 0.01 wt%-0.8 wt% of the total mass of the polyorganosiloxane elastomer ViSE. The third functional component includes vinyl acetate, allyl acetate, 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, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, polypropylene glycol diallyl ether, and propylene glycol diallyl ether. The ethylene polysiloxane has vinyl groups and / or side chains, and its main chain consists of diphenylsiloxane, dimethylsiloxane, diethylsiloxane, methylphenylsiloxane, and methyl C. 2-18 Siloxane copolymers of at least one or more copolymer units in alkylsiloxanes; The raw materials for acrylic resin include 40-70 parts methyl methacrylate, 27-60 parts other acrylates, and 0-3 parts crosslinking agent.

2. The acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization 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, and methylC. 2-18 A siloxane copolymer of at least two copolymer units in an alkylsiloxane.

3. The acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization according to claim 2, characterized in that, The Si-H bond content in the hydrogen-containing polysiloxane is 0.05%-1.6%.

4. The acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization according to claim 1, characterized in that, The vinyl content in the ethylene polysiloxane is 0.1wt%-3wt%.

5. The acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization according to claim 1, characterized in that, The acrylic resin is a copolymer of methyl methacrylate and other acrylates, or a copolymer of methyl methacrylate and other acrylates and a crosslinking agent; the other acrylates contain C in their structure. 2-12 Alkyl or C 5-12 Cycloalkyl acrylates or methacrylates.

6. A method for preparing an acrylic resin-coated silicone elastomer PA@SE prepared by aqueous suspension emulsion polymerization according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1 Preparation of polyorganosiloxane elastomers: With a Si-H bond to vinyl molar ratio of less than 1, hydrogen-containing polysiloxane, ethylene polysiloxane, and the third functional component were mixed, a platinum catalyst was added, and the mixture was stirred until homogeneous. The mixture was heated to 75-120℃ and reacted for 30-120 min. After cooling, the mixture was pulverized to obtain a polyorganosiloxane elastomer ViSE with residual vinyl in its structure. The residual vinyl content was 0.01wt%-0.8wt% of the total mass of the polyorganosiloxane elastomer ViSE. S2 Preparation of pre-emulsified suspension: Take methyl methacrylate, other acrylates, and optional crosslinking agent, stir and mix them to obtain acrylic monomer mixture A; then add molecular weight regulator, polyorganosiloxane elastomer ViSE obtained in step S1, and oil-soluble initiator to obtain monomer mixture B containing oil-soluble initiator; separately take surfactant, dissolve it in water, and then add it to monomer mixture B for pre-emulsification treatment to obtain pre-emulsified suspension. Based on the total mass of acrylic monomer mixture A, the molecular weight regulator is added at 1wt%-2wt%, the polyorganosiloxane elastomer ViSE is added at 10wt%-50wt%, and the oil-soluble initiator is added at 1wt%-3wt%. The amount of surfactant added is 5wt%-10wt% based on the total mass of monomer mixture B; S3 Preparation of acrylic resin-coated silicone elastomer PA@SE and post-demulsification treatment: First, divide the pre-emulsified suspension into two portions. Take one portion of the pre-emulsified suspension, stir it, heat it 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 it to room temperature, add a demulsifier to demulsify it, filter out the solid, wash and dry it to obtain acrylic resin-coated silicone elastomer PA@SE.

7. The method for preparing acrylic resin-coated silicone elastomer PA@SE by aqueous suspension emulsion polymerization according to claim 6, characterized in that, In step S2, the other acrylates contain C in their structure. 2-12 Alkyl or C 5-12 cycloalkyl acrylates or methacrylates; The crosslinking agent is selected from one or more of 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, and tripropylene glycol di(meth)acrylate.

8. The acrylic resin-coated silicone elastomer PA@SE according to any one of claims 1 to 5, or the acrylic resin-coated silicone elastomer PA@SE prepared by the preparation method according to claim 6 or 7, is applied to resin materials.

Images