Acrylate resin-g-organosilicone elastomer flexibilizer as well as preparation method and application thereof

Abstract

The invention relates to the technical field of PC resin flexibilizers, and particularly discloses an acrylate resin-g-organic silicon elastomer flexibilizer as well as a preparation method and application thereof, aiming at the problems of poor intersolubility of an organic silicon material and PC resin and insufficient mechanical properties of a target product. The preparation method of the flexibilizer comprises the following steps: uniformly mixing hydrogen-containing silicone oil, vinyl silicone oil, a third alkenyl functional component and a platinum catalyst, and pre-emulsifying under the action of a surfactant and a thickener to obtain an organic silicon pre-emulsion; uniformly mixing methyl methacrylate with other acrylic ester and / or a cross-linking agent, adding a molecular weight regulator and an oil-soluble initiator, and pre-emulsifying under the action of a surfactant to obtain an acrylic ester pre-emulsion; and taking the organic silicon pre-emulsion, carrying out heating reaction to obtain an organic silicon elastomer suspension with residual vinyl, dropwise adding the acrylate pre-emulsion and a water-soluble initiator, carrying out heat preservation reaction, and carrying out demulsification to obtain the acrylate resin-g-organic silicon elastomer flexibilizer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of PC resin toughening agent, in particular to an acrylate resin-g-silicone elastomer toughening agent and a preparation method and application thereof. BACKGROUND

[0002] PC resin is a resin material with good heat stability, electrical insulation, impact resistance, rigidity, flexibility, aging resistance and low temperature impact resistance. Polyorganosiloxane is a kind of high molecular compound connected by silicon atoms and oxygen atoms alternately, which has excellent high temperature resistance, low temperature resistance and chemical stability, and the chain segment is flexible, hydrophobic, resistant to high and low temperature, and has good ultraviolet aging resistance. Therefore, it is theoretically feasible to modify PC resin and other resins with polyorganosiloxane. However, traditional polyorganosiloxane, such as polydimethylsiloxane, although the chain segment is flexible, the structure, solubility parameter and molecular polarity are quite different from PC resin, so when the two are compounded, phase separation and layering may easily occur.

[0003] At present, by utilizing the structural characteristics of benzene ring groups in the molecular structure of PC resin, the compounding and combining effect between the toughening agent and PC resin is enhanced through the design of the molecular structure of the core-shell structure. For example, the patent with publication number CN109293856A discloses an organic silicon toughening agent of polymer-coated inorganic nano-material and a synthesis method thereof. The patent first hybridizes organic silicon and inorganic nano-particles, and then coats acrylate soft monomers and hard monomers in sequence to synthesize an organic silicon toughening agent with a multi-layer core-shell structure.

[0004] However, the existing toughening agent and its preparation process, the core of which is usually prepared by ring-opening polymerization of organic silicon monomers, or hydrolytic polycondensation reaction of methyl or phenyl silane with reactive vinyl silane or methacryloyl propyl silane, still has the problem of poor mutual solubility between the toughening agent and bisphenol A polycarbonate resin base when used for modifying bisphenol A polycarbonate resin material, which further causes the mechanical properties such as toughness and impact resistance of the modified target PC resin to be insufficient. SUMMARY

[0005] The present application aims to solve the problem of poor mutual solubility between the existing polyorganosiloxane toughening agent and PC resin base, which further causes the mechanical properties of the PC resin modified by the toughening agent to be insufficient.

[0006] The present application is realized by the following technical scheme:

[0007] The present application provides a preparation method of an acrylate resin-g-silicone elastomer toughening agent, comprising the following steps: S1 preparing an organic silicon pre-emulsion: With a vinyl to Si-H bond molar ratio greater than 1, hydrogen-containing silicone oil, vinyl silicone oil, third alkenyl functional component and platinum catalyst were taken, mixed well, and organosilicon mixture SiM was obtained; then, under the action of surfactant SA and thickener and deionized water, pre-emulsification was carried out to obtain organosilicon pre-emulsion SiE. S2 Preparation of acrylate preemulsion: Take 40-70 parts by weight of methyl methacrylate, 17-60 parts of other acrylates and 0-3 parts of crosslinking agent, mix them well to obtain acrylate monomer mixture A; then add molecular weight regulator and oil-soluble initiator, mix well to obtain monomer mixture B containing oil-soluble initiator; then, pre-emulsify under the action of surfactant SB and deionized water to obtain acrylate pre-emulsion; S3 Preparation of acrylate resin-g-organic silicone elastomer toughening agent: Take the silicone preemulsion SiE and heat it to 75-90℃ for an aqueous hydrosilylation addition reaction for 2-6 hours to obtain a silicone elastomer suspension; then add the acrylate preemulsion and water-soluble initiator dropwise, and keep it at 75-85℃ for 1-4 hours to obtain an acrylate resin-g-silicone elastomer suspension. S4 Suspension Demulsification Treatment: Take the acrylate resin-g-organosilicon elastomer suspension, add a demulsifier to demulsify, filter out the solid, wash and dry to obtain the acrylate resin-g-organosilicon elastomer toughening agent.

[0008] Preferably, the third functional component is selected from vinyl acetate, allyl acetate, 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, (poly)ethylene glycol dielyl ether, and (poly)propylene glycol dielyl ether.

[0009] Preferably, the hydrogen-containing silicone oil is a phenyl or C40-containing silicone oil with Si-H bonds in its terminal group and / or side chain. 2-18 Alkyl-substituted) polyorganosiloxanes, the molar content of Si-H bonds in hydrogen-containing silicone oil (calculated as the number of moles of Si-H bonds per 100g of silicone oil) is 0.05%-1.6%. 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 field, the molar content of Si-H bonds is used to define the key component, active hydrogen.

[0010] Hydrogen-containing silicone oils can be specifically selected from Si-H end-capped polydimethylsiloxane, polydiethylsiloxane, poly(dimethylsiloxane-diethylsiloxane), poly(dimethylsiloxane-methylphenylsiloxane), poly(dimethylsiloxane-diphenylsiloxane), and poly(dimethylsiloxane-methylC) 2-18Alkylsiloxanes), or poly(methylhydrosiloxane-dimethylsiloxane), poly(methylhydrosiloxane-diethylsiloxane), poly(methylhydrosiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-diphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-diphenylsiloxane), poly(methylhydrosiloxane-dimethylsiloxane-methylC) terminated with Si-H bonds. 2-18 Alkylsiloxanes), or dimethylsiloxane-terminated poly(methylhydrosiloxane-dimethylsiloxane), or dimethylsiloxane-terminated poly(methylhydrosiloxane-diethylsiloxane), poly(methylhydrosiloxane-diphenylsiloxane), poly(methylhydrosiloxane-methylphenylsiloxane), poly(methylhydrosiloxane-methylC) 2-18 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 Jiangxi Huarunzhi New Materials Co., Ltd., Wuhan Huaxiang Kejie Biotechnology Co., Ltd., Zhejiang Hengyecheng Organosilicon Co., Ltd., Zhejiang Hanbang New Materials Co., Ltd., Lanxing Group, etc.

[0011] Preferably, the ethylene silicone oil is a polysiloxane containing vinyl groups at the ends and / or side chains, and the vinyl content in the ethylene polysiloxane is 0.1wt%-3wt%. Herein, the vinyl content in the vinyl silicone oil refers to the mass percentage of reactive vinyl groups.

[0012] Specifically, the ethylene polysiloxane can be selected from vinyl-terminated polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, poly(dimethylsiloxane-diethylsiloxane), poly(dimethylsiloxane-methylphenylsiloxane), poly(dimethylsiloxane-diphenylsiloxane), and poly(dimethylsiloxane-methylC) 2-18 Alkylsiloxanes), or poly(methylvinylsiloxane-dimethylsiloxane), poly(methylvinylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-methylphenylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-diphenylsiloxane), poly(methylvinylsiloxane-dimethylsiloxane-methylC) with vinyl groups attached to the side chain. 2-18Alkylsiloxanes, or vinyl dimethicone-terminated poly(methylvinylsiloxane-dimethylsiloxane), poly(methylvinylsiloxane-diethylsiloxane), poly(methylvinylsiloxane-methylphenylsiloxane), poly(methylvinylsiloxane-diphenylsiloxane), poly(methylvinylsiloxane-methylC) with vinyl groups and side chains attached to both the end group and the side chain. 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 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.

[0013] Preferably, in step S1, the surfactant SA is first dissolved in water, and then the organosilicon mixture SiM is added for pre-emulsification, and the total mass of the hydrogen-containing silicone oil, vinyl silicone oil, third alkenyl functional component and surfactant SA is controlled to be 25wt%-35wt% of the mass of the organosilicon pre-emulsion SiE; The amount of thickener added is 0.1wt%-1wt% of the mass of the silicone preemulsion (SiE).

[0014] Preferably, the other acrylates contain C in their structure. 2-12 Alkyl or C 5-12 The crosslinking agent is an acrylate or methacrylate containing two reactive alkenyl groups in its structure.

[0015] Preferably, the amount of thickener added is such that the viscosity of the adjusted silicone pre-emulsion SiE system is about 10-100 mPa·s.

[0016] Preferably, in step S2, based on the mass of the acrylate monomer mixture A, the amount of molecular weight regulator added is 0.1wt%-1.0wt% and the amount of oil-soluble initiator added is 1wt%-3wt%. The amount of surfactant SB added is 1wt%-5wt% based on the mass of monomer mixture B.

[0017] Preferably, during pre-emulsification, the surfactant SB is first dissolved in water, and then the monomer mixture B is added for pre-emulsification treatment, and the total mass of the acrylate monomer mixture A and the surfactant SB is controlled to be 25wt%-35wt% of the mass of the acrylate pre-emulsion.

[0018] Preferably, surfactant SA and surfactant SB are both mixtures of anionic and nonionic surfactants.

[0019] Preferably, in step S3, the amount of aqueous initiator is 0.1wt%-1.0wt% of the mass of the acrylate preemulsion.

[0020] The acrylate resin-g-organic silicone elastomer toughening agent proposed in this invention can be used in the production and processing of PC resin.

[0021] The technical solution of the present invention has the following beneficial effects: This invention utilizes high-shear emulsification under the action of anionic / nonionic surfactants to pre-emulsify PHMS, VPS, and VF in an aqueous system and then perform a suspension hydrosilylation addition reaction to prepare an organosilicon elastomer suspension with a certain amount of reactive vinyl groups remaining in the structure. Then, using this suspension intermediate as the source material for the core organosilicon elastomer, it is further copolymerized with acrylate monomers containing initiators and molecular weight modifiers, crosslinking agents, etc., in a suspension emulsion to obtain a shell-core structure acrylate resin-g-organosilicon elastomer toughening agent with an acrylate resin outer shell, an addition-type silicone rubber elastomer core, and covalent bonds between the inner and outer layers. This invention, through the design of the shell resin structure, molecular weight regulation, and control of the core organosilicon elastomer structure and particle size, enables the preparation of a shell-core structure acrylate resin-g-organosilicon elastomer toughening agent. This agent not only achieves mutual compatibility with PC resin and PC alloy resin, solving the problems of traditional organosilicon polymers such as polydimethylsiloxane (PDMS) used in PC and its alloy processing, such as structural incompatibility, easy phase separation, and the lubrication and isolation of PDMS segments leading to a decline in the mechanical properties of PC materials, but also allows the newly synthesized target toughening agent to be used in the processing of PC resin and PC alloy resin, significantly improving the application performance of PC resin such as flexibility and low-temperature impact resistance while significantly reducing the impact on the mechanical properties of PC materials. Detailed Implementation

[0022] 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.

[0023] This invention provides a method for preparing an acrylate resin-g-organic silicone elastomer toughening agent, comprising the following steps: (1) Preparation of silicone preemulsion: With a vinyl to Si-H bond molar ratio greater than 1, hydrogen-containing silicone oil (PHMS), vinyl silicone oil (VPS), and third alkenyl functional component (VF) were taken, mixed, and then a platinum catalyst was added and stirred evenly to obtain an organosilicon mixture SiM. Separately, surfactant SA is dissolved in water, and the amount of water is controlled 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 organosilicon pre-emulsion SiE. Then, a thickener is added to adjust the viscosity of the system to about 10-100 mPa·s to obtain a pre-emulsified mixture. The organosilicon mixture SiM is mixed with the pre-emulsified mixture, and then a high-shear emulsifier is used to perform high-shear pre-emulsification for 3-10 min to obtain organosilicon pre-emulsion SiE, in which the effective components (i.e., the sum of PHMS, VPS, VF and SA) account for 25wt%-35wt% of the total mass of the organosilicon pre-emulsion SiE.

[0024] Among them, the hydrogen-containing silicone oil is a polyorganosiloxane with Si-H bonds in the end group and / or side chain. The molar content of Si-H bonds (based on the number of moles of silicon-hydrogen bonds contained in 100g of polysiloxane) is about 0.05%-1.6%, and the viscosity is about 10-1000mPa.s.

[0025] Ethylene silicone oil is a polyorganosiloxane containing vinyl (Vi) at the end groups and / or side chains. The vinyl Vi content (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.

[0026] The third functional component 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 and polyacrylate resins. Specifically, it can be selected from vinyl acetate, allyl acetate, 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, (poly)ethylene glycol dielyl ether, (poly)propylene glycol dielyl ether, etc.

[0027] The platinum catalyst can be selected from an alcoholic solution of chloroplatinic acid and / 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 homogeneous complex formed by the coordination complexation of a vinyl-containing silane or polysiloxane with platinum. Specifically, it can be selected from one or more of the following: a caster catalyst (such as 1,3-diethylene-1,1,3,3-tetramethyldisiloxane complexed platinum KP-22) or a platinum complex PC11-PC16 with a platinum content of about 1000-30000 ppm. The amount used is usually 0.05wt%-0.5wt% of the total mass of PHMS, VPS, and VF, and can be provided by companies such as Shanghai Neutron Star Chemical Technology Co., Ltd. and Shenzhen Kejunchi Technology Co., Ltd.

[0028] In the hydrosilylation addition reaction of PHMS with VPS and VF, the amount of each component should be such that the residual vinyl content in the silicone rubber elastomer obtained after the hydrosilylation addition of PHMS with VPS and VF is about 0.01wt%-1.2wt% of the total mass of the silicone rubber elastomer.

[0029] Thickeners are substances that can significantly increase the viscosity of aqueous systems. Specifically, they can be selected from one or more of the following: carbomer, acrylic resin thickeners, hydroxyethyl cellulose, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, polyurethane thickeners, polyoxyethylene ether distearate, polyethylene glycol, etc.

[0030] (2) Preparation of acrylate preemulsion: Take 40-70 parts by mass of methyl methacrylate, 17-60 parts by mass of other acrylates (AE), and 0-3 parts by mass of crosslinking agent (CA), mix them well to obtain acrylate monomer mixture A; then, based on the mass of acrylate monomer mixture A, add 0.1wt%-1.0wt% of molecular weight regulator and 1wt%-3wt% of oil-soluble initiator, and ultrasonically disperse for 10-20 minutes to obtain monomer mixture B; separately, based on the mass of monomer mixture B, take 1wt%-5wt% of surfactant SB, dissolve it in water, and control the amount of water to ensure that the content of the effective component (i.e., the sum of acrylate monomer mixture A and surfactant SB) accounts for 25wt%-35wt% of the total mass of the acrylate preemulsion. Then, mix monomer mixture B with the aqueous solution of surfactant SB, and perform high-shear preemulsification treatment for 3-5 minutes using a high-shear emulsifier to obtain the acrylate preemulsion.

[0031] Among them, other acrylates contain C in their structure. 2-12 Alkyl or C 5-12The cycloalkyl acrylates or methacrylates may be selected from one or more of the following: ethyl acrylate (EA), ethyl methacrylate (EMA), propyl acrylate (n-PA), propyl methacrylate (n-PMA), butyl acrylate (BA), butyl methacrylate (n-BMA), isobutyl methacrylate (i-BMA), tert-butyl acrylate (t-BMA), tert-butyl methacrylate (t-BMA), octyl acrylate (OA), n-octyl methacrylate (n-OMA), isooctyl acrylate (i-OA), isooctyl methacrylate (i-OMA), lauryl acrylate (LA), lauryl methacrylate (LMA), cyclopentyl acrylate (CPA), cyclopentyl methacrylate (CPMA), cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), isobornyl acrylate (IBOA), and isobornyl methacrylate (IBOMA), with preference given to acrylates and their complexes having a higher glass transition temperature (Tg).

[0032] The crosslinking agent is an acrylate or acrylamide containing two or more reactive alkenyl groups in its structure. Specifically, it can be selected from one or more of the following: ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, triethylene glycol dimethacrylate, methylenebisacrylamide, etc. The amount of crosslinking agent used is approximately 0-3 wt% of the total mass of the acrylate mixture (i.e., acrylate and crosslinking agent).

[0033] Molecular weight regulators are substances that can terminate or regulate the copolymerization reaction of acrylates with crosslinking agents and vinyl-containing silicone rubber elastomers and other monomers using multi-component free radical suspension emulsions. 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, 2,6-dimethylmercaptophenol, etc. The amount of molecular weight regulator used is 0.1wt%-1.0wt% of the total mass of the acrylate monomers. It can be used directly or diluted fully with solvents such as alcohols or esters such as ethyl acetate, butyl acetate, isopropanol, etc. before use.

[0034] The oil-soluble initiator is a substance that can dissolve in the mixture of acrylate monomers in the oil phase, and can generate free radicals after thermal decomposition, and can effectively initiate the free radical copolymerization reaction of unsaturated acrylate monomers. Specifically, it can be selected from one or more of benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), percarbonate, tert-butyl peroxide, etc. The amount of oil-soluble initiator is 1wt%-3wt% of the total mass of acrylate monomers.

[0035] (3) Preparation of acrylate resin-g-organosilicon elastomer toughening agent: Take the silicone preemulsion SiE, stir and heat to 75-90℃ for an aqueous hydrosilylation addition reaction for 2-6 hours, so that PHMS, VPS and VF in the preemulsion micelles can fully undergo hydrosilylation addition reaction and be converted into a silicone rubber elastomer with a certain amount of residual vinyl groups in the structure. The resulting suspension contains a large number of fine elastic solids, which is the intermediate silicone rubber elastomer with reactive vinyl groups in the structure. Control the suspension at 75-85℃, and while stirring, add the acrylate preemulsion and water-soluble initiator dropwise at a uniform rate. The amount of aqueous initiator is 0.1wt%-0.5wt% of the mass of the acrylate preemulsion. The two substances were added dropwise over 2-3 hours, and then the reaction was maintained at a constant temperature for 1-4 hours to carry out a free radical suspension emulsion polymerization reaction, resulting in an acrylate resin-g-organosilicon elastomer suspension with a shell of polyacrylate resin and a core of silicone rubber elastomer. Then, the mixture was cooled to room temperature, and a demulsifier was added while stirring to demulsify the mixture, resulting in a fine mud-like solid. The solid was then filtered, washed with deionized water and rinsed with ethanol, and dried at 50-70℃ for 1-2 hours to obtain a white powdery acrylate resin-g-organosilicon elastomer toughening agent with an average particle size of 50-300 μm, denoted as PASE.

[0036] The water-soluble initiator can be selected from ammonium persulfate or potassium persulfate, and the amount of water-soluble initiator is 0.1wt%-1.0wt% of the mass of the acrylate preemulsion.

[0037] The demulsifier is an inorganic salt or a small molecule organic alcohol. Specifically, the inorganic 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, potassium sulfate, magnesium sulfate, zinc sulfate, etc., and the small molecule organic alcohol can be selected from ethanol and / or isopropanol, etc.

[0038] 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 acrylate monomers. The anionic surfactant can be selected from one or more of the following: sodium fatty alcohol polyoxyethylene ether sulfate (AES), ammonium fatty alcohol polyoxyethylene ether sulfate, sodium dodecylbenzene sulfonate (DBSA-Na), potassium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, sodium secondary alkyl sulfonate (AOS), sodium dodecyl sulfate (SDS), potassium dodecyl sulfate (K12), and sodium salts of carboxyethylated fatty alcohol polyoxyethylene ethers, such as AEC-9 and AEC-10. The nonionic surfactant can be selected from one or more of the following: fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, fatty acid polyoxyethylene ether ester, isomeric tridecyl alcohol polyoxyethylene ether, and isomeric decayl alcohol polyoxyethylene ether.

[0039] In this invention, the acrylate resin-g-organosilicone elastomer toughening agent prepared by the above-described method has a shell layer of linear or slightly cross-linked polyacrylate resin and a core layer of fine, uniform, and small-particle-size silicone rubber elastomer obtained through an aqueous hydrosilylation addition reaction. The core and shell layers are connected by chemical bonds (-g-). Because the outer acrylate resin layer has good miscibility with conventional acrylate resins, bisphenol A polycarbonate (PC resin), epoxy resins, etc., and the cross-linked polyorganosiloxane core possesses excellent high and low temperature resistance, as well as good flexibility and impact resistance, it is used as a toughening agent or flexibility modifier for thermoplastic polymer PC resins, PC / ABS alloys, and thermosetting epoxy resin coatings, significantly increasing the flexibility and impact resistance of resin coatings and processed parts.

[0040] Example 1 Step 1: Weigh 10.0g of PHMS-1 (poly(methylhydrosiloxane-dimethylsiloxane)) containing approximately 0.5% Si-H bond molar content, 27.0g of VPS-1 (vinyl dimethylsilyl-terminated poly(dimethylsiloxane-diphenylsiloxane), Shanghai Jiancheng Organosilicon Co., Ltd.) containing approximately 3wt% Vi end vinyl silicone oil, 2.50g of allyl acetate and 0.20g of complexed platinum catalyst KP-22, stir and mix well to obtain 39.70g of organosilicon mixture SiM-1 containing complexed platinum catalyst; Separately weigh 1.98g of anionic / nonionic surfactant SA-1, composed of 0.99g K12 and 0.99g isomeric tridecyl alcohol polyoxyethylene ether 1390, and dissolve it in 97.25g 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 an 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 138.93g of organosilicon pre-emulsion SiE-1 with an effective component content of approximately 30wt%, for later use.

[0041] Step 2: Weigh 40.08g of methyl methacrylate (MMA) and 17.18g of other acrylates composed of 11.45g of butyl acrylate (BA) and 5.73g of cyclohexyl methacrylate (CHMA), stir and mix well to obtain approximately 57.26g of acrylate monomer mixture A1. Then add approximately 0.11g of dodecanethiol and 1.15g of 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 acrylate monomer mixture B1 containing oil-soluble initiator. Take another 1.40g K12 and 1.46g 1390, dissolve them in 139.02g deionized water to form a transparent aqueous solution, then add the acrylate monomer mixture B1 containing the oil-soluble initiator, and pre-emulsify it for 3 minutes using a high-shear emulsifier to obtain about 200.40g of acrylate pre-emulsion AEE-1 with an effective component content of about 30wt%, for later use.

[0042] Step 3: Take 100.0g of organosilicon 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 6h to obtain an organosilicon elastomer (Vi-SE-1) suspension with a Vi residual content of about 0.34wt% in the intermediate structure. The reaction temperature of the intermediate Vi-SE-1 suspension was adjusted to 75℃. While stirring, about 200.0g of acrylate pre-emulsion AEE-1 and an aqueous initiator solution containing about 2.0g of APS, prepared by dissolving in 8g of deionized water, were added dropwise. The dropwise addition rate of both was controlled so that the addition was completed within 2 hours. Then the reaction was kept at 80℃ for 4 hours to obtain about 310.0g of shell-core structure acrylate resin-g-organosilicon elastomer (PASE-1) suspension.

[0043] Step 4: Take the core-shell structure PASE-1 suspension, add 15.56g of inorganic salt KBr while stirring, stir for 5min to break the emulsion and form a fine 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 1h. During the drying process, stir or shake intermittently to prevent the solid powder particles from sticking together, and obtain about 73.01g of white elastic powder, namely core-shell structure acrylate resin (MMA-co-BA-co-CHMA)-g-organic silicone elastomer toughening agent, denoted as PASE-1.

[0044] Example 2 Step 1: Weigh 15.0g of PHMS-2 (dimethylhydrosilane-terminated poly(methylhydrosiloxane-diethylsiloxane)) with a Si-H bond molar content of approximately 0.1%, 21.60g of VPS-2 (vinyl dimethylsilane-terminated poly(dimethylsiloxane-co-diphenylsiloxane) VPS-2, Shandong Huanzheng Chemical Co., Ltd.) with a Vi content of approximately 1.5wt%, 0.52g of vinyl acetate, and approximately 0.13g of platinum complex catalyst (Shenzhen Kejunchi Technology Co., Ltd.) with a platinum content of 20000ppm. Stir and mix to obtain 37.22g of organosilicon mixture SiM-2. Separately, take approximately 4.65g of anionic / nonionic surfactant SA-2, composed of 1.05g SDS and 3.60g isomeric tridecyl alcohol polyoxyethylene ether 1390, and dissolve it in 125.70g deionized water to form a transparent aqueous solution. Then, adjust the viscosity of the system to approximately 90.02mPa·s with hydroxyethyl cellulose (average molecular weight Mn approximately 3×104, Dow Chemical Company, USA). Next, add a silicone oil mixture SiM-2 containing a complexed platinum catalyst, and pre-emulsify it for 10min using an IKA high-shear emulsifier with a rotation speed of approximately 10000r / min to obtain a total of approximately 167.6g of organosilicon pre-emulsified SiE-2 liquid with an effective component content of approximately 25wt%, for later use.

[0045] Step 2: Weigh 40.0g of methyl methacrylate (MMA), 57.0g of other acrylates composed of 22.0g of ethyl methacrylate (EMA) and 35.0g of cyclohexyl methacrylate (CHMA), and 3.0g of ethylene glycol diacrylate crosslinking agent (GDA). Stir and mix well to obtain approximately 100.0g of acrylate monomer mixture A2. Then add approximately 0.5g of dodecanethiol and approximately 1.0g of oil-soluble free radical initiator BPO. Use a 1000W ultrasonic cleaner to ultrasonically disperse for 20 minutes to obtain a total of approximately 203.0g of acrylate monomer mixture B2. Take approximately 0.76g of K12 and 0.76g of 1390, dissolve them in 309.06g of deionized water to prepare a transparent aqueous solution, then add the acrylate monomer mixture B2, and pre-emulsify using a high-shear emulsifier for 5 minutes to obtain approximately 412.08g of acrylate pre-emulsion AEE-2, with an effective component content of approximately 25wt%, for later use.

[0046] Step 3: Take 100.0g of organosilicon pre-emulsion SiE-2 and transfer it to a reaction flask equipped with a thermometer, reflux condenser and electric stirrer. Stir and heat to 75℃ for 2h to obtain an organosilicon elastomer (Vi-SE-2) suspension with an intermediate Vi residual amount of about 0.22wt%. The reaction temperature of the intermediate Vi-SE-2 suspension was adjusted to 80℃. While stirring, about 500.0g of acrylate preemulsion AEE-2 and an aqueous initiator solution containing about 3.0g of APS, prepared by dissolving in 27.0g of deionized water, were added dropwise. The dropwise addition rate of both was controlled so that the addition was completed within 3 hours. Then the reaction was kept at 80℃ for 1 hour to obtain about 630.0g of shell-core structure acrylate resin (MMA-co-EMA-co-CHMA-co-GDA)-g-organosilicon elastomer (PASE-2) suspension.

[0047] Step 4: Take the core-shell structure PASE-2 suspension and add 69.61g of inorganic salt NaCl while stirring. Stir for 10 minutes to break the emulsion and form a fine solid. Filter with a 180-mesh nylon mesh. Wash the filtered solid three times with an equal amount of deionized water, then rinse once with ethanol. Dry at 60℃ for 2 hours. Stir or shake intermittently during the drying process to prevent the solid powder particles from sticking together. About 120.67g of white elastic powder is obtained, which is the core-shell structure acrylate resin (MMA-co-EMA-co-CHMA-co-GDA)-g-organic silicone elastomer toughening agent, denoted as PASE-2.

[0048] Example 3 Step 1: Weigh 10.0g of PHMS-3 (a trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane) with a Si-H bond molar content of approximately 0.36%), 63.18g of VPS-3 (a vinyl-dimethylsilyl-terminated poly(dimethylsiloxane-methylphenylsiloxane)) with a Vi content of approximately 1wt%, 2.27g of cyclohexylvinyl ether (CHVE), and approximately 0.30g of a platinum complex catalyst (Shenzhen Kejunchi Technology Co., Ltd.) with a platinum content of 30000ppm. Stir and mix well to obtain 75.85g of organosilicon monomer mixture SiM-3. Next, weigh approximately 7.59g of anionic / nonionic surfactant SA-3, composed of 2.52g AES and 5.06g isomeric decayl alcohol polyoxyethylene ether XP-90, and dissolve it in 154.98g of deionized water to form a transparent aqueous solution. Then, adjust the viscosity of the system to approximately 33.60mPa·s using thickener Acrysol RM8W (Rohm & Haas, USA). Next, add the silicone monomer mixture SiM-3 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 238.40g of silicone pre-emulsion with an effective component content of approximately 35wt%, for later use.

[0049] Step 2: Weigh 55.80g of methyl methacrylate (MMA), 43.63g of other acrylates composed of 18.26g of butyl acrylate (BA) and 25.37g of isobornyl methacrylate (IBOMA), and 2.03g of hexanediol diacrylate crosslinking agent (HAD). Stir and mix well to obtain approximately 101.47g of acrylate monomer mixture A3. Then add approximately 0.20g of mercaptoethanol (diluted with 1.8g of IPA before adding) and approximately 1.52g of oil-soluble free radical initiator AIBN. Use a 1000W ultrasonic cleaner to ultrasonically disperse for 15 minutes to obtain a total of approximately 104.99g of acrylate monomer mixture B3 containing oil-soluble initiator. Take approximately 1.0g of AES and 2.04g of XP-90, dissolve them in 190.57g of deionized water to prepare a transparent aqueous solution, and then add a mixture of acrylate monomers B3 containing an oil-soluble initiator. Pre-emulsify the mixture for 5 minutes using a high-shear emulsifier to obtain 298.60g of acrylate pre-emulsion (AEE-3), with an effective component content of approximately 35wt%, for later use.

[0050] Step 3: Take 88.0g 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 3 hours to obtain a silicone elastomer (Vi-SE-3) intermediate suspension with a Vi residual content of approximately 0.19wt%. Adjust the reaction temperature of the intermediate suspension to 82℃, and add 293.33g of acrylate pre-emulsion AEE-3 and an aqueous initiator solution containing approximately 0.60g of KPS prepared by dissolving in 5.4g of deionized water dropwise while stirring. Control the dropwise addition rate of both to complete the addition within 2 hours, and then continue to keep the reaction at 82℃ for another 2 hours to obtain approximately 381.33g of acrylate resin-g-silicone elastomer (PASE-3) suspension containing a core-shell structure.

[0051] Step 4: Take the core-shell structure PASE-3 suspension, add 20.97g of inorganic salt KBr, stir for 5min to break the emulsion and generate a fine solid, filter with a 200-mesh nylon mesh, wash the filtered solid three times with an equal amount of deionized water, rinse once with ethanol, and then dry at 65℃ for 2h. During the drying process, stir or shake intermittently to prevent the solid powder particles from sticking together, and obtain about 113.45g of white elastic powder, namely core-shell structure acrylate resin (MMA-co-BA-co-IBOMA-co-HDA)-g-organic silicone elastomer toughening agent, denoted as PASE-3.

[0052] Example 4 Step 1: Weigh 10.0g of PHMS-4 (a trimethylsilyl-terminated poly(methylhydrosiloxane-dimethylsiloxane-methylphenylsiloxane) with a Si-H bond molar content of approximately 0.25%), 67.50g of VPS-4 (a vinyl silicone oil with a Vi content of approximately 0.5wt% (a vinyl-dimethylsilyl-terminated poly(vinylsiloxane-dimethylsiloxane-diphenylsiloxane) with vinyl groups attached to both ends and sides, Shandong Huanzheng Chemical Co., Ltd.), 2.22g of allyl benzyl ether (ABE), and approximately 0.20g of a platinum complex catalyst with a platinum content of 30000ppm (Shenzhen Kejunchi Technology Co., Ltd.), stir and mix well to obtain 79.92g of organosilicon monomer mixture SiM-4; Separately, approximately 4.80 g of anionic / nonionic surfactant SA-4, composed of 1.60 g DBSA-Na and 3.20 g isomeric tridecyl alcohol polyoxyethylene ether 13100, was dissolved in 180.03 g deionized water to form a transparent aqueous solution. Thickener 638 (polyethylene glycol 6000 distearate, Tianjin Zhonghe Shengteng Chemical Co., Ltd.) was then added to adjust the viscosity of the system to approximately 27.50 mPa·s. Next, a silicone oil mixture SiM-4 containing a platinum complex catalyst was added, and the mixture was pre-emulsified for 5 min using an IKA high-shear emulsifier at a speed of approximately 10000 r / min to obtain a total of approximately 264.75 g of silicone pre-emulsion SiE-4, with an effective component content of approximately 32.0 wt%, for later use.

[0053] Step 2: Weigh 53.0g of methyl methacrylate (MMA), 45.5g of a mixture of other acrylates consisting of 20.0g of tert-butyl acrylate, 15.0g of cyclopentyl methacrylate (BMA), and 10.50g of isobornyl methacrylate (IBOMA), and 1.50g of tripropylene glycol diacrylate (TPGDA) crosslinking agent. Stir and mix well to obtain approximately 100.0g of acrylate monomer mixture A4. Then add approximately 0.3g of mercaptoacetic acid molecular weight regulator and approximately 2.20g of oil-soluble free radical initiator AIBN. Disperse the mixture using a 1000W ultrasonic cleaner for 10 minutes to obtain a total of approximately 102.5g of acrylate mixture B4 containing oil-soluble initiator. Set aside. Another 3.59g of surfactant made from 1.20g DBSA-Na and 2.39g 13100 was dissolved in 217.63g deionized water to prepare a transparent aqueous solution. Then, an acrylate mixture B4 containing an oil-soluble initiator was added, and the mixture was pre-emulsified for 5 minutes using a high-shear emulsifier to obtain 323.72g of acrylate pre-emulsion AEE-4 with an effective component content of approximately 32.0wt%, which was set aside for later use.

[0054] Step 3: Take 70.0g of organosilicon pre-emulsion SiE-4 and transfer it to a reaction flask equipped with a thermometer, reflux condenser and electric stirrer. Stir and heat to 80℃ for 4h to obtain an organosilicon elastomer (Vi-SE-4) suspension with an intermediate Vi residual amount of about 0.08wt%. The reaction temperature of the intermediate suspension was adjusted to 80℃. While stirring, about 200.0g of acrylate preemulsion AEE-4 and an aqueous initiator solution containing about 1.0g of KPS, prepared by dissolving in 9.0g of deionized water, were added dropwise. The dropwise addition rate of both was controlled so that the addition was completed within 2 hours. Then the reaction was kept at 80℃ for 1 hour to obtain about 270.0g of a suspension of acrylate resin (MMA-co-BMA-co-IBOMA-co-TPGDA)-g-organosilicon elastomer (PASE-4) containing a core-shell structure.

[0055] Step 4: Take the core-shell structure PASE-4 suspension, stir, add 17.37g of inorganic salt MgCl2, stir for 6min to break the emulsion and generate a fine solid, filter with a 200-mesh nylon mesh, wash the filtered solid three times with an equal amount 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 72.14g of white elastic powder, namely core-shell structure acrylate resin (MMA-co-BA-co-IBOMA-co-TPGDA)-g-organic silicone elastomer toughening agent, denoted as PASE-4.

[0056] Comparative Example 1 The difference between this comparative example and Example 1 is that the amount of vinyl-terminated silicone oil (VPS, Shanghai Jiancheng Organosilicon Co., Ltd.) with a Vi content of approximately 3 wt% was increased to 50 g, while the remaining components and their amounts remained unchanged, to prepare an organosilicon pre-emulsion SiE. Then, this organosilicon pre-emulsion SiE was mixed with the acrylate pre-emulsion from Example 1 to prepare the target product, a core-shell structured acrylate resin-g-organosilicon elastomer toughening agent. Results: When mixed with the acrylate pre-emulsion, excessive residual vinyl groups on the surface of the silicone rubber elastomer in the system caused a large amount of gelation in the acrylate pre-emulsion during polymerization, leading to reaction failure and the inability to obtain the target product, the core-shell structured acrylate resin-g-organosilicon elastomer toughening agent.

[0057] Through the preparation process of this comparative example, it can be seen that when preparing the core-shell structure acrylic resin-g-organic silicone elastomer toughening agent, the raw materials and dosage of the organosilicon pre-emulsion SiE are key factors affecting whether the product can be successfully prepared. When the dosage exceeds the range specified in this invention, the core-shell structure acrylic resin-g-organic silicone elastomer toughening agent with the specific structure and morphology conceived in this invention cannot be successfully prepared.

[0058] Comparative Example 2 The difference between this comparative example and Example 3 is that in step 3, the amount of propylene glycol methacrylate was increased to 10.0 g, while the remaining components and preparation method remained unchanged. The results showed that due to the excessive amount of crosslinking agent in the acrylate monomers, the system gelled during the addition of the acrylate monomer pre-emulsion, preventing further reaction.

[0059] Through the preparation process of this comparative example, it can be seen that when preparing a core-shell structure acrylate resin-g-organosilicon elastomer suspension by mixing organosilicon monomer pre-emulsion and acrylate pre-emulsion, the amount of each component raw material is also a key factor affecting whether the core-shell structure acrylate resin-g-organosilicon elastic toughening agent can be successfully synthesized in subsequent steps. When the amount of raw materials and dosages exceeds the range specified in this invention, it is impossible to successfully obtain the core-shell structure acrylate resin-g-organosilicon elastic toughening agent product with the specific structure and morphology conceived in this invention.

[0060] Test case The acrylate resin-g-organic silicone elastomer toughening agents PASE-1, PASE-2, PASE-3, and PASE-4 prepared in Examples 1-4 were used as toughening agent samples to prepare PASE toughening modified PC resins.

[0061] The preparation process of PASE toughening modified PC resin is as follows: PC resin masterbatch (PC resin selected from Lotte's PC-1100 from South Korea) and PASE are mixed at a mass ratio of 1:24. Then, antioxidant-225 (0.1 wt% of PC resin mass) is added and mixed evenly. Using an XSS-300 torque rheometer (Shanghai Kechuang Rubber & Plastic Equipment Co., Ltd.), the mixture is melt-mixed for 5 minutes at 250℃ and approximately 120 rpm. 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 2mm 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.

[0062] Then, the prepared PASE toughened modified PC resins were used as a control group, with the unmodified blank PC resin as the control group, and the silicone pre-emulsion from Example 1 reacted at 80°C for 6 hours, dried, and then compounded with PC resin at a ratio of 1:24 for toughening modification as a reference group. Application performance tests were conducted according to relevant standard injection molding specimens, as detailed below: (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 PASE 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 PASE is miscible in PC resin, the more uniformly it is dispersed, and the better the PC sample scatters light.

[0063] (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 PASE toughened modified PC resins was determined within 3 minutes using a Shimadzu AGS-X electronic universal testing machine.

[0064] (3) The tensile strength of different PASE toughened modified PC resins was determined using the standard sample preparation method of GB / T1040-2006.9 "Determination of tensile properties of plastics" and the Shimadzu AGS-X electronic universal testing machine.

[0065] The results of the above performance tests are summarized in Table 1 below: Table 1. Material property test results of different samples

[0066] The results of the above tests and performance measurements show that: In Examples 1 to 4, the acrylate resin-g-organosilicon elastomer toughening agent PASE and its preparation method proposed in this invention showed significantly higher torque and energy consumption compared to the blank group and the reference group. Furthermore, the modified PC resin prepared using the acrylate resin-g-organosilicon elastomer toughening agent PASE from Examples 1 to 4 exhibited lower light transmittance, and significantly higher fogging, impact resistance, and tensile strength than the blank PC resin in the blank group and the organosilicon monomer-modified PC resin in the reference group. This demonstrates that the acrylate resin-g-organosilicon elastomer toughening agent PASE 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.

[0067] 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 an acrylate resin-g-organic silicone elastomer toughening agent, comprising the following steps: S1 Preparation of silicone pre-emulsion: Take hydrogen-containing silicone oil, vinyl silicone oil, third alkenyl functional component and platinum catalyst, mix them well to obtain silicone mixture SiM; then pre-emulsify it under the action of surfactant SA and thickener to obtain silicone pre-emulsion SiE; S2 Preparation of acrylate preemulsion: Methyl methacrylate, other acrylates, and / or crosslinking agents are mixed to obtain acrylate monomer mixture A; then a molecular weight regulator and an oil-soluble initiator are added to obtain a monomer mixture B containing an oil-soluble initiator; then preemulsification is carried out under the action of surfactant SB to obtain acrylate preemulsion; S3 Preparation of acrylate resin-g-organosilicon elastomer suspension: Take the organosilicon pre-emulsion SiE, heat it to 75-90℃ for aqueous phase hydrosilylation addition reaction for 2-6h to obtain organosilicon elastomer suspension; then add acrylate pre-emulsion and water-soluble initiator dropwise, keep the reaction at 75-85℃ for 1-4h to obtain acrylate resin-g-organosilicon elastomer suspension; S4 Suspension Demulsification Treatment: Take the acrylate resin-g-organosilicon elastomer suspension, add a demulsifier to demulsify, filter out the solid, wash and dry to obtain the acrylate resin-g-organosilicon elastomer toughening agent.

2. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, The third functional component is selected from 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, (poly)ethylene glycol dielyl ether, and (poly)propylene glycol dielyl ether.

3. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, Hydrogen-containing silicone oils are those with Si-H bonds in their terminal groups and / or side chains (phenyl or C). 2-18 Alkyl-substituted) polyorganosiloxanes, with a Si-H bond molar content of 0.05%-1.6% in the hydrogen-containing silicone oil; Ethylene silicone oil is a polyorganosiloxane containing vinyl groups at the end groups and / or side chains, and the vinyl content in ethylene polysiloxane is 0.1wt%-3wt%.

4. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, In step S1, the surfactant SA is first dissolved in water, and then the organosilicon mixture SiM is added for pre-emulsification. The total mass of the hydrogen-containing silicone oil, vinyl silicone oil, third alkenyl functional component, and surfactant SA is controlled to be 25wt%-35wt% of the mass of the organosilicon pre-emulsion SiE. The amount of thickener added is 0.1wt%-1wt% of the mass of the silicone preemulsion (SiE).

5. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, Other acrylates contain C in their structure. 2-12 Alkyl or C 5-12 The crosslinking agent is an acrylate or methacrylate containing two reactive alkenyl groups in its structure.

6. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, In step S2, based on the mass of acrylate monomer mixture A, the amount of molecular weight regulator added is 0.1wt%-1.0wt%, and the amount of oil-soluble initiator added is 1wt%-3wt%. The amount of surfactant SB added is 1wt%-5wt% based on the mass of monomer mixture B; During pre-emulsification, surfactant SB is first dissolved in water, and then added to monomer mixture B for pre-emulsification treatment. The total mass of acrylate monomer mixture A and surfactant SB is controlled to be 25wt%-35wt% of the mass of acrylate pre-emulsion.

7. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, Surfactant SA and surfactant SB are both mixtures of anionic and nonionic surfactants.

8. The method for preparing the acrylate resin-g-organic silicone elastomer toughening agent according to claim 1, characterized in that, In step S3, the amount of water-soluble initiator is 0.1wt%-1.0wt% of the mass of the acrylate preemulsion.

9. An acrylate resin-g-organosilicon elastomer toughening agent prepared by any one of claims 1 to 8.

10. The application of the acrylate resin-g-organosilicon elastomer toughening agent prepared by any one of claims 1 to 8, or the acrylate resin-g-organosilicon elastomer toughening agent of claim 9, in PC resin.

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