A shell-core structure phenylpropane resin modified silicone elastomer toughening agent, a preparation method and application thereof

Abstract

The present application relates to PC resin toughening agent technical field, aiming at the problems of poor mutual solubility of organic silicon material and PC resin, poor low-temperature toughening performance of traditional toughening agent, etc., the present application discloses a kind of shell-core structure phenylpropene resin modified organic silicon elastomer toughening agent and its preparation method and application, including the following steps: hydrogen-containing silicone oil, vinyl silicone oil, third alkenyl functional component and catalyst are uniformly mixed, pre-emulsification is carried out under the action of surface active agent and thickening agent, and organic silicon pre-emulsion SiE is obtained;Another alkenyl phenyl compound, acrylic ester and / or crosslinking agent are uniformly mixed, then molecular weight regulator and oil-soluble initiator are added, pre-emulsification is carried out under the action of surface active agent and water, and phenylpropene pre-emulsion SAE is obtained;Then, organic silicon pre-emulsion is heated first to carry out water-phase silicon hydrogenation addition reaction, then phenylpropene pre-emulsion is added dropwise to carry out suspension emulsion copolymerization, then demulsification, drying, and the shell-core structure phenylpropene resin modified organic silicon elastomer toughening agent can be obtained.

Description

Technical Field

[0001] This invention relates to the field of PC resin toughening agent technology, and more specifically, to a core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent, its preparation method, and its application. Background Technology

[0002] Polysiloxanes are a class of polymeric compounds composed of alternating silicon and oxygen atoms. They possess excellent high and low temperature resistance and chemical stability, and exhibit flexible, hydrophobic, and UV-resistant chain segments. Therefore, using polysiloxanes to toughen and modify bisphenol A polycarbonate (PC) resins, which have high rigidity, poor aging resistance, and low-temperature impact resistance, is theoretically feasible. However, traditional polysiloxanes, such as polydimethylsiloxane (PDMS), while flexible in chain segment, differ significantly from PC resins in molecular structure, solubility parameters, and polarity. Consequently, combining the two can easily lead to phase separation and delamination, resulting in a substantial decrease in the mechanical properties of the modified PC resin.

[0003] Currently, by utilizing the structural features of PC resin molecules, such as the presence of benzene ring groups, and through core-shell molecular structure design, it is hoped that this defect can be improved. For example, patent CN106957396A disclosed a self-cleaning wear-resistant organosilicon toughening agent and its preparation method and application. In the preparation of this toughening agent, small molecule organosiloxane monomers are first mixed evenly, subjected to high-speed shearing, and added to an aqueous solution containing a catalyst and emulsifier for reaction to obtain an organopolysiloxane core emulsion. The pH value of the organosilicon core emulsion is adjusted with an alkaline solution, and then a system of fluorinated acrylate monomers, comonomers, initiators, and chain transfer agents is added for reaction to obtain an organopolysiloxane-grafted fluorinated acrylate polymer emulsion. The organopolysiloxane-grafted fluorinated acrylate polymer emulsion is diluted, demulsified, centrifuged, dried, and pulverized to obtain a self-cleaning wear-resistant organosilicon toughening agent.

[0004] However, existing toughening agents and their preparation processes often employ ring-opening polymerization of small-molecule organosilicon monomers, or hydrolytic condensation reactions of methyl or phenyl silanes with reactive vinyl silanes or methacryloyloxypropyl silanes, to obtain core-shell structure toughening agents. When used to modify bisphenol A polycarbonate resin materials, these toughening agents still suffer from poor miscibility with the bisphenol A polycarbonate resin matrix, resulting in insufficient toughness and impact resistance, among other mechanical properties, in the modified target PC resin. Summary of the Invention

[0005] The purpose of this invention is to solve the problem of poor miscibility between existing materials such as polyorganosiloxane toughening agents and PC resin base materials, which leads to insufficient low-temperature toughening performance of PC resin after toughening agent modification.

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

[0007] This invention provides a method for preparing a core-shell structured styrene-acrylic resin modified organosilicon elastomer toughening agent, comprising the following steps:

[0008] S1 Preparation of organosilicon pre-emulsion SiE: With an alkenyl (Vi) to Si-H bond molar ratio greater than 1, hydrogen-containing silicone oil (PHMS), vinyl silicone oil (VPS), third alkenyl functional component (VF) and platinum catalyst are taken, stirred and mixed to obtain organosilicon mixture SiM; pre-emulsification is carried out under the action of surfactant SA and thickener to obtain organosilicon pre-emulsion SiE.

[0009] S2 Preparation of styrene-acrylic preemulsion SAE: Take 17-60 parts by mass of alkenylphenyl compound, 40-70 parts by mass of acrylate and 0-3 parts by mass of crosslinking agent and mix them to obtain styrene-acrylic monomer mixture A; then add molecular weight regulator and oil-soluble initiator, stir and mix to obtain styrene-acrylic monomer mixture B containing oil-soluble initiator; then, preemulsify under the action of surfactant SB to obtain styrene-acrylic preemulsion SAE.

[0010] S3 Preparation of styrene-acrylic resin modified organosilicon elastomer suspension: Take organosilicon pre-emulsion SiE, stir, heat to 75-90℃, and carry out aqueous phase hydrosilylation addition reaction for 2-6h to obtain organosilicon elastomer suspension with intermediate vinyl residue of about 0.05wt%-1.0wt%; then, add styrene-acrylic pre-emulsion SAE and water-soluble initiator dropwise, and keep the reaction at 75-85℃ for 1-4h to obtain styrene-acrylic resin modified organosilicon elastomer suspension.

[0011] Under the condition of the same effective component content, the mass ratio of organosilicon preemulsion SiE to styrene-acrylic preemulsion SAE is controlled to be (1-5):10 (wt / wt).

[0012] S4 Suspension Demulsification Treatment: Take a suspension of styrene-acrylic resin modified organosilicon elastomer, add a demulsifier to demulsify, filter out the solid, wash and dry to obtain a core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent.

[0013] Preferably, the hydrogen-containing silicone oil (PHMS) is a polyorganosiloxane with Si-H bonds in its molecular end groups and / or side chains. The molar content of Si-H bonds in the hydrogen-containing silicone oil (based on the number of moles of silicon-hydrogen bonds in 100g of polysiloxane) is approximately 0.05%-1.0%, and the viscosity is approximately 10-1000 mPa·s. Here, the molar content of Si-H bonds in the hydrogen-containing silicone oil refers to the molar amount of Si-H bonds, i.e., the content of reactive active hydrogen. According to conventional practice in the art, the key component, reactive hydrogen, is defined by the molar content of Si-H bonds.

[0014] Specifically, the hydrogen-containing silicone oil can be selected from Si-H end-capped polydimethylsiloxane, polydiethylsiloxane, 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. 2-18 Alkylsiloxanes), 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 One or more of alkylsiloxanes, etc., can be 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.

[0015] Vinyl silicone oil (VPS) is a polyorganosiloxane containing vinyl (Vi) groups at the end groups and / or side chains. The vinyl Vi content in vinyl silicone oil (based on the mass fraction of vinyl in 100g of silicone oil) is approximately 0.1wt%-3wt%, and the viscosity is approximately 20-60000mPa.s. Here, the vinyl content in vinyl silicone oil refers to the mass percentage of reactive vinyl groups.

[0016] Specifically, the vinyl silicone oil can be selected from vinyl-terminated polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, poly(dimethylsiloxane-diethylsiloxane), poly(dimethylsiloxane-methylphenylsiloxane), poly(dimethylsiloxane-diphenylsiloxane), poly(dimethylsiloxane-diphenylsiloxane), poly(dimethylsiloxane-methylC) 2-18Alkylsiloxanes), 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. 2-18 Alkylsiloxanes), 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., can be ordered or commissioned for processing from companies such as Shanghai Jiancheng Organosilicon Co., Ltd., Jiangxi Huarunzhi New Materials Co., Ltd., Tangshan Sanyou Silicon Industry Co., Ltd., Shenzhen Jiefengchuan Chemical Technology Co., Ltd., and Wuhan Kangqiong Biomedical Technology Co., Ltd.

[0017] The third functional component is selected from styrene, p-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, and (poly)propylene glycol dielyl ether.

[0018] Preferably, the surfactant SA is dissolved in deionized water to prepare a transparent aqueous solution, and then a silicone oil mixture SiM is added for pre-emulsification using a high-shear emulsifier. The amount of deionized water is controlled such that the total mass of vinyl silicone oil, hydrogen-containing silicone oil, third alkenyl functional component and surfactant SA accounts for 25wt%-35wt% of the mass of the organosilicon pre-emulsion SiE.

[0019] Preferably, the amount of thickener added is such that the viscosity of the adjusted system is approximately 10-100 mPa·s.

[0020] Preferably, in step S2, the amount of molecular weight regulator added is 0.1wt%-1.0wt% and the amount of oil-soluble initiator added is 1wt%-2wt% based on the mass of the styrene-propane monomer mixture A.

[0021] Preferably, the amount of surfactant SB added is 1wt%-5wt% based on the mass of styrene-acrylic monomer mixture B. The surfactant SB is first added to deionized water to prepare an aqueous solution, and then styrene-acrylic monomer mixture B is added. The mixture is pre-emulsified using a high-shear emulsifier to obtain styrene-acrylic pre-emulsion SAE. The total mass of the effective components in the styrene-acrylic pre-emulsion SAE accounts for 25wt%-35wt% of the mass of the styrene-acrylic pre-emulsion SAE.

[0022] Preferably, in step S3, after the organosilicon pre-emulsion undergoes an aqueous hydrosilylation addition reaction, an organosilicon elastomer suspension with reactive vinyl groups remaining in the intermediate molecular structure is obtained, and the residual amount of reactive vinyl groups is controlled to be 0.05wt%-1.0wt% of the total mass of the organosilicon elastomer formed by the reaction of vinyl silicone oil, hydrogen-containing silicone oil and the third functional component.

[0023] Preferably, in step S3, the amount of aqueous initiator is 0.1wt%-0.5wt% of the mass of the styrene-acrylic preemulsion.

[0024] Preferably, the demulsifier is an inorganic salt demulsifier, specifically selected from one or more of sodium chloride, sodium bromide, potassium chloride, potassium bromide, magnesium chloride, magnesium bromide, zinc chloride, zinc bromide, sodium sulfate, potassium sulfate, magnesium sulfate, and zinc sulfate.

[0025] The technical solution of the present invention has the following beneficial effects:

[0026] This invention utilizes aqueous hydrosilylation addition and suspension emulsion polymerization, specifically the aqueous hydrosilylation addition reaction of reactive polysiloxane macromolecules, to first form an organosilicon core with good elasticity and impact resistance. Then, a layer of styrene-acrylic resin miscible with bisphenol A polycarbonate is chemically bonded to the surface of this core. Thus, the shortcomings of PC resin can be improved by modifying the organosilicon elastomer with this core-shell structured styrene-acrylic resin.

[0027] Under the combined action of anionic and nonionic surfactants, and with the aid of high-shear emulsification, vinyl silicone oil (VPS) containing a complexed platinum catalyst is first pre-emulsified with hydrogen-containing silicone oil (PHMS) and a third functional component (VF) in an aqueous phase. Then, a hydrosilylation addition reaction is carried out in micelles to obtain an intermediate, i.e., a silicone rubber elastomer suspension, in which reactive vinyl groups remain in the structure and the hydrosilylation addition product is uniformly suspended in water as a fine solid elastomer. Then, using this intermediate suspension as the source material for the silicone rubber elastomer core, this material is further subjected to suspension emulsion polymerization in an aqueous phase with styrene-acrylic monomers composed of alkenyl phenyl compounds, acrylates and / or crosslinking agents, under the action of free radical initiators and molecular weight modifiers. This yields a shell-core styrene-acrylic resin with a linear or slightly crosslinked shell and an addition-type silicone rubber elastomer core, g-silicone rubber elastomer toughening agent (SASE). This invention, through the design of the SASE shell resin structure, the control of average molecular weight, and the control of the core silicone rubber elastomer structure and particle size, not only enables the target shell-core SASE toughening agent to achieve mutual compatibility and solubility with PC resin and its alloys, solving the problem that traditional polyorganosiloxanes (such as polydimethylsiloxane) are immiscible with PC resin and easily separate from PC resin, resulting in a decrease in the mechanical properties and impact resistance of PC resin systems, but also enables the toughening agent to be used in the processing of PC resin and PC / ABS alloy resin, significantly improving the application properties of PC resin such as flexibility and impact resistance while having little impact on the mechanical properties of PC materials. 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 discloses a core-shell structured styrene-acrylic resin modified organosilicon elastomer toughening agent and its preparation method, comprising the following steps:

[0030] (1) Preparation of silicone preemulsion:

[0031] Weigh out hydrogen-containing silicone oil (PHMS), vinyl silicone oil (VPS), and third alkenyl functional component (VF) according to an alkenyl (Vi) to Si-H bond molar ratio greater than 1, mix them evenly, then add 0.1wt%-0.5wt% of platinum catalyst according to the total mass of VPS, PHMS and VF, stir evenly, and obtain the organosilicon mixture SiM containing platinum catalyst.

[0032] Separately, dissolve surfactant SA in water to prepare a transparent aqueous solution, taking care to control the amount of water used so that the content of the effective components (i.e., the sum of PHMS, VPS, VF and SA) in the above system accounts for 25wt%-35wt% of the total mass of the silicone preemulsion SiE. Then, adjust the viscosity of the system to about 10-100 mPa·s with a thickener. Next, add the silicone mixture SiM containing platinum catalyst and preemulsify it for 3-10 min using a high-shear emulsifier to obtain the silicone preemulsion SiE. The effective components in the silicone preemulsion SiE account for 25wt%-35wt% of the total mass of the silicone preemulsion.

[0033] Furthermore, the amounts of hydrogen-containing silicone oil (PHMS), vinyl silicone oil (VPS), and third alkenyl functional component (VF) should be such that the residual vinyl content in the silicone rubber elastomer obtained after the hydrosilylation addition of PHMS, VPS, and VF is approximately 0.01 wt% to 1 wt% of the total mass of the silicone rubber elastomer.

[0034] The third functional component (VF) is a substance containing 1-2 alkenyl groups in its structure, capable of undergoing hydrosilylation addition reactions with Si-H bonds and increasing the miscibility of silicone rubber elastomers with styrene-acrylic resins. Specifically, it can be selected from styrene (ST), p-styrene, allyl phenyl ether (APE), allyl benzyl ether (ABE), cyclohexyl vinyl ether (CHVE), 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, etc.

[0035] The platinum catalyst can be selected from an alcoholic solution of chloroplatinic acid or a complexed platinum catalyst. Specifically, the alcohol is one or more of ethanol, isopropanol, n-propanol, tert-butanol, etc., and the amount of chloroplatinic acid used is usually 10-200 ppm of the total mass of PHMS, VPS, and VF. The complexed platinum catalyst is a vinylsilane, vinyl (low)polysiloxane, or vinyl silicone oil mixed with Pt. 4+ The transparent homogeneous complex formed by coordination complexation can be selected from one or more of the following: a cassette catalyst (such as 1,3-diethylene-1,1,3,3-tetramethyldisiloxane platinum complex KP-22) or a vinyl polysiloxane platinum complex PC11-PC16 with a platinum content of about 1000-30000ppm. The amount used is usually 0.1wt%-0.5wt% of the total mass of PHMS, VPS and VF. It can be ordered from companies such as Shanghai Neutron Star Chemical Technology Co., Ltd. and Shenzhen Kejunchi Technology Co., Ltd. or processed on commission.

[0036] Hydrogen-containing silicone oil (PHMS) undergoes a hydrosilylation addition reaction with vinyl silicone oil (VPS) and a third functional component (VF) in pre-emulsified micelles. The resulting intermediate silicone rubber elastomer contains approximately 0.05 wt% to 1.0 wt% vinyl residue, which is about 0.05 wt% to 1.0 wt% of the total mass of the silicone rubber elastomer.

[0037] The thickener may be selected from one or more of the following: carbomer, acrylic resin thickener, hydroxyethyl cellulose, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, polyurethane thickener, polyoxyethylene ether distearate, polyethylene glycol, etc.

[0038] (2) Preparation of styrene-acrylic preemulsion:

[0039] Based on mass parts, take 17-60 parts of alkenylphenyl compound (VB), 40-70 parts of acrylate (AE), and 0-3 parts of crosslinking agent (CA), mix well to obtain styrene-acrylic monomer mixture A; then, based on the mass of styrene-acrylic monomer mixture A, add 0.1wt%-1.0wt% of molecular weight regulator and 1wt%-2wt% of oil-soluble initiator, and ultrasonically disperse for 10-20 min to obtain styrene-acrylic monomer mixture B containing oil-soluble initiator; separately, based on the mass of styrene-acrylic monomer mixture B, take 1wt%-5wt% of surfactant SB, and add it to deionized water to prepare... Prepare a transparent aqueous solution, carefully controlling the amount of water used to ensure that the content of the effective component (i.e., the sum of styrene-acrylic monomer mixture A and surfactant SB) accounts for 25wt%-35wt% of the total mass of the styrene-acrylic preemulsion. Then, add styrene-acrylic monomer mixture B containing an oil-soluble initiator to the aqueous solution of surfactant SB, and preemulsify using a high-shear emulsifier for 3-5 minutes to obtain styrene-acrylic preemulsion SAE. The content of the effective component (i.e., the percentage of the sum of styrene-acrylic monomer mixture A and surfactant SB to the total mass of the styrene-acrylic preemulsion) in the styrene-acrylic preemulsion SAE is approximately 25wt%-35wt%.

[0040] Alkenylphenyl compounds are unsaturated compounds containing reactive vinyl or allyl groups and phenyl groups in their structure. Specifically, they can be selected from one or more of styrene, 4-chlorostyrene, allylphenyl ether, 4-vinylbiphenyl, etc.

[0041] Acrylates are structures containing C 1-12 Alkyl acrylates or methacrylates, specifically selected from one or more of the following: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, etc.

[0042] The crosslinking agent is an ester, or / and aromatic hydrocarbon, or / and amide compound containing two reactive alkenyl groups in its structure. Specifically, it can be 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, dipropylene glycol di(meth)acrylate, and methylenebispropionamide.

[0043] Molecular weight regulators are substances that can terminate the free radical copolymerization reaction of alkenylphenyl compounds with monomers such as acrylates, or can regulate the reaction rate between the two. Specifically, they can be selected from one or more of the following: dodecyl mercaptoethanol, mercaptopropanol, mercaptoformic acid, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, mercaptobenzoic acid, mercaptophenol, and 2,6-dimethylmercaptophenol. Thiols and thiophenols can be used directly or diluted to a certain concentration with ester or alcohol solvents before use.

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

[0045] (3) Preparation of styrene-acrylic resin modified organosilicon elastomer suspension:

[0046] Take the silicone pre-emulsion SiE, stir and heat to 75-90℃, and carry out an aqueous hydrosilylation addition reaction for 2-6 hours so that VPS, PHMS and VF in the pre-emulsion micelles can fully undergo hydrosilylation addition reaction and be converted into silicone rubber elastomer ViSE with a vinyl residue of about 0.05wt%-1.0wt% in the structure. The resulting suspension contains a large number of fine elastic solids in the aqueous system, which is the intermediate silicone rubber elastomer ViSE suspension with reactive vinyls in the structure.

[0047] The temperature of the intermediate silicone rubber elastomer ViSE suspension is adjusted to approximately 75-85℃. While stirring, styrene-acrylic pre-emulsion SAE and a water-soluble initiator are added dropwise at a uniform rate. The amount of the aqueous initiator is 0.1wt%-0.5wt% of the mass of the styrene-acrylic pre-emulsion SAE. The dropping rate is controlled so that the addition of both is completed in 2-3 hours. Then, the reaction is maintained at the temperature for 1-4 hours to obtain a styrene-acrylic resin-g-organosilicon elastomer (SASE) suspension with a styrene-acrylic resin shell, a silicone rubber elastomer core, and the inner and outer shells and cores being chemically bonded together.

[0048] Among them, the water-soluble initiator can be selected from ammonium persulfate (APS) or potassium persulfate (KPS), and under the condition that the effective component content is the same, the mass ratio of organosilicon pre-emulsion SiE to styrene-acrylic pre-emulsion SAE is controlled to be (1-5):10 (wt / wt).

[0049] (4) Demulsification treatment of suspension:

[0050] Take a suspension of styrene-acrylic resin modified organosilicon elastomer SASE, cool it to room temperature, add a demulsifier while stirring to demulsify, filter out the solid, wash it with an equal amount of deionized water, rinse it with ethanol, and then dry it at 50-70℃ for 1-2 hours to obtain a white powdery core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent with an average particle size of 50-300μm, denoted as SASE.

[0051] The demulsifier is an inorganic salt demulsifier, specifically selected from one or more of the following: sodium chloride, sodium bromide, potassium chloride, potassium bromide, magnesium chloride, magnesium bromide, zinc chloride, zinc bromide, sodium sulfate, potassium sulfate, magnesium sulfate, and zinc sulfate.

[0052] In this invention, surfactants SA and SB are mixtures of anionic and nonionic surfactants, with a mass ratio of 1:1-5. The amount of surfactant SA added is typically 5wt%-15wt% of the total mass of PHMS, VPS, and VF, and the amount of surfactant SB added is typically 1wt%-5wt% of the mass of the styrene-propane monomer. The components of surfactants SA and SB can be the same or different. 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), ammonium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid-triethanolamine salt, sodium secondary alkyl sulfonate (AOS), sodium dodecyl sulfate (SDS), potassium dodecyl sulfate (K12), and sodium salts of carboxyethylated fatty alcohol polyoxyethylene ether (AEC, such as AEC-9, AEC-10). The nonionic surfactant can be selected from fatty alcohol polyoxyethylene ethers with an EO number of 3-25. The nonionic surfactant is selected from one or more of the following: alkenyl ether, secondary alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether ester, isomeric tridecyl alcohol polyoxyethylene ether, isomeric decayl alcohol polyoxyethylene ether, etc. The preferred nonionic surfactant is an isomeric fatty alcohol polyoxyethylene ether with good emulsifying ability to polyorganosiloxane, such as isomeric tridecyl alcohol polyoxyethylene ether 1350, 1370, 1390, 13100, 13120, or isomeric decayl alcohol polyoxyethylene ether such as XP-30, XP-70, XP-90, XL-40, XL-70, XL-90, etc.

[0053] In this invention, the core-shell structure styrene-acrylic resin modified silicone elastomer toughening agent prepared by the above-described method has a shell of styrene-acrylic resin and a core of fine, uniform silicone rubber elastomer with small particle size, obtained by aqueous hydrosilylation addition reaction of PHMS, VPS, and VF. The core and shell are connected by chemical bonds (-g-). Furthermore, the core-shell structure styrene-acrylic resin modified silicone elastomer toughening agent SASE of this invention has good miscibility with PC resin due to the similarity and compatibility of its shell structure with PC resin. Moreover, SASE can significantly improve the flexibility, elasticity, and low-temperature impact resistance of PC resin when used in the processing and molding of thermoplastic PC resin and PC alloys such as PC / ABS. Therefore, it can be widely used as a toughening agent for thermoplastic PC resin materials.

[0054] Example 1

[0055] Step 1: Weigh 10.0g of PHMS-1 [poly(methylhydrosiloxane-dimethylsiloxane)] containing approximately 0.5% silane-hydrogen bond content, 27.0g of VPS-1 [vinyldimethylsilyl-terminated poly(dimethylsiloxane-diphenylsiloxane), Shanghai Jiancheng Organosilicon Co., Ltd.] containing approximately 3wt% vinyl end vinyl content, 3.36g of allyl phenyl ether (APE), and approximately 0.20g of complexed platinum catalyst KP-22, and stir to mix well to obtain 40.56g of organosilicon mixture SiM-1 containing complexed platinum catalyst.

[0056] Next, weigh approximately 2.03g of surfactant SA-1, which consists of 1.0g K12 and 1.03g isomeric tridecyl alcohol polyoxyethylene ether (1390), and dissolve it in 98.71g deionized water to form a transparent aqueous solution. Then, add carbomer thickener to adjust the viscosity of the system to approximately 30.3mPa·s. Next, add the organosilicon mixture SiM-1 containing a complexed platinum catalyst and pre-emulsify it for 5 minutes using an IKA high-shear emulsifier with a rotation speed of approximately 10000r / min to obtain a total of approximately 141.30g of organosilicon pre-emulsion SiE-1. The effective component content (i.e., the percentage of the total mass of SiM-1 and SA-1 to the mass of organosilicon pre-emulsion SiE-1) is approximately 30%, and set aside for later use.

[0057] Step 2: Weigh 14.32g MMA, 8.58g butyl acrylate (BA), and 34.36g styrene (ST), stir and mix well to obtain approximately 57.26g of styrene-acrylic monomer mixture A-1. Then, add approximately 0.11g dodecanethiol and approximately 1.15g oil-soluble free radical initiator BPO, and ultrasonically disperse using a 1000W ultrasonic cleaner for 10 minutes to obtain a total of approximately 58.52g of monomer mixture B-1 containing oil-soluble initiator.

[0058] Another 2.86g of surfactant SB-1, composed of 0.95g DBSA-Na and 1.91g 1390, was dissolved in 139.02g of deionized water to prepare a transparent aqueous solution. Then, monomer mixture B-1 containing an oil-soluble initiator was added and pre-emulsified for 3 minutes using a high-shear emulsifier to obtain 200.4g of styrene-acrylic monomer pre-emulsion SAE-1. The effective component content (i.e., the percentage of the total mass of monomer mixture B-1 and surfactant SB-1 to the mass of styrene-acrylic pre-emulsion SAE-1) was approximately 30%, and it was set aside for later use.

[0059] Step 3: Take 100.0g of silicone pre-emulsion SiE-1 and transfer it to a reaction flask equipped with a thermometer, reflux condenser, and electric stirrer. Stir and heat to 80℃ for 6 hours to obtain a silicone elastomer suspension with an intermediate Vi residue of about 0.12wt%. Continue to maintain the reaction temperature at 80℃ and add about 200.4g of styrene-acrylic monomer pre-emulsion SAE-1 and an aqueous initiator solution containing about 1.0g of APS prepared by dissolving 9.0g of deionized water dropwise while stirring. Control the dropwise addition rate of both to complete the addition within 2 hours. Then keep the reaction at 80℃ for 4 hours to obtain a suspension of about 310.4g of core-shell structure styrene-acrylic resin (MMA-co-BA-co-ST)-g-silicone elastomer (SASE-1).

[0060] Step 4: Take the core-shell structured styrene-acrylic resin (MMA-co-BA-co-ST)-g-organic silicone elastomer (SASE-1) suspension, add 15.56g of inorganic salt NaCl, stir to break the emulsion of the suspension to form a fine mud-like solid, filter with a 200-mesh nylon mesh, wash the filtered solid three times with an equal mass of deionized water, rinse once with ethanol, and then dry at 70℃ for 1 hour. During the drying process, stir or shake intermittently to prevent the solid powder particles from sticking together, and obtain about 76.60g of white elastic powder, which is the core-shell structured styrene-acrylic resin (MMA-co-BA-co-ST)-g-organic silicone elastomer toughening agent, denoted as SASE-1.

[0061] Example 2

[0062] Step 1: Weigh out 10g of PHMS-2 [trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane)] containing approximately 0.36% silane-hydrogen bond, 47.52g of VPS-2 [vinyldimethylsilyl-terminated poly(dimethylsiloxane-methylphenylsiloxane), Shandong Huanzheng Chemical Co., Ltd.] containing approximately 1wt% vinyl end vinyl ether, 3.0g of cyclohexyl vinyl ether, and approximately 0.15g of platinum complex catalyst (Shenzhen Kejunchi Technology Co., Ltd.) containing 30,000ppm platinum. Stir and mix well to obtain 60.67g of organosilicon mixture SiM-2.

[0063] Separately, take approximately 6.06 g of surfactant SA-2, composed of 2.02 g K12 and 4.04 g isomeric decayl alcohol polyoxyethylene ether XP-90, and dissolve it in 123.82 g deionized water to form a transparent aqueous solution. Then, add Acrysol RM 8W thickener (Rohm & Haas, USA) to adjust the viscosity of the system to approximately 34.8 mPa·s. Next, add the organosilicon mixture SiM-2 containing a complexed platinum catalyst, and pre-emulsify it for 5 min using an IKA high-shear emulsifier with a rotation speed of approximately 10000 r / min to obtain a total of approximately 190.49 g of organosilicon pre-emulsion SiE-2. The effective component content (i.e., the percentage of the total mass of SiM-2 and SA-2 to the mass of organosilicon pre-emulsion SiE-2) is approximately 35%, and set aside for later use.

[0064] Step 2: Weigh 45.02g MMA, 14.98g isobornyl methacrylate (IBOMA), 20.34g ST, 17.66g allyl phenyl ether (APE), and 2.03g 4,4'-divinylbiphenyl (DVBP) crosslinking agent, stir and mix well to obtain approximately 100.03g of styrene-propyl monomer mixture A-2. Then add approximately 0.11g mercaptoethanol and approximately 1.68g oil-soluble free radical initiator AIBN, and ultrasonically disperse using a 1000W ultrasonic cleaner for 15 minutes to obtain a total of approximately 101.82g of styrene-propyl monomer mixture B-2 containing oil-soluble initiator AIBN.

[0065] Separately, take approximately 3.36g of surfactant SB-2, which consists of 1.12g K12 and 2.24g XP-90, and dissolve it in 190.22g deionized water to prepare a transparent aqueous solution. Then, add a mixture of styrene-acrylic monomers B-2 containing an oil-soluble initiator, and pre-emulsify it for 5 minutes using a high-shear emulsifier to obtain 295.40g of styrene-acrylic monomer pre-emulsion SAE-2. The effective component content (i.e., the percentage of the total mass of monomer mixture B-2 and surfactant SB-2 to the mass of styrene-acrylic pre-emulsion SAE-2) is approximately 35%, and set aside for later use.

[0066] Step 3: Take 90.0g of silicone pre-emulsion SiE-2 and transfer it to a reaction flask equipped with a thermometer, reflux condenser, and electric stirrer. Stir and heat to 85℃ for 3 hours to obtain a silicone elastomer suspension with an intermediate vinyl residue of about 0.24wt%. Adjust the reaction temperature of the silicone elastomer suspension to 82℃. While stirring, add about 300.0g of styrene-acrylic monomer pre-emulsion SAE-2 and an aqueous initiator solution containing about 1.0g of KPS prepared by dissolving in 9.0g of deionized water. Control the dropping rate of both to complete the addition within 2 hours. Then keep the reaction at 82℃ for 2 hours to obtain about 400.0g of shell-core structure styrene-acrylic resin (MMA-co-IBOMA-co-ST-co-APE-co-DVBP)-g-silicone elastomer suspension.

[0067] Step 4: Take the core-shell structured styrene-acrylic resin (MMA-co-IBOMA-co-ST-co-APE-co-DVBP)-g-organosilicone elastomer suspension, add 20.51g of inorganic salt KCl to demulsify the suspension and generate a fine solid. Use a Buchner funnel with two layers of 200-mesh nylon mesh for vacuum filtration. Wash the filtered solid three times with an equal mass of deionized water, then rinse once with ethanol, and then dry at 60℃ for 1.5h. During the drying process, stir or shake intermittently to prevent the solid powder particles from sticking together. About 116.03g of white elastic powder is obtained, which is the core-shell structured styrene-acrylic resin (MMA-co-IBOMA-co-ST-co-APE-co-DVBP)-g-organosilicone elastomer toughening agent, denoted as SASE-2.

[0068] Example 3

[0069] Step 1: Weigh out 10.0g of PHMS-3 [trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methyldodecylsiloxane)] containing approximately 0.25% silane-hydrogen bond, 67.50g of VPS-3 [vinyl dimethylsilyl-terminated poly(vinylsiloxane-dimethylsiloxane-diphenylsiloxane) with vinyl groups attached to both ends, Shandong Huanzheng Chemical Co., Ltd.] containing approximately 0.5wt% Vi, 2.22g of allyl benzyl ether, and approximately 0.20g of complexed platinum catalyst KP-22, and stir to mix well to obtain 79.92g of organosilicon mixture SiM-3.

[0070] Separately, take approximately 5.60g of surfactant SA-3, composed of 1.40g AES and 4.20g isomeric decayl alcohol polyoxyethylene ether (13100), and dissolve it in 190.35g of deionized water to prepare a transparent aqueous solution. Then, add Acrysol RM8W thickener (Rohm & Haas, USA) to adjust the viscosity of the system to approximately 69.30mPa·s. Next, add the organosilicon mixture SiM-3 containing a complexed platinum catalyst, and pre-emulsify it for 5 minutes using an IKA high-shear emulsifier with a rotation speed of approximately 10000r / min to obtain a total of approximately 275.87g of organosilicon pre-emulsion SiE-3. The effective component content (i.e., the percentage of the total mass of SiM-3 and SA-3 to the mass of organosilicon pre-emulsion SiE-3) is approximately 31%, and set aside for later use.

[0071] Step 2: Weigh 38.01g MMA, 15.50g isobutyl methacrylate (i-BMA), 25.02g ST, 20.0g 4-vinylbiphenyl (VBP), and 1.48g 1,4-divinylbenzene (DVB), stir and mix well to obtain approximately 100.01g of styrene-propyl monomer mixture A-3. Then add approximately 0.18g mercaptopropionic acid and approximately 1.45g oil-soluble free radical initiator BPO, and ultrasonically disperse using a 1000W ultrasonic cleaner for 15 minutes to obtain a total of approximately 101.64g of styrene-propyl monomer mixture B-3 containing oil-soluble initiator BPO.

[0072] Another 3.05g of surfactant SB-3, composed of 1.02g AES and 2.03g 13100, was dissolved in 233.0g of deionized water to prepare a transparent aqueous solution. Then, a mixture of styrene-acrylic monomers B-3 containing an oil-soluble initiator was added, and the mixture was pre-emulsified for 5 minutes using a high-shear emulsifier to obtain 337.68g of styrene-acrylic monomer pre-emulsion SAE-3. The effective component content (i.e., the percentage of the total mass of monomer mixture B-3 and surfactant SB-3 to the mass of styrene-acrylic pre-emulsion SAE-3) was approximately 31%, which was then set aside.

[0073] Step 3: Take 80.0g of silicone pre-emulsion SiE-3 and transfer it to a reaction flask equipped with a thermometer, reflux condenser, and electric stirrer. Stir and heat to 80℃ for 4 hours to obtain a silicone rubber elastomer suspension with an intermediate vinyl residue of about 0.08wt%. Adjust the reaction temperature of the silicone rubber elastomer suspension to 83℃. While stirring, add about 200.0g of styrene-acrylic monomer pre-emulsion SAE-3 and an aqueous initiator solution containing about 0.36g of KPS prepared by dissolving in 3.24g of deionized water. Control the dropping rate of both to complete the addition within 2 hours. Then keep the reaction at 83℃ for 1.5 hours to obtain about 283.60g of shell-core structure styrene-acrylic resin (MMA-co-BMA-co-ST-co-VBP-co-DVB)-g-silicone elastomer suspension.

[0074] Step 4: Take the core-shell structured styrene-acrylic resin (MMA-co-BMA-co-ST-co-VBP-co-DVB)-g-organosilicone elastomer suspension, add 15.40g of inorganic salt MgCl2, stir to break the emulsion of the suspension to form a fine mud-like solid, filter with a 200-mesh copper screen, wash the filtered solid three times with an equal mass of deionized water, rinse once with ethanol, and then dry at 70℃ for 2h. During the drying process, stir or shake intermittently to prevent the solid powder particles from sticking together, and obtain about 69.44g of white elastic powder, which is the core-shell structured styrene-acrylic resin (MMA-co-BMA-co-ST-co-VBP-co-DVB)-g-organosilicone elastomer toughening agent, denoted as SASE-3.

[0075] Comparative Example 1

[0076] The difference between this comparative example and Example 1 is that PHMS-1 with a Si-H content of approximately 0.5% and VPS-1 with a Vi content of approximately 3 wt% were mixed with APE at a Si-H bond to vinyl molar ratio of 1:2.3. This mixture was then pre-emulsified as in Example 1 and subjected to an aqueous hydrosilylation addition reaction using the same method to prepare an intermediate suspension with a high vinyl residue (approximately 1.55%). This suspension was then subjected to suspension emulsion polymerization with the styrene-acrylic monomer pre-emulsion from Example 1 using the same method and conditions. The results showed that a large amount of gel formed in the system during the dropwise addition of the styrene-acrylic monomer pre-emulsion, and this gel solidified into large clumps in the later stages of the reaction, resulting in failure to prepare the target product.

[0077] Through the preparation process of this comparative example, it can be seen that when preparing silicone rubber elastomer suspension, the amount of raw materials and other conditions are key factors affecting whether the product can be successfully produced. When the amount exceeds the range specified in this invention, it is impossible to successfully produce the silicone rubber elastomer intermediate product with the specific structure and morphology conceived in this invention and the core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent final product.

[0078] Comparative Example 2

[0079] The difference between this comparative example and Example 2 is that in step 2, the amount of crosslinking agent DVBP was increased to 10.0 g, the amount of MMA was decreased to 40 g, and the remaining components and preparation method remained unchanged. The results showed that during the polymerization reaction of the intermediate suspension and the shell styrene-acrylic monomer pre-emulsion, the system gelled approximately 1 hour after the pre-emulsion was added due to the excessive crosslinking density of the shell styrene-acrylic resin, preventing further reaction and indicating reaction failure.

[0080] 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 styrene-acrylic preemulsion is also a key factor affecting whether the core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent can be successfully synthesized in subsequent steps. When the amount of raw materials and usage exceeds the range specified in this invention, it is impossible to successfully obtain the core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent product with the specific structure and morphology conceived in this invention.

[0081] Test case

[0082] The styrene-acrylic resin modified silicone elastomers SASE-1, SASE-2, and SASE-3 prepared in Examples 1-3 were used as toughening agent samples to prepare SASE toughened modified PC resins.

[0083] The preparation process of SASE toughening modified PC resin is as follows: PC resin masterbatch (PC-1100 from Lotte, South Korea) and SASE are mixed at a mass ratio of 1:24. Antioxidant-225 (0.1 wt% of PC resin mass) 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. 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. Alternatively, the toughening agent, PC resin masterbatch, and antioxidant-225 are mixed at the above mass ratio, melt-mixed at 250℃ using a twin-screw extruder, extruded and granulated, and then injection molded into notched impact and mechanical property test strips.

[0084] Then, using unmodified blank PC resin as the blank group, and Vi-SE-1 prepared by reacting the silicone pre-emulsion from Example 1 at 80°C for 6 hours and then drying it, was physically compounded with PC resin as the reference group. The different SASE toughened modified PC resins and the reference group were subjected to application performance tests according to relevant standard injection molding test strips, as detailed below:

[0085] (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 SASE toughened modified PC resins was measured using a TH-100 haze meter (Hangzhou Caipu Technology Co., Ltd.). The larger the haze value, the better the toughening agent SASE is miscible in PC resin, the more uniformly it is dispersed, and the better the PC sample scatters light.

[0086] (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 SASE toughened modified PC resins was determined within 3 minutes using a Shimadzu AGS-X electronic universal testing machine.

[0087] (3) The tensile strength of different SASE toughened modified PC resins was determined by referring to the standard sample preparation of GB / T1040-2006.9 "Determination of tensile properties of plastics" and using the Shimadzu AGS-X electronic universal testing machine.

[0088] The results of the above performance tests are summarized in Table 1 below:

[0089] Table 1. Material property test results of different samples

[0090]

[0091] The results of the above tests and performance measurements show that:

[0092] The core-shell structure styrene-acrylic resin-modified silicone elastomers (SASEs) prepared using the method of this invention in Examples 1 to 3 exhibit significantly higher torque and energy consumption compared to the blank group and the reference group. Furthermore, the modified PC resin made using the styrene-acrylic resin-modified silicone elastomers (SASEs) from Examples 1 to 3 has lower light transmittance, and its haze, impact resistance, and tensile strength are significantly higher than those of the blank PC resin in the blank group and the silicone-modified PC resin in the reference group. This demonstrates that the acrylic resin-coated silicone elastomer (SASE) and its preparation method proposed in this invention can improve the mechanical properties of modified PC resins, such as impact resistance and tensile strength, 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 method for preparing a core-shell structured styrene-acrylic resin modified organosilicon elastomer toughening agent, characterized in that, Includes the following steps: S1 Preparation of organosilicon pre-emulsion: Take hydrogen-containing silicone oil, vinyl silicone oil, third alkenyl functional component and platinum catalyst, mix them well to obtain organosilicon mixture SiM; under the action of surfactant SA and thickener, pre-emulsify to obtain organosilicon pre-emulsion SiE; S2 Preparation of styrene-acrylic preemulsion: Take 17-60 parts by mass of alkenylphenyl compound, 40-70 parts by mass of acrylate and 0-3 parts by mass of crosslinking agent and mix them to obtain styrene-acrylic monomer mixture A; then add molecular weight regulator and oil-soluble initiator to obtain styrene-acrylic monomer mixture B containing oil-soluble initiator; then preemulsify under the action of surfactant SB to obtain styrene-acrylic preemulsion SAE; S3 Preparation of styrene-acrylic resin modified organosilicon elastomer suspension: Take organosilicon pre-emulsion SiE, heat to 75-90℃ for aqueous phase hydrosilylation addition reaction for 2-6h, to obtain organosilicon elastomer suspension with intermediate vinyl residue of 0.05wt%-1.0wt%; then, continue to add styrene-acrylic pre-emulsion SAE and water-soluble initiator, and keep the reaction at 75-85℃ for 1-4h to obtain styrene-acrylic resin modified organosilicon elastomer suspension; The mass ratio of silicone preemulsion (SiE) to styrene-acrylic preemulsion (SAE) was controlled to be (1-5):

10. S4 Suspension Demulsification Treatment: Take a suspension of styrene-acrylic resin modified organosilicon elastomer, add a demulsifier to demulsify, filter out the solid, wash and dry to obtain a core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent.

2. The method for preparing the core-shell structured styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, In step S1, the amount of surfactant SA added is 5wt%-15wt% of the mass of the silicone mixture SiM; and in the silicone preemulsion SiE, the sum of the mass of the silicone mixture SiM and the surfactant SA accounts for 25wt%-35wt% of the total mass of the silicone preemulsion SiE.

3. The method for preparing the shell-core structure styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, Hydrogen-containing silicone oils have Si-H bonds in their end groups and / or side chains, and their main chain contains dimethylsiloxane, or / and diethylsiloxane, or / and methylphenylsiloxane, or / and diphenylsiloxane, or / and methylC. 2-18 The siloxane copolymer of alkylsiloxane units has a Si-H bond molar content of 0.05%-1.6% in the hydrogen-containing silicone oil; Vinyl silicone oil has vinyl groups and / or side chains attached to it, and its main chain contains dimethylsiloxane or / and diethylsiloxane, or / and methylphenylsiloxane, or / and diphenylsiloxane, or / and methylC. 2-18 Siloxane copolymers with alkylsiloxane linkages, wherein the vinyl content in the vinyl silicone oil is 0.1wt%-3wt%.

4. The method for preparing the shell-core structure styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, The third alkenyl functional component is selected from styrene, allyl phenyl ether, allyl benzyl ether, cyclohexyl vinyl ether, α-C 8-18 One or more mixtures of olefins, 1,6-hexadiene, 1,9-decadiene, polyethylene glycol dielyl ether, ethylene glycol dielyl ether, polypropylene glycol dielyl ether, and propylene glycol dielyl ether.

5. The method for preparing the shell-core structure styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, Acrylates selected from C1- 12 Alkyl acrylates, C1- 12 One or more of alkyl methacrylates, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, and isobornyl methacrylate; The alkenylphenyl compound is selected from one or more of styrene, 4-chlorostyrene, allylphenyl ether, and 4-vinylbiphenyl; 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, and tripropylene glycol di(meth)acrylate.

6. The method for preparing the shell-core structure styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, In step S2, based on the mass of styrene-acrylic monomer mixture A, the amount of molecular weight regulator is 0.1wt%-1.0wt%, and the amount of oil-soluble initiator is 1wt%-2wt%; based on the mass of styrene-acrylic monomer mixture B, the amount of surfactant SB is 1wt%-5wt%, and the content of effective components in styrene-acrylic preemulsion SAE is 25wt%-35wt%.

7. The method for preparing the shell-core structure styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, In step S3, the amount of water-soluble initiator is 0.1wt%-0.5wt% of the mass of the styrene-acrylic preemulsion.

8. The method for preparing the core-shell structured styrene-acrylic resin modified organosilicon elastomer toughening agent according to claim 1, characterized in that, In step S4, the demulsifier is selected from one or more of the following: sodium chloride, sodium bromide, potassium chloride, potassium bromide, magnesium chloride, magnesium bromide, zinc chloride, zinc bromide, sodium sulfate, potassium sulfate, magnesium sulfate, and zinc sulfate.

9. A core-shell structured styrene-acrylic resin modified organosilicon elastomer toughening agent prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent prepared by any one of the preparation methods of claims 1 to 8, or the core-shell structure styrene-acrylic resin modified organosilicon elastomer toughening agent of claim 9, in PC resin.

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