Multilayer core-shell structure polymer containing fluorine and silicon, preparation method for resin composition comprising same, and use thereof

Abstract

Disclosed are a multilayer core-shell structure polymer containing fluorine and silicon, a preparation method for a resin composition comprising same, and use thereof. The present invention belongs to the field of polymer materials. The multilayer core-shell structure polymer containing fluorine and silicon comprises an inner core, an outer shell layer, and an optional intermediate shell layer. The outer shell layer is obtained by reacting a vinyl siloxane, a fluorine-containing siloxane, and an alkyl siloxane, and is bridged to the inner core or the intermediate layer by means of vinyl siloxane. The prepared multilayer core-shell polymer with fluorine-containing polysiloxane as an outer shell layer helps to subsequently improve the hydrophobicity and chemical resistance of a resin composition comprising same.

Description

A fluorinated silicon multilayer core-shell polymer, a method for preparing a resin composition comprising the same, and its applications. Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a fluorinated silicon multilayer core-shell structure polymer, a method for preparing a resin composition including the same, and its application. Background Technology

[0002] When polybutadiene rubber grafted with SAN impact modifiers is blended with SAN, classic island-type ABS resin can be produced. This resin possesses good rigidity, processability, and impact resistance, and is widely used in the automotive and home appliance industries. With advancements in polymer synthesis technology, the demand for specialized properties in ABS materials continues to increase. For example, automotive and home appliance parts require good hydrophobicity and chemical resistance; they should also possess a certain degree of self-cleaning ability to prevent sweat and dirt from penetrating the material; and improved chemical resistance will allow the material to maintain dimensional stability during electroplating and finishing processes, preventing cracking and splitting of the finished product.

[0003] Existing technologies for improving the hydrophobicity and chemical resistance of ABS resin mainly focus on modifying and reinforcing the marine structure, while high-resin content (island structure) is often overlooked for performance improvement. Directly adding fluorosiloxanes to extruded ABS resin results in poor dispersibility, and the overall hydrophobicity and chemical resistance of the resin are usually still poor due to the performance defects of high-resin content. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems or defects existing in the prior art and provide a fluorinated silicon multilayer core-shell structure polymer, a resin composition including the same, and the resulting resin composition has good hydrophobicity and chemical resistance.

[0005] Another object of the present invention is to provide a method for preparing the fluorinated silicon multilayer core-shell structure polymer.

[0006] Another object of the present invention is to provide a resin composition comprising the fluorinated silicon multilayer core-shell structure polymer.

[0007] Another object of the present invention is to provide a method for preparing the resin composition comprising a multilayer core-shell structure polymer containing fluorine silicon.

[0008] Another object of the present invention is to provide the application of the resin composition comprising the fluorinated silicon multilayer core-shell structure polymer.

[0009] To achieve the above objectives, the present invention employs the following technical solution:

[0010] A fluorinated silicon multilayer core-shell polymer, with an outer shell comprising the following components, based on 100 parts by dry weight of the core and intermediate layers:

[0011] 5-25 parts of fluorosiloxane;

[0012] Vinylsiloxane 5-15 parts;

[0013] Alkylsiloxane 0-20 parts;

[0014] The number of layers in the intermediate layer is n, where n is a positive integer from 0 to 10; the core comprises diene polymers.

[0015] The above-described solution provides a fluorinated silicone multilayer core-shell polymer, comprising a core, an outer shell, and an optional intermediate shell. The outer shell is obtained through the reaction of vinylsiloxanes, fluorinated silicones, and alkylsiloxanes, and is bridged to the core or intermediate shell by a vinylsiloxane. The resulting multilayer core-shell polymer with a fluorinated polysiloxane as the outer shell helps to improve the hydrophobicity and chemical resistance of resin compositions comprising it.

[0016] Furthermore, n is 0 to 5; even further, n is 1 to 3.

[0017] Furthermore, the core comprises polyconjugated diene and / or inorganic particles coated with polyconjugated diene.

[0018] Specifically, the polyconjugated diene is obtained by polymerizing conjugated diene monomers.

[0019] The average particle size of the core is 290–330 nm, the solid content of the core is 40%–60%, the gel content of the core is 60%–95%, and the core is usually dispersed in water in the form of an emulsion.

[0020] Specifically, the method for determining the average particle size involves dispersing and diluting the sample in water, then adding the sample to the sample cell of a Malvern laser particle size analyzer. Each sample is scanned and measured three times, with a measurement equilibration time set to 10 seconds and a single scan time of 60 seconds.

[0021] Specifically, the conjugated diene monomer is selected from at least one of 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and chloroprene.

[0022] The polyconjugated diene described in this invention can be commercially available or self-made.

[0023] Specifically, the polyconjugated diene is prepared by the following method:

[0024] It is obtained by emulsion polymerization of conjugated diene monomers.

[0025] Specifically, the emulsion polymerization temperature is 60–90°C, and the emulsion polymerization time is 12–36 h.

[0026] Specifically, the emulsion polymerization may incorporate one or more of an initiator, emulsifier, defoamer, chain transfer agent, or electrolyte.

[0027] In some specific embodiments, the core is an inorganic particle coated with polyconjugated diene, and the preparation method is as follows:

[0028] The conjugated diene monomer is obtained by emulsion polymerization in the presence of inorganic particles; or

[0029] It is obtained by emulsifying polyconjugated diene latex with inorganic particles.

[0030] Specifically, the inorganic particles are one or more of inorganic silicon dioxide, aluminum oxide, zinc oxide, magnesium oxide, titanium dioxide, or rare earth oxides; the inorganic particles can be surface-modified particles or unmodified particles.

[0031] The surface modification includes silane modification.

[0032] The inorganic particles can be commercially available or prepared in-house. Preparation methods include the sol-gel method.

[0033] In a specific embodiment, the inorganic silica is vinyltriethoxysilane-modified nano-silica.

[0034] Furthermore, the intermediate layer is obtained by emulsion polymerization of a component comprising the following compounds:

[0035] A11: Based on the intermediate layer, 40 to 79.9 wt% of at least one vinyl aromatic olefin; preferably 45 to 70 wt% of at least one vinyl aromatic olefin; preferably 48 to 60 wt%; more preferably 50 to 65 wt%;

[0036] A12: Based on the intermediate layer, 10 to 39.9 wt% acrylonitrile monomer; preferably 15 to 30 wt% acrylonitrile monomer; preferably 22 to 28 wt%; more preferably 24 to 26 wt%;

[0037] A13: Based on the intermediate layer, 10 to 29.9 wt% of a divinyl compound; preferably 15 to 28 wt% of a divinyl compound; preferably 18 to 27 wt%; more preferably 20 to 25 wt%;

[0038] The mass ratio of the intermediate layer to the core is 20:80 to 80:20 on a dry basis.

[0039] Furthermore, the structural formula of the divinyl compound is as follows:

[0040] Wherein, R1 is selected from substituted or unsubstituted alkylene, cycloalkylene, alkylene ester, cycloalkylene ester, alkeneoxy, cycloalkeneoxy, arylene, arylalkylene, and heteroarylene; wherein the number of carbon atoms in R1 is 1 to 20;

[0041] R2 and R3 are independently selected from hydrogen, alkyl, cycloalkyl, alkyl ester, cycloalkyl ester, alkoxy, cycloalkoxy, aryl, aralkyl, and heteroaryl groups having 1 to 20 carbon atoms.

[0042] Further, the divinyl compound is one or more of the following: divinylbenzene, polyethylene glycol dimethacrylate (n=1-60), polyethylene glycol diacrylate (n=1-60), propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, aryl methacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, polybisphenol A-ethylene oxide diacrylate (n=1-40), tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, or divinyl ether.

[0043] Furthermore, the divinyl compound is one or more of divinylbenzene, ethylene glycol dimethacrylate, or divinyl ether.

[0044] Furthermore, the divinyl compound is divinylbenzene.

[0045] Furthermore, the fluorinated siloxane includes one or more of trifluoropropylmethylcyclotrisiloxane, tetramethyltri-3-trifluoropropylcyclotetrasiloxane, or 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane.

[0046] Furthermore, the fluorinated siloxane is trifluoropropylmethylcyclotrisiloxane and / or tetramethyltri-3-trifluoropropylcyclotetrasiloxane.

[0047] Furthermore, the vinylsiloxane includes one or more of tetramethyltetravinylcyclotetrasiloxane, γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltriisopropoxysilane.

[0048] Furthermore, the vinylsiloxane is tetramethyltetravinylcyclotetrasiloxane and / or γ-methacryloyloxypropyltrimethoxysilane.

[0049] Furthermore, the alkylsiloxane includes one or more of octamethylcyclotetrasiloxane, hexamethyldisiloxane, hexaethyldisiloxane, methyltriethoxysilane, or 1,3-octyltetramethyldisiloxane.

[0050] Furthermore, the alkylsiloxane is one or more of octamethylcyclotetrasiloxane, hexamethyldisiloxane, or hexaethyldisiloxane.

[0051] Furthermore, the outer shell layer comprises the following components:

[0052] 17.5 to 22.5 parts of fluorinated siloxane.

[0053] Vinylsiloxane 8-15 parts.

[0054] 8-15 parts of alkylsiloxane.

[0055] Furthermore, the preparation method of the fluorinated silicon multilayer core-shell structure polymer includes the following steps:

[0056] S1. Prepare or fabricate the kernel;

[0057] S2. Preparation of core-shell emulsion: Emulsion polymerization of A11, A12 and A13 in the presence of the core;

[0058] S3. The product obtained in step S2, fluorinated siloxane, alkyl siloxane and vinyl siloxane are polymerized to obtain a polymer emulsion. The polymer emulsion is then subjected to high-temperature coagulation to obtain a fluorinated silicon multilayer core-shell structure polymer.

[0059] Specifically, the emulsion polymerization temperature is 60–90°C, and the emulsion polymerization time is 2–6 hours.

[0060] Specifically, the emulsion polymerization may include 0.1 to 10 parts by weight of other component C1 based on 100 parts of dry base core.

[0061] Specifically, the polymerization reaction is carried out at a temperature of 60–90°C for 2–6 hours.

[0062] Specifically, the temperature at which the high-temperature condensation occurs is 80–100°C.

[0063] Specifically, the other component C1 can be selected from one or more of redox initiators, reducing agents, co-reducing agents, lubricants, chain transfer agents, or defoamers.

[0064] Specifically, the polymerization reaction may include 0.1 to 10 parts by weight of other component C2, based on 100 parts of the dry basis product of step S2.

[0065] Specifically, the other component C2 may be selected from initiators and / or emulsifiers. Preferably, the initiator is a redox initiator.

[0066] Specifically, based on 100 parts of the dry-based product of step S2, there are 0.1 to 5 parts by weight of initiator, 0.1 to 5 parts by weight of emulsifier, and 60 to 350 parts by weight of water.

[0067] In a specific embodiment, the fluorinated silicon multilayer core-shell polymer is prepared by the following method:

[0068] S1. Prepare or fabricate the kernel;

[0069] S2. The core, a portion of the vinyl aromatic olefins and acrylonitrile monomers, based on 100 parts of dry core, 0.3-0.8 parts by weight of reducing agent, 1.5-2.5 parts by weight of co-reducing agent, 0.3-0.8 parts by weight of emulsifier and 80-200 parts by weight of water are added to the reactor. The temperature is raised to 65±3℃, 1 part by weight of initiator is added and reacted for 0.5-1.5 h. Then the temperature is raised to 78±3℃, and the remaining vinyl aromatic olefins, the remaining acrylonitrile monomers and divinyl compounds and 1 part by weight of initiator are continuously added dropwise for 1.0-5.0 h.

[0070] S3. The product of step S2 (solid content 40-65%), fluorosiloxane, vinylsiloxane, and alkylsiloxane are added to a reaction vessel with 0.8-2 parts by weight of initiator, 0.8-2 parts by weight of emulsifier, and 80-200 parts by weight of water, based on 100 parts dry basis of step S2. The mixture is reacted at 65-75°C for 2.5-3.5 hours to obtain a multilayer core-shell polymer emulsion with a solid content of 40-65%. This emulsion is then transferred to a coagulation reactor and heated to 80°C. At 0–90°C, sulfuric acid with a mass concentration of 3–8% (30%–50% of the amount added to the multilayer core-shell polymer emulsion) is gradually added over 2.5–3.5 hours. The temperature is then raised to 90–99°C and maintained for 2–4 hours. The resulting coagulated latex is filtered using a filter (e.g., a 200–500 mesh filter) and dried in a fluidized bed dryer at 65–75°C for 5–8 hours to obtain a fluorinated silicon multilayer core-shell polymer with a water content of less than 1%.

[0071] Furthermore, the vinyl aromatic olefins include one or more of styrene, p-methylstyrene, and α-methylstyrene.

[0072] In this invention, commonly used redox initiators can be selected, such as, but not limited to, one or more of hydrogen peroxide, benzoyl peroxide or cyclohexylbenzene hydrogen peroxide.

[0073] In this invention, commonly used reducing agents can be selected, such as, but not limited to, ferrous sulfate and / or ferric sulfate.

[0074] In this invention, commonly used reducing agents can be selected, such as, but not limited to, one or more of lactose, glucose, maltose, and formaldehyde hyposulfite.

[0075] In this invention, commonly used emulsifiers can be selected, such as, but not limited to, one or more of potassium disproportionate, potassium fatty acid, or dodecylbenzenesulfonic acid.

[0076] In this invention, commonly used chain transfer agents can be selected, such as, but not limited to, n-dodecyl mercaptan and / or tert-dodecyl mercaptan.

[0077] In this invention, commonly used electrolytes can be selected, such as, but not limited to, one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, or potassium hydroxide.

[0078] In this invention, commonly used defoamers can be selected, such as, but not limited to, polyether-type defoamers, silicone-type defoamers, or non-silicone-type defoamers.

[0079] The present invention also provides a polymer composition comprising the following components in parts by weight:

[0080] 15-40 parts of the above-mentioned fluorinated silicon multilayer core-shell structure polymer or the fluorinated silicon multilayer core-shell structure polymer prepared by the above preparation method; 60-80 parts of styrene-acrylonitrile copolymer and / or styrene-acrylonitrile-acrylate copolymer.

[0081] Specifically, the styrene-acrylonitrile copolymer and the styrene-acrylonitrile-acrylate copolymer contain 60 to 80 wt% styrene.

[0082] In a specific embodiment, the polymer composition further includes 0.1 to 5 parts by weight of other components.

[0083] In specific embodiments, the other components include, but are not limited to, one or more of the following: fillers, reinforcing agents, dyes, lubricants, mold release agents, stabilizers, antioxidants, UV absorbers, plasticizers, impact modifiers, antistatic agents, flame retardants, bactericides, or foaming agents.

[0084] Specifically, the filler or reinforcing agent includes, but is not limited to, one or more of silicates, amorphous silica, calcium silicate, quartz, mica, metal oxides, metal hydroxides, graphite, barium sulfate, calcium carbonate, magnesium carbonate, talc, kaolin, carbon fiber, or glass fiber.

[0085] Specifically, the pigments include, but are not limited to, one or more of titanium dioxide, phthalocyanine, ultramarine, iron oxide, or carbon black.

[0086] Specifically, the stabilizer includes, but is not limited to, one or more of resorcinol diphenyl, salicylate, benzotriazole or benzophenone.

[0087] Specifically, the release agent includes, but is not limited to, fatty acids having 12 to 30 carbon atoms, their salts and their derivatives, such as stearic acid, stearate, palmitic acid, palmitate, stearyl alcohol, amide wax and polyolefin wax.

[0088] In this invention, commonly used antioxidants can be selected, such as, but not limited to, one or more of hindered phenolic antioxidants, phosphite antioxidants, or thioester antioxidants.

[0089] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, or spiroethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0090] Specifically, the phosphite antioxidant is 2,4-di-tert-butylphenol and / or bis(2,6-di-tert-butyl-4-tolyl) pentaerythritol phosphite.

[0091] Specifically, the thioester antioxidant is one or more of distearate thiodipropionate, dilaurate thiodipropionate, or pentaerythritol-based dodecathiopropyl ester.

[0092] In this invention, commonly used lubricants can be selected, such as, but not limited to, at least one of amide lubricants, stearate lubricants, ester lubricants, or silicone lubricants.

[0093] The present invention also provides a method for preparing the polymer composition, comprising the following steps:

[0094] The components are mixed, extruded through a twin-screw extruder, cooled, and granulated to obtain a polymer composition.

[0095] Specifically, the extrusion temperature is 185–220°C.

[0096] Specifically, the screw speed of the twin-screw extruder is 250–350 rpm.

[0097] Specifically, the screw length-to-diameter ratio of the twin-screw extruder is 25:1.

[0098] The present invention also provides the application of the above polymer composition in the preparation of materials for automobiles, home appliances and office equipment, especially in automobile door handles, automobile interiors, automobile steering wheels, juicers, coffee machines or printers.

[0099] Compared with the prior art, the present invention has the following beneficial effects:

[0100] This invention provides a fluorinated silicon multilayer core-shell structure polymer, wherein the outer shell is composed of fluorinated siloxanes and vinyl siloxanes, and the polymer composition obtained by using it has good hydrophobicity and chemical resistance. Detailed Implementation

[0101] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0102] 1. Raw materials used in each embodiment and comparative example:

[0103] Core 1: Polybutadiene latex: self-made, with an average particle size of 325.1 nm and a solid content of 45.8%;

[0104] The specific preparation method is as follows:

[0105] One part by weight of sodium hydroxide, 1.5 parts by weight of potassium disproportionated rosinate, 0.5 parts by weight of tert-dodecyl mercaptan and 130 parts by weight of water were added to a high-pressure reactor. Then, 90 parts by weight of butadiene monomer and 1 part by weight of potassium persulfate were injected into the reactor under medium-pressure nitrogen gas. The temperature was raised to 60°C and reacted for 18 hours. Finally, the temperature was raised to 80°C and reacted for 10 hours to obtain polybutadiene latex.

[0106] Core 2: Polybutadiene-coated inorganic silica: self-made, with an average particle size of 329.1 nm and a solid content of 50.2%;

[0107] 50 parts by weight of water, 20 parts by weight of methanol, 5.0 parts by weight of sodium hydroxide, 10 parts by weight of nano-silica with an average particle size of 30 nm, and 5.0 parts by weight of vinyltriethoxysilane were added to a high-pressure reactor. Stirring was started, and the reactor was heated to 80°C and held for 20 min. The temperature was then lowered to 60°C, and 1 part by weight of sodium hydroxide, 1.5 parts by weight of potassium disproportionated rosinate, 0.5 parts by weight of tert-dodecyl mercaptan, and 130 parts by weight of water were added to the high-pressure reactor. Subsequently, 90 parts by weight of butadiene monomer and 1 part by weight of potassium persulfate were injected into the reactor under medium-pressure nitrogen gas. The temperature was raised to 60°C and reacted for 18 h. Finally, the temperature was raised to 80°C and reacted for 10 h to obtain polybutadiene latex coated with inorganic silica.

[0108] Specifically, the average particle size was tested as follows: the sample was dispersed and diluted in water, and then added to the sample cell of the Malvern laser particle size analyzer. Each sample was scanned and measured three times, and the average value was taken. The measurement equilibration time was set to 10 s, and the single scan time was 60 s.

[0109] Specifically, the solid content test method is as follows: First, weigh the aluminum foil used for sampling, W1; after sampling, to avoid monomer volatilization, immediately weigh the total mass of the aluminum foil and latex, W2; place the aluminum foil and latex together in a forced-air drying oven and dry at 110℃ until constant weight, then weigh the dried material, W3. The solid content is calculated as follows: Solid content = (W3 - W2) / (W1 ... 1) / (W2-W1)×100%, where

[0110] W1: Aluminum foil mass, g;

[0111] W2: Mass of aluminum foil and latex, in g;

[0112] W3: Weight of aluminum foil and adhesive, g;

[0113] A11: Vinyl aromatic olefin, industrial grade styrene, purity greater than 99.5%, purchased from Inokai;

[0114] A12: Acrylonitrile monomer, industrial grade acrylonitrile, purity greater than 99%, purchased from Innovent.

[0115] A13: Divinyl compounds

[0116] A13-1: Divinylbenzene, purity greater than 98%, purchased from Inokai;

[0117] A13-2: Ethylene glycol dimethacrylate, purity greater than 98.5%, purchased from Sinopharm Reagent.

[0118] A13-3: Divinyl ether, purity greater than 98%, purchased from Inokai;

[0119] Fluorosiloxanes:

[0120] Fluorosiloxane 1: Trifluoropropylmethylcyclotrisiloxane, purity greater than 98%, purchased from Innocare;

[0121] Fluorosiloxane 2: Tetramethyltri-3-trifluoropropylcyclotetrasiloxane, purity greater than 96%, purchased from Innocare;

[0122] Vinylsiloxane:

[0123] Vinylsiloxane 1: γ-methacryloyloxypropyltrimethoxysilane, purity greater than 98%, purchased from Maclean's;

[0124] Vinylsiloxane 2: Tetramethyltetravinylcyclotetrasiloxane, purity greater than 97%, purchased from Bailingwei;

[0125] Alkylsiloxane: Octamethylcyclotetrasiloxane; purchased from Aladdin;

[0126] Nano silica, 20-30nm, purchased from Innocare, purity greater than 99%, powder, catalog number A66412;

[0127] Vinyltriethoxysilane, with a purity greater than 98%, was purchased from Inokai;

[0128] Initiator: Potassium persulfate, commercially available;

[0129] Initiator: Benzoyl peroxide, commercially available;

[0130] Electrolyte: Sodium carbonate, commercially available;

[0131] Emulsifier: Potassium disproportionate, commercially available;

[0132] Chain transfer agent: tert-dodecyl mercaptan, commercially available;

[0133] Reducing agent: Ferrous sulfate, commercially available;

[0134] Reducing agent: Sodium formaldehyde sulfoxylate, commercially available;

[0135] Styrene-acrylonitrile copolymer: KFA-130, styrene content 76wt%, purchased from Liaoning Kingfa Science & Technology Co., Ltd.

[0136] Other component C3:

[0137] Antioxidants: Phosphite antioxidants, commercially available;

[0138] Lubricant: A commercially available mixture of ethylene bis-stearamide and magnesium stearate in a 1:1 mass ratio; it should be noted that the raw materials used in the parallel experiments of the examples and comparative examples are the same commercially available products.

[0139] Examples 1-12 and Comparative Examples 1-2

[0140] In the examples and comparative examples, the fluorinated silicon multilayer core-shell structure polymer, with the raw material ratios shown in Tables 1-2 by weight, was prepared by the following method, including the following steps:

[0141] S1. According to the formula in Table 1, the core (emulsion, the amount of which is calculated on a dry basis), part of styrene and acrylonitrile monomers (each added at 50 wt%), 0.5 parts by weight of ferrous sulfate, 2 parts by weight of sodium formaldehyde sulfoxylate, 1.5 parts by weight of potassium disproportionated rosinate and 100 parts by weight of water are added to the reaction vessel based on 100 parts of dry basis core. The system is heated to 65°C, 1 part by weight of benzoyl peroxide is added and reacted for 1 hour, then the temperature is raised to 78°C, and the remaining styrene, acrylonitrile monomers and divinyl compounds and 1 part by weight of benzoyl peroxide are continuously added dropwise. The reaction time is maintained at 78°C for 4 hours to obtain a core-shell structured emulsion (solid content of 48.4%) (the specific amounts of each component are detailed in Table 1).

[0142] S2. According to the formula in Table 2, the product of step S1 (emulsion, the amount of which is calculated on a dry basis), fluorinated siloxane, vinyl siloxane, alkyl siloxane, 1% potassium persulfate, 1% potassium disproportionate and 100% water are added to the reactor. The system is heated to 70°C and reacted for 3 hours to obtain a multilayer core-shell polymer emulsion with a solid content of 42.5%. While maintaining the temperature, 1500 parts by weight of the product are transferred to a coagulation reactor and heated to 85°C. 550 parts by weight of 5% sulfuric acid are gradually added over 3 hours. The temperature is then raised to 95°C and maintained for 3 hours. The resulting coagulated latex is filtered through a 325-mesh filter and dried in a fluidized bed dryer at 70°C for 6 hours to obtain a multilayer core-shell polymer with a water content of <1%.

[0143] Table 1 shows the selection and dosage of raw materials for the core and intermediate layers in step S1 of the embodiments and comparative examples. (Unit: parts by weight)

[0144] Note: A11, A12 and A13 are all based on the intermediate layer. The intermediate layer is obtained by emulsion polymerization of A11, A12 and A13, and the sum of the percentages of the three is 100%.

[0145] Table 2 shows the selection and amount of each raw material in step S2 of the examples and comparative examples (unit: parts by weight).

[0146] Examples 13-24 and Comparative Examples 3-4

[0147] In Examples 13-24 and Comparative Examples 3-4, the polymer compositions were prepared according to the formulations in Table 3 by the following method, which included the following steps:

[0148] A polymer composition is obtained by uniformly mixing a fluorinated silicon multilayer core-shell structure polymer, a styrene-acrylonitrile copolymer, an antioxidant, and a lubricant, followed by extrusion, cooling, and granulation using a twin-screw extruder; the extrusion temperature is 185–220°C, the screw speed is 300 rpm, and the screw length-to-diameter ratio is 25:1.

[0149] Table 3 Formulations of the polymer compositions in Examples 13-24 (unit: parts by weight)

[0150] Performance testing

[0151] The polymer compositions prepared in the above examples and comparative examples were subjected to performance tests. The specific test items and test methods are as follows:

[0152] 1. Testing method:

[0153] (1) Notched impact performance test: The impact strength of the polymer compositions described in the above examples and comparative examples was tested according to ISO 179 (1993) based on the reference simply supported beam.

[0154] (2) Contact Angle Test: The hydrophobicity of the polymer composition was characterized using a contact angle measuring instrument (OCA20, Data Physics, Germany). The procedure was as follows: At room temperature, a 1 μL water droplet was rapidly dropped onto the surface of a 10cm*10cm square plate molded from plastic particles. Images of the droplet on the film surface were continuously captured by a camera to determine the droplet profile and baseline. An appropriate method was selected to fit the droplet profile curve to obtain the static contact angle of the square plate surface. To reduce experimental error, five points were randomly selected on the sample surface for measurement. The measurements were recorded, calculated, and the average value was taken as the final result. A contact angle ≥85° was considered to have good self-cleaning ability.

[0155] (3) Crack time determination: The polymer compositions described in the above examples and comparative examples were prepared into 60*10*2mm samples and placed in a mixed solution of ethyl acetate / ethanol volume ratio = 1 / 1. Cracks were observed on the sample surface and recorded as cracks. The time when cracks first appeared was calculated to reduce experimental error. Five average measurements were performed on each sample, and the average value was recorded and calculated as the final result.

[0156] 2. Test Results

[0157] The test results for each embodiment and comparative example are shown in Table 4.

[0158] Table 4 Test results of the examples and comparative examples

[0159] As can be seen from Table 6, the polymer composition obtained by this invention has good resistance to chemical solvents and water, as well as good mechanical properties; specifically, the notched impact strength is not less than 18 kJ / m. 2 The contact angle is not less than 85° and the cracking time is not less than 360s.

[0160] As can be seen from Comparative Example 3, if vinylsiloxane is not added during the synthesis of fluorinated silicon multilayer core-shell polymers, the resulting polymer compositions have poor hydrophobicity and chemical resistance.

[0161] As can be seen from Comparative Example 4, if the amount of fluorosiloxane is too large, the impact of the polymer composition obtained later will be significantly reduced. This may be because if the amount of fluorosiloxane is too large, the polybutadiene content in the fluorosilicone multilayer core-shell structure polymer will decrease, thus reducing the impact performance of ABS resin.

[0162] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A fluorinated silicon multilayer core-shell polymer, comprising a core, an intermediate layer, and an outer shell layer, characterized in that, Based on a dry weight of 100 parts for the core and intermediate layers, the outer shell layer comprises the following components: 5-25 parts of fluorosiloxane; 5-15 parts of vinylsiloxane; and 0-20 parts of alkylsiloxane. The intermediate layer has n layers, where n is a positive integer from 0 to 10; the core comprises diene polymers.

2. The fluorinated silicon multilayer core-shell polymer according to claim 1, characterized in that, The fluorinated siloxane includes one or more of trifluoropropylmethylcyclotrisiloxane, tetramethyltri-3-trifluoropropylcyclotetrasiloxane, or 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane.

3. The fluorinated silicon multilayer core-shell polymer according to claim 1, characterized in that, The vinylsiloxane includes one or more of tetramethyltetravinylcyclotetrasiloxane, γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltriisopropoxysilane.

4. The fluorinated silicon multilayer core-shell polymer according to claim 1, characterized in that, The alkylsiloxane includes one or more of octamethylcyclotetrasiloxane, hexamethyldisiloxane, hexaethyldisiloxane, methyltriethoxysilane, or 1,3-octyltetramethyldisiloxane.

5. The fluorinated silicon multilayer core-shell polymer according to claim 1, characterized in that, The average particle size of the core is 290-330 nm; preferably, the core comprises polyconjugated diene and / or inorganic particles coated with polyconjugated diene; further, the inorganic particles are one or more of silicon dioxide, aluminum oxide, zinc oxide, magnesium oxide, titanium dioxide or rare earth oxides.

6. The fluorinated silicon multilayer core-shell polymer according to claim 1, characterized in that, The intermediate layer is obtained by emulsion polymerization of a component comprising the following compounds: A11: Based on the intermediate layer, 40 to 79.9 wt% of at least one vinyl aromatic olefin; A12: Based on an intermediate layer, 10 to 39.9 wt% acrylonitrile monomer; A13: Based on the intermediate layer, 10 to 29.9 wt% of divinyl compounds; The mass ratio of the intermediate layer to the core is 20:80 to 80:20 on a dry basis.

7. The fluorinated silicon multilayer core-shell polymer according to claim 6, characterized in that, The divinyl compound has the following structural formula: Wherein, R1 is selected from substituted or unsubstituted alkylene, cycloalkylene, alkylene ester, cycloalkylene ester, alkeneoxy, cycloalkeneoxy, arylene, arylalkylene, and heteroarylene; wherein the number of carbon atoms in R1 is 1 to 20; R2 and R3 are independently selected from hydrogen, alkyl, cycloalkyl, alkyl ester, cycloalkyl ester, alkoxy, cycloalkoxy, aryl, aralkyl, and heteroaryl groups having 1 to 20 carbon atoms.

8. A method for preparing the fluorinated silicon multilayer core-shell structure polymer according to any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Prepare or fabricate the kernel; S2. Preparation of core-shell emulsion: Emulsion polymerization of A11, A12 and A13 in the presence of the core; S3. The product obtained in step S2, fluorinated siloxane, alkyl siloxane and vinyl siloxane are polymerized to obtain a polymer emulsion. The polymer emulsion is then subjected to high-temperature coagulation to obtain a fluorinated silicon multilayer core-shell structure polymer.

9. The preparation method according to claim 8, characterized in that, The polymerization reaction is carried out at a temperature of 60–90°C for 2–6 hours; the high-temperature condensation is carried out at a temperature of 80–100°C.

10. A polymer composition, characterized in that, Includes the following components, calculated in parts by weight: 15-40 parts of the fluorinated silicon multilayer core-shell polymer as described in any one of claims 1 to 7 or the fluorinated silicon multilayer core-shell polymer prepared by the preparation method described in claim 8 or 9; 60-80 parts of styrene-acrylonitrile copolymer and / or styrene-acrylonitrile-acrylate copolymer.

11. The polymer composition according to claim 10, characterized in that, It also includes 0.1 to 5 parts by weight of other components, which include one or more of the following: fillers, reinforcing agents, dyes, lubricants, mold release agents, stabilizers, antioxidants, UV absorbers, plasticizers, impact modifiers, antistatic agents, flame retardants, bactericides, or foaming agents.

12. A method for preparing the polymer composition according to claim 10 or 11, characterized in that, Includes the following steps: The components are mixed, extruded through a twin-screw extruder, cooled, and granulated to obtain a polymer composition.

13. The use of the polymer composition of claim 12 in the preparation of materials for automobiles, home appliances and office equipment.

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