Fluorine-containing styrene-acrylonitrile copolymer composition as well as preparation method and application thereof

Abstract

The invention provides a fluorine-containing styrene-acrylonitrile copolymer composition as well as a preparation method and application thereof. The fluorine-containing styrene-acrylonitrile copolymer composition comprises the following components in percentage by mass: 90-100% of a component A and 0-10% of a component B, the weight-average molecular weight of the fluorine-containing styrene-acrylonitrile copolymer composition ranges from 80000 g / mol to 150000 g / mol; the molecular weight distribution of the fluorine-containing styrene-acrylonitrile copolymer composition is 2.15 to 2.60. The fluorine-containing styrene-acrylonitrile copolymer composition provided by the invention has good lubricity, and the ABS composition prepared from the fluorine-containing styrene-acrylonitrile copolymer composition has good processability and mechanical properties, is low in insertion and extraction force, and can improve the problem of precipitation of an external lubricant.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a fluorostyrene-acrylonitrile copolymer composition, a preparation method thereof, and an application thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS), as a general-purpose plastic, has excellent properties such as good chemical resistance, wear resistance, and processability, and is widely used in automotive engineering, medical devices, construction engineering and other fields. ABS can also be used in children's toys, such as building blocks, which need to meet the requirements of safety, durability, suitable insertion and extraction force, beautiful color, etc. At present, the children's building block toys made of ABS materials used in China are prone to problems such as high insertion and extraction force, difficult insertion and extraction for children, and excessive noise during insertion and extraction.

[0003] CN115386177A discloses a high-gloss scratch-resistant ABS material for toy manufacturing, a preparation method thereof, and an application thereof. The high-gloss scratch-resistant ABS material for toy manufacturing includes the following components calculated by mass fraction: 50-60 parts of AS resin, 15-25 parts of toughening high rubber powder, 5-10 parts of silicone additive, 10-20 parts of TPEE, 0.2-0.4 parts of light stabilizer, 0.2-0.4 parts of antioxidant, and 0.2-0.6 parts of lubricant; wherein, the modulus of the AS resin is greater than 2400 MPa, the toughening high rubber powder is acrylonitrile-butadiene-styrene copolymer, and the toughening high rubber powder includes a butadiene segment with a content greater than or equal to 60%, an acrylonitrile segment with a content of 10-14%, and a styrene segment with a content of 26-30%. This technical solution improves the rigidity and toughness of the ABS material by adding the linear block copolymer TPEE combining hard and soft segments to change the crystal structure of the ABS material from amorphous state to crystalline state; in addition, a silicone additive with a lubricating effect is added to improve the hand feeling and have a good scratch-resistant effect. Although this technical solution can improve the lubricity of toys, since the silicone additive is an external lubricant, if the addition amount is poorly controlled, it is easy to have an excessive amount, gradually migrate to the surface, and appear exudation, greasy hand feeling and other situations.

[0004] Styrene-acrylonitrile copolymer can be used as one of the components of ABS material, and can provide good rigidity, heat resistance and processing performance for ABS material. When the physical properties such as the chemical structure, molecular weight and molecular weight distribution of styrene-acrylonitrile copolymer change, the macroscopic properties of the composed ABS material will change, such as mechanical properties, processing properties, etc.

[0005] In addition, the compatibility of color powder will affect the color uniformity of the obtained product, affect the appearance effect and aesthetics of the product, and the compatibility with color powder also needs to be considered during the preparation of ABS material.

[0006] Therefore, it is necessary to develop a styrene-acrylonitrile copolymer resin that can improve the high insertion and extraction force of ABS materials and solve the problem of external lubricant precipitation, and prepare an ABS composition with good mechanical properties, processing properties, and low insertion and extraction force. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a fluorinated styrene-acrylonitrile copolymer composition, its preparation method and application. The fluorinated styrene-acrylonitrile copolymer composition has a low surface energy and good lubricity. The prepared ABS composition has good mechanical properties and processing properties, low insertion and extraction force, and can solve the problem of external lubricant precipitation.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a fluorinated styrene-acrylonitrile copolymer composition, which comprises the following components by mass percentage: Component A 90% - 100% (such as 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%, etc.) and Component B 0 - 10% (such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.).

[0010] The Component A comprises a fluorinated styrene-acrylonitrile copolymer, which is mainly made of the following monomers by mass percentage: styrene monomers 40% - 80% (such as 45%, 50%, 55%, 60%, 65%, 70% or 75%, etc.), acrylonitrile monomers 10% - 40% (such as 15%, 20%, 25%, 30% or 35%, etc.), fluorinated acrylate 1% - 35% (such as 5%, 10%, 15%, 20%, 25% or 30%, etc.) and other copolymerizable monomers 0 - 10% (such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.), and the sum of the mass percentages of the monomers is 100%.

[0011] The Component B comprises additives and / or processing aids.

[0012] The weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition is 80,000 to 150,000 g / mol, such as 90,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol or 140,000 g / mol, etc.; the molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition is 2.15 to 2.60, such as 2.20, 2.25, 2.30, 2.35, 2.40, 2.45, 2.50 or 2.55, etc.

[0013] In the present invention, a fluorinated acrylate is introduced to form a fluorinated styrene-acrylonitrile copolymer, which has a fluorinated side chain and contains a C-F bond. The C-F bond structure is compact and stable, and has a high electronegativity, which reduces the intermolecular attraction. The obtained fluorinated styrene-acrylonitrile copolymer composition has a low surface energy and good lubricity. By controlling the weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition to be 80,000 to 150,000 g / mol and the molecular weight distribution to be 2.15 to 2.60, the obtained fluorinated styrene-acrylonitrile copolymer composition has good mechanical properties, processing properties and lubricity. When it is used to prepare an ABS composition, the obtained ABS composition has self-lubricity on the surface, low insertion force and good compatibility with color powder; there is no need to add an external lubricant, which increases the hand feeling and auditory comfort during use and improves the problem of external lubricant precipitation.

[0014] In the present invention, the weight-average molecular weight and molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition refer to the weight-average molecular weight and molecular weight distribution obtained by testing the fluorinated styrene-acrylonitrile copolymer composition with a gel permeation chromatograph.

[0015] Preferably, the styrene monomer includes any one or a combination of at least two of styrene, α-methylstyrene or p-methylstyrene.

[0016] Preferably, the acrylonitrile monomer includes acrylonitrile and / or methacrylonitrile.

[0017] Preferably, the fluorinated acrylate includes any one or a combination of at least two of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, nonafluorohexyl acrylate, nonafluorohexyl methacrylate or heptafluoroisopropyl acrylate, and is further preferably hexafluorobutyl methacrylate.

[0018] In the present invention, different fluorinated chain lengths in the fluorinated acrylate can affect the enrichment degree of fluorine atoms on the surface of the injection molded part, thereby affecting the lubricity. Although it is generally considered that when the fluorinated acrylate contains more fluorine atoms, the hydrophobic effect is better, but when the proportion of the fluorinated acrylate gradually increases, the enrichment ability of fluorine atoms during polymerization will gradually exceed the influence of the fluorinated chain length. Therefore, the lubricity effect of the fluorinated styrene-acrylonitrile copolymer resin prepared from the fluorinated acrylate with a lower fluorinated chain length will be better than that with a higher fluorinated chain length; and the steric hindrance of the fluorine-containing group in the molecule with a benzene ring is greater than that in the straight-chain molecule, and the residual internal stress during injection molding is larger. Therefore, the fluorinated acrylate is preferably hexafluorobutyl methacrylate.

[0019] Preferably, the other copolymerizable monomers include any one or a combination of at least two of methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenyl maleimide, maleic anhydride, acrylamide, or vinyl methyl ether.

[0020] Preferably, the fluorinated styrene-acrylonitrile copolymer is mainly made of the following monomers by mass percentage: 40% - 80% of styrene monomers (such as 45%, 50%, 55%, 60%, 65%, 70%, or 75%, etc.), 10% - 40% of acrylonitrile monomers (such as 15%, 20%, 25%, 30%, or 35%, etc.), 8% - 20% of fluorinated acrylate (9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%, etc.), and 0 - 10% of other copolymerizable monomers (such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.), and the sum of the mass percentages of the monomers is 100%.

[0021] In the present invention, based on the total mass of the monomers being 100%, controlling the mass percentage of the fluorinated acrylate to be 8% - 20% can effectively balance the insertion and extraction force and the toner compatibility, so that the ABS composition containing the fluorinated styrene-acrylonitrile copolymer composition simultaneously has a lower insertion and extraction force and better toner compatibility.

[0022] Preferably, the fluorinated styrene-acrylonitrile copolymer includes a random copolymerization block of styrene monomers and acrylonitrile monomers and a random copolymerization block of styrene monomers, acrylonitrile monomers, and fluorinated acrylate.

[0023] In the present invention, the fluorinated acrylate in the fluorinated styrene-acrylonitrile copolymer can be concentrated in a part of the chain segment, which can better play the role of reducing the surface energy and improving the lubricity, thereby reducing the insertion and extraction force of the ABS composition.

[0024] In the present invention, the fluorinated styrene-acrylonitrile copolymer composition may include 0 - 10% of additives and / or processing aids.

[0025] Preferably, the processing aid includes any one or a combination of at least two of an emulsifier, a molecular weight regulator, or an oil-soluble initiator.

[0026] Preferably, the molecular weight regulator includes mercaptan.

[0027] Preferably, the mercaptan includes any one or a combination of at least two of n-dodecyl mercaptan, tert-dodecyl mercaptan, or 3-mercaptohexanol, and is further preferably n-dodecyl mercaptan.

[0028] In the present invention, the mercaptan preferably includes any one or a combination of at least two of n-dodecyl mercaptan, tert-dodecyl mercaptan, or 3-mercaptohexanol. Among them, a fluorostyrene-acrylonitrile copolymer composition obtained by preferably using n-dodecyl mercaptan or tert-dodecyl mercaptan as the molecular weight regulator is used to prepare an ABS composition, and its lubricating performance and toner compatibility change little. However, n-dodecyl mercaptan is a straight-chain alkyl mercaptan with a relatively simple molecular structure and is more likely to react with fluoropolymers; 3-mercaptohexanol has low chain transfer efficiency due to side reactions easily caused by hydroxyl groups, as well as steric hindrance and stability problems, making it difficult to meet the requirements for precise control of molecular weight in industrial polymerization. Therefore, it is further preferably n-dodecyl mercaptan.

[0029] Preferably, the oil-soluble initiator includes any one or a combination of at least two of azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), or benzoyl peroxide (BPO), and is further preferably benzoyl peroxide.

[0030] In the present invention, the additive can be, for example, any one or a combination of at least two of a plasticizer, an antistatic agent, a light stabilizer, a lubricant, a foaming agent, a tackifier, a filler, a surface active substance, a flame retardant, a dye, a pigment, an antioxidant, a hydrolysis stabilizer, a heat stabilizer, an anti-fading agent, or a reinforcing agent.

[0031] In the present invention, the additive can be added during the preparation of the fluorostyrene-acrylonitrile copolymer, or the prepared fluorostyrene-acrylonitrile copolymer can be mixed with the additive.

[0032] In the present invention, the light stabilizer can be all common light stabilizers. For example, compounds based on any one of benzophenone, benzotriazole, cinnamic acid, organic phosphites or phosphonates, and hindered amine compounds.

[0033] In the present invention, the lubricant can be any one or a combination of at least two of hydrocarbon compounds, fatty alcohol compounds, ketone compounds, carboxylic acid compounds, oxidized polyethylene wax, carboxamide compounds, or carboxylic acid ester compounds.

[0034] Exemplarily, the hydrocarbon compound includes any one or a combination of at least two of an oil compound, a paraffin compound, a polyethylene wax compound, or a polypropylene wax compound.

[0035] Exemplarily, the carboxylic acid compound includes a carboxylic acid compound having 6 - 30 (such as 9, 12, 15, 18, 21, 24, or 27, etc.) carbon atoms.

[0036] Exemplarily, the fatty acid compound having 6 - 30 (such as 9, 12, 15, 18, 21, 24, or 27, etc.) carbon atoms includes montanic acid.

[0037] Exemplarily, the carboxylic acid ester compound is prepared from an alcohol compound and a long - chain carboxylic acid compound having 6 - 30 (such as 9, 12, 15, 18, 21, 24, or 27, etc.) carbon atoms. The alcohol compound includes a fatty alcohol compound, and the fatty alcohol compound includes any one or a combination of at least two of ethanol, glycerol, ethylene glycol, or pentaerythritol.

[0038] In the present invention, the antioxidant can be a common antioxidant, such as a phenolic antioxidant and / or benzotriazole.

[0039] Exemplarily, the phenolic antioxidant includes any one or a combination of at least two of an alkylated monophenol, an ester of β-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionic acid, or an amide of β-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionic acid.

[0040] Exemplarily, the phenolic antioxidant includes any one or a combination of at least two of 2,6 - di - tert - butyl - 4 - methylphenol, pentaerythritol tetra[3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate], or N,N'-bis(3,5 - di - tert - butyl - 4 - hydroxyphenylpropionyl)hexamethylenediamine.

[0041] In a second aspect, the present invention provides a method for preparing a fluorinated styrene - acrylonitrile copolymer composition as described in the first aspect. The preparation method includes the following steps: The preparation method includes the following steps: mixing a styrene monomer, an acrylonitrile monomer, a fluorinated acrylate, optionally other copolymerizable monomers, and optionally component B, and reacting to obtain the fluorinated styrene - acrylonitrile copolymer composition.

[0042] In the present invention, a fluorinated acrylate is added to the reaction system to generate a fluorinated styrene - acrylonitrile copolymer by a polymerization reaction.

[0043] Preferably, the preparation method includes the following steps:

[0044] (1) Mix a part of styrenic monomers, a part of acrylonitrile monomers, optionally a part of other copolymerizable monomers, component B and a solvent uniformly, and react to obtain an intermediate product.

[0045] (2) Mix the remaining styrenic monomers, the remaining acrylonitrile monomers, a fluorinated acrylate, and optionally the remaining other copolymerizable monomers with the intermediate product prepared in step (1), and react to obtain the fluorinated styrene-acrylonitrile copolymer composition.

[0046] Preferably, based on the total mass of the styrenic monomers being 100%, the mass of the part of styrene in step (1) is 20% - 80%, such as 30%, 40%, 50%, 60% or 70%, etc.

[0047] Preferably, based on the total mass of the acrylonitrile monomers being 100%, the mass of the part of acrylonitrile in step (1) is 20% - 80%, such as 30%, 40%, 50%, 60% or 70%, etc.

[0048] Preferably, based on the total mass of the other copolymerizable monomers being 100%, the mass of the part of the other copolymerizable monomers in step (1) is 0 - 100%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, etc.

[0049] In the present invention, in order to make the fluorinated acrylate concentrate at one end of the chain segment more, a two-step feeding method is preferably adopted, and the fluorinated acrylate is added in step (2), so that the effect of reducing the insertion and extraction force of the prepared fluorinated styrene-acrylonitrile copolymer composition is better.

[0050] Preferably, the mass of the molecular weight regulator is 0.1% - 1% of the total mass of the styrenic monomers, acrylonitrile monomers, fluorinated acrylate and other copolymerizable monomers, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, etc.

[0051] Preferably, the mass of the oil-soluble initiator is 0.1% - 1% of the total mass of the styrenic monomers, acrylonitrile monomers, fluorinated acrylate and other copolymerizable monomers, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, etc.

[0052] Preferably, the mass of the solvent is 5% - 12% of the total mass of the styrenic monomers, acrylonitrile monomers, fluorinated acrylate and other copolymerizable monomers, such as 6%, 7%, 8%, 9%, 10% or 11%, etc.

[0053] Preferably, the reaction in step (1) is carried out with stirring in a reaction kettle. The reaction temperature is 60-150 °C (such as 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C or 140 °C, etc.), the reaction pressure is 0.2-0.8 MPa (such as 0.25 MPa, 0.30 MPa, 0.35 MPa, 0.40 MPa, 0.45 MPa, 0.50 MPa, 0.55 MPa, 0.60 MPa, 0.65 MPa, 0.70 MPa or 0.75 MPa, etc.), the reaction time is 0.5-4 h (such as 1 h, 1.5 h, 2 h, 2.5 h, 3.0 h or 3.5 h, etc.), and the stirring speed is 10-300 r / min (such as 30 r / min, 60 r / min, 90 r / min, 120 r / min, 150 r / min, 180 r / min, 210 r / min, 240 r / min or 270 r / min, etc.).

[0054] Preferably, the solvent includes organic solvents.

[0055] Preferably, the organic solvent includes any one or a combination of at least two of ethylbenzene, toluene or xylene.

[0056] Preferably, the reaction in step (2) is carried out with stirring in a reaction kettle. The reaction temperature is 90-150 °C (such as 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C or 145 °C, etc.), the reaction pressure is 0.2-0.8 MPa (such as 0.25 MPa, 0.30 MPa, 0.35 MPa, 0.40 MPa, 0.45 MPa, 0.50 MPa, 0.55 MPa, 0.60 MPa, 0.65 MPa, 0.70 MPa or 0.75 MPa, etc.), the reaction time is 0.5-4 h (such as 1 h, 1.5 h, 2 h, 2.5 h, 3.0 h or 3.5 h, etc.), and the stirring speed is 10-300 r / min (such as 30 r / min, 60 r / min, 90 r / min, 120 r / min, 150 r / min, 180 r / min, 210 r / min, 240 r / min or 270 r / min, etc.).

[0057] Preferably, the reaction kettle includes a tank reactor.

[0058] Preferably, after the reaction in step (2), there are also steps of devolatilization, extrusion granulation and drying.

[0059] In the present invention, the devolatilization gas removed under vacuum in the devolatilization step can be fully recovered via a condenser for reuse.

[0060] In a third aspect, the present invention provides a fluorine-containing ABS resin, which comprises a fluorine-containing styrene-acrylonitrile copolymer composition as described in the first aspect and an ABS high rubber powder.

[0061] Preferably, the mass percentage content of butadiene in the ABS high rubber powder is 55% to 65%, such as 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63% or 64%, etc.

[0062] Preferably, the fluorine-containing ABS resin comprises the following components by weight: 60 to 85 parts (such as 63 parts, 66 parts, 69 parts, 72 parts, 75 parts, 78 parts, 81 parts or 84 parts, etc.) of the fluorine-containing styrene-acrylonitrile copolymer composition as described in the first aspect and 15 to 40 parts (such as 18 parts, 21 parts, 24 parts, 27 parts, 30 parts, 33 parts, 36 parts or 39 parts, etc.) of the ABS high rubber powder.

[0063] Preferably, the fluorine-containing ABS resin comprises the following components by mass percentage: 60% to 85% (such as 63%, 66%, 69%, 72%, 75%, 78%, 81% or 84%, etc.) of the fluorine-containing styrene-acrylonitrile copolymer composition as described in the first aspect and 15% to 40% (such as 18%, 21%, 24%, 27%, 30%, 33%, 36% or 39%, etc.) of the ABS high rubber powder.

[0064] In the present invention, the fluorine-containing styrene-acrylonitrile copolymer composition can be mixed and extruded with the ABS high rubber powder to obtain a fluorine-containing ABS resin, which has good lubricants, low insertion and extraction force, and can improve the problem of external lubricant precipitation.

[0065] In a fourth aspect, the present invention provides an ABS composition, which comprises 60 to 85 parts (such as 63 parts, 66 parts, 69 parts, 72 parts, 75 parts, 78 parts, 81 parts or 84 parts, etc.) of the fluorine-containing styrene-acrylonitrile copolymer composition as described in the first aspect, 15 to 40 parts (such as 18 parts, 21 parts, 24 parts, 27 parts, 30 parts, 33 parts, 36 parts or 39 parts, etc.) of the ABS high rubber powder and 0.01 to 150 parts (such as 20 parts, 40 parts, 60 parts, 80 parts, 100 parts, 120 parts or 140 parts, etc.) of an auxiliary agent.

[0066] Or it comprises 100 parts of the fluorine-containing ABS resin as described in the third aspect and 0.01 to 150 parts (such as 20 parts, 40 parts, 60 parts, 80 parts, 100 parts, 120 parts or 140 parts, etc.) of an auxiliary agent.

[0067] Preferably, the auxiliary agent includes any one or a combination of at least two of a flame retardant, an antioxidant, a lubricant, a colorant or an antistatic agent.

[0068] Preferably, the flame retardant in the ABS composition includes any one or a combination of at least two of antimony trioxide, magnesium hydroxide, or aluminum hydroxide.

[0069] Preferably, the antioxidant in the ABS composition includes any one or a combination of at least two of antioxidant 1010, antioxidant 168, antioxidant 1076, or antioxidant 618.

[0070] Preferably, the lubricant in the ABS composition includes any one or a combination of at least two of ethylene bisstearamide (lubricant EBS), zinc stearate, glycerol monostearate, or pentaerythritol fatty acid ester.

[0071] Preferably, the colorant in the ABS composition includes any one or a combination of at least two of phthalocyanine blue, phthalocyanine green, titanium dioxide, or carbon black.

[0072] Preferably, the antistatic agent in the ABS composition includes any one or a combination of at least two of carbon nanotubes (CNTs), carbon black (CB), or quaternary ammonium salt-based maleimide copolymer.

[0073] In a fifth aspect, the present invention provides an application of any one of the fluorinated styrene-acrylonitrile copolymer composition as described in the first aspect, the fluorinated ABS resin as described in the third aspect, or the ABS composition as described in the fourth aspect in automotive interior and exterior trim materials, home appliance housing materials, toy materials, food container materials, or medical supply materials, and is further preferably applied to toy building blocks.

[0074] Compared with the prior art, the present invention has the following beneficial effects:

[0075] In the present invention, by introducing fluorinated acrylate to form a fluorinated styrene-acrylonitrile copolymer composition and controlling the weight average molecular weight and molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition within a specific range, the surface energy of the fluorinated styrene-acrylonitrile copolymer composition is low, it has self-lubricity, good mechanical properties and processing properties. When it is used to prepare an ABS composition, the prepared ABS composition has a low insertion and extraction force, can reduce the noise during insertion and extraction, increase the hand feeling and auditory comfort during use, has good color powder compatibility, and can be used to prepare children's toy products with uniform and beautiful colors. Specific Embodiments

[0076] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0077] Some components in the examples and comparative examples are as follows:

[0078] n-Dodecyl mercaptan: The manufacturer is Phillips in the United States, and its structure is as follows:

[0079]

[0080] tert-Dodecyl mercaptan, the structure is as follows:

[0081]

[0082] Example 1

[0083] This example provides a fluorinated styrene-acrylonitrile copolymer composition and a preparation method thereof. The raw materials for preparing the fluorinated styrene-acrylonitrile copolymer composition include the following components in parts by weight: 60 parts of styrene, 27 parts of acrylonitrile, 5 parts of fluorinated acrylate, 0.15 part of molecular weight regulator (n-dodecyl mercaptan), 0.1 part of oil-soluble initiator (benzoyl peroxide), and 8 parts of solvent (ethylbenzene).

[0084] The preparation method of the above-mentioned fluorinated styrene-acrylonitrile copolymer composition includes the following steps:

[0085] (1) Mix 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.15 part by weight of molecular weight regulator (n-dodecyl mercaptan), 0.1 part by weight of oil-soluble initiator (benzoyl peroxide), and 8 parts by weight of solvent (ethylbenzene) evenly, add them into a kettle reactor, stir, the reaction temperature is 80 °C, the reaction pressure is 0.3 MPa, the stirring speed is 70 r / min, and the reaction time is 2 h to obtain an intermediate;

[0086] (2) Pre-mix 30 parts by weight of styrene, 17 parts by weight of acrylonitrile, and 5 parts by weight of fluorinated acrylate (hexafluorobutyl methacrylate) evenly, and drop them into the kettle reactor to mix with the intermediate prepared in step (1). The temperature of the kettle reactor is 120 °C, the pressure is 0.3 MPa, the stirring speed is 70 r / min, the reaction time is 2 h, and devolatilization is carried out in a devolatilizer, and extrusion granulation is carried out by a twin-screw extruder. The twin-screw extruder has a total of 6 temperature zones, and the temperatures of the first zone to the sixth zone are 200 °C, 220 °C, 240 °C, 210 °C, 230 °C, and 220 °C in sequence. Then, it is dried at 60 °C for 4 h to obtain the fluorinated styrene-acrylonitrile copolymer composition. The weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition in the fluorinated styrene-acrylonitrile copolymer composition is 130,000, and the molecular weight distribution is 2.20.

[0087] Examples 2 to 13 and Comparative Examples 1 to 5 adopt the same preparation method as Example 1, the difference lies in the added raw materials, contents, and process parameters. The contents of the raw materials are in parts by weight, and the specific details are shown in Tables 1, 2, and 3.

[0088] Table 1

[0089]

[0090]

[0091] In Table 1, “ / ” means that the raw material was not added.

[0092] Table 2

[0093]

[0094]

[0095] In Table 2, “ / ” means that the raw material was not added.

[0096] Table 3

[0097]

[0098]

[0099] In Table 3, “ / ” means that the raw material was not added.

[0100] The molecular weight and molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer compositions provided in the above Examples 1 to 13 and Comparative Examples 1 to 5 were tested as follows: tetrahydrofuran was used as a solvent, and the weight average molecular weight and molecular weight distribution of the prepared fluorinated styrene-acrylonitrile copolymer compositions were tested by gel permeation chromatography, pure tetrahydrofuran was used as an eluent, and linear polystyrene was used as a standard to obtain a calibration curve.

[0101] Application Example 1

[0102] This application example provides an ABS composition. The preparation method of the ABS composition is as follows: 75 parts by weight of the fluorinated styrene-acrylonitrile copolymer composition provided in Example 1, 25 parts by weight of ABS high-rubber powder (Kumho HR-181), 0.15 parts by weight of antioxidant 1010, 0.15 parts by weight of antioxidant 168 and 0.4 parts by weight of lubricant EBS are mixed, and the mixture is extruded and granulated through a twin-screw extruder at an extrusion temperature of 240° C. to obtain the ABS composition.

[0103] Application Examples 2 to 13

[0104] Application Examples 2 to 13 respectively provide an ABS composition, which differs from Application Example 1 only in that the fluorinated styrene-acrylonitrile copolymer composition obtained in Examples 2 to 13 is used to replace the fluorinated styrene-acrylonitrile copolymer composition obtained in Example 1, and other conditions are the same as those in Application Example 1.

[0105] Application Example 14

[0106] This application example provides an ABS composition, the difference from Application Example 1 being only that the weight part of the fluorinated styrene-acrylonitrile copolymer composition provided in Example 1 is adjusted to 62 parts, and the weight part of the ABS high rubber powder (Kumho HR-181) is adjusted to 38 parts, with other conditions being the same as those in Application Example 1.

[0107] Application Example 15

[0108] This application example provides an ABS composition, the difference from Application Example 1 being only that the weight part of the fluorinated styrene-acrylonitrile copolymer composition provided in Example 1 is adjusted to 82 parts, and the weight part of the ABS high rubber powder (Kumho HR-181) is adjusted to 18 parts, with other conditions being the same as those in Application Example 1.

[0109] Comparative Application Examples 1-5

[0110] Comparative Application Examples 1-5 respectively provide an ABS composition, the difference from Application Example 1 being only that the styrene-acrylonitrile copolymer resin obtained in Comparative Examples 1-5 is used to replace the fluorinated styrene-acrylonitrile copolymer composition obtained in Example 1, with other conditions being the same as those in Application Example 1.

[0111] The following performance tests were carried out on the ABS compositions provided in Application Examples 1-15 and Comparative Application Examples 1-5:

[0112] (1) Insertion and extraction force test: The ABS composition was melt-injected into a building block mold to form a building block plug-in connector. The building block plug-in connector was correctly installed on the fixture of the experimental equipment to ensure accurate alignment between the plug and the socket of the building block plug-in connector. The insertion and extraction stroke was set to 20 mm, the insertion and extraction speed was 30 times, and 10 times were tested per minute. The insertion and extraction force values for each insertion and extraction were recorded by a sensor, and the average insertion and extraction force value was calculated.

[0113] (2) Compatibility of color powder: The ABS composition and yellow color powder (brand organic pigment yellow H2R, manufacturer Clariant) were injection-molded according to a weight ratio of 1:0.0003 to obtain a color plate. The chromaticity a, b, and c values were measured using a colorimeter. Among them, b represents the value of the yellow and blue color of the object, with positive values for yellow and negative values for blue. Four points were taken at different positions on the color plate to measure their b values, denoted as b1, b2, b3, and b4, and their average value M and variance s were calculated 2 , and the specific formula is as follows:

[0114]

[0115] If s 2 ≤0.2, the compatibility of the color powder is considered good; if s 2 >0.2, it is considered that the compatibility of the color powder is poor.

[0116] The results of the tests are shown in Table 4 below.

[0117] Table 4

[0118]

[0119]

[0120] In Table 4, " / " represents that this test item was not carried out.

[0121] From the content of Table 4, it can be seen that the insertion and extraction force of the ABS compositions provided in Application Examples 1-15 is 20-34 N, and the toner compatibility s 2 ≤0.2.

[0122] Comparing Application Examples 4-8, it can be known that based on the total mass of styrene monomers, acrylonitrile monomers, fluorinated acrylate and other copolymerizable monomers being 100%, controlling the mass of fluorinated acrylate at 8%-20% can balance the insertion and extraction force and the toner compatibility.

[0123] Comparing Application Example 6, Application Example 9 and Application Example 10, it can be known that compared with dodecafluoroheptyl methacrylate and heptafluoroisopropyl acrylate, the fluorinated styrene-acrylonitrile copolymer composition prepared by adding hexafluorobutyl methacrylate has better performance.

[0124] Comparing with Application Example 6, if a fluorinated acrylate is added in step (1) (Application Example 13), the fluorinated chain segments will be randomly embedded between the acrylonitrile and styrene copolymers, the fluorinated side chains will be buried, and fewer fluorine atoms will be exposed on the surface of the workpiece. Therefore, the reduction in the insertion and extraction force is lower and the insertion and extraction force is higher.

[0125] Comparing with Application Example 6, if no fluorinated acrylate is added (Comparative Application Example 1), the insertion and extraction force increases and the stain resistance deteriorates.

[0126] Comparing with Application Example 6, if the weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition used is too large (Comparative Application Example 2), the fluorinated styrene-acrylonitrile copolymer composition has a high melt viscosity, and it is difficult to disperse the toner in the ABS composition, resulting in agglomeration or uneven distribution, and the toner compatibility is reduced; if the weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition used is too small (Comparative Application Example 3), the fluorinated styrene-acrylonitrile copolymer composition has a high fluidity, and the situation of toner interfacial migration occurs, and the toner compatibility is reduced.

[0127] Compared with Application Example 6, if the molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition used is too large (Comparative Application Example 4), the insertion and extraction force of the prepared ABS composition increases, and the compatibility with color powder decreases. The inventors speculate that this may be due to uneven melt flow, resulting in an increase in the surface roughness of the injection-molded parts, leading to an increase in the insertion and extraction force. In addition, the high mobility of the low molecular weight chain segments brought about by the too large molecular weight distribution causes color powder migration and local aggregation, while the high molecular weight chain segments hinder the dispersion of color powder, further forming uneven hue regions, resulting in a decrease in the compatibility with color powder; if the molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition used is too small (Comparative Application Example 3), the surface lacks the lubricating effect of low molecular weight components, the friction coefficient increases, the insertion and extraction force of the prepared ABS composition rises, and the relatively small molecular weight distribution makes the melt viscosity high during injection molding, the color powder is not easily dispersed and is prone to agglomeration, resulting in uneven hue and a decrease in the compatibility with color powder.

[0128] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate a fluorinated styrene-acrylonitrile copolymer composition, its preparation method and application of the present invention, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A fluorostyrene-acrylonitrile copolymer composition, characterized in that, The fluorinated styrene-acrylonitrile copolymer composition comprises the following components by mass percentage: 90% - 100% of component A and 0 - 10% of component B; Component A includes a fluorinated styrene-acrylonitrile copolymer, which is mainly made of the following monomers by mass percentage: 40% - 80% of styrene monomers, 10% - 40% of acrylonitrile monomers, 1% - 35% of fluorinated acrylate, and 0 - 10% of other copolymerizable monomers; Component B includes additives and / or processing aids; The weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition is 80,000 - 150,000 g / mol; the molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition is 2.15 - 2.

60.

2. The fluorostyrene-acrylonitrile copolymer composition according to claim 1, characterized in that, The styrene monomers include any one or at least two combinations of styrene, α-methylstyrene, or p-methylstyrene; Preferably, the acrylonitrile monomers include acrylonitrile and / or methacrylonitrile; Preferably, the fluorinated acrylate includes any one or at least two combinations of hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, nonafluorohexyl acrylate, nonafluorohexyl methacrylate, or heptafluoroisopropyl acrylate, and more preferably hexafluorobutyl methacrylate; Preferably, the other copolymerizable monomers include any one or at least two combinations of methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenyl maleimide, maleic anhydride, acrylamide, or vinyl methyl ether.

3. The fluorine-containing styrene-acrylonitrile copolymer composition according to claim 1, wherein The fluorinated styrene-acrylonitrile copolymer is mainly made of the following monomers by mass percentage: 40% - 80% of styrene monomers, 10% - 40% of acrylonitrile monomers, 8% - 20% of fluorinated acrylate, and 0 - 10% of other copolymerizable monomers.

4. A method for preparing a fluorinated styrene-acrylonitrile copolymer composition according to any one of claims 1-3, characterized in that, The preparation method comprises the following steps: mixing styrene monomers, acrylonitrile monomers, fluorinated acrylate, optionally other copolymerizable monomers, and optionally component B, and reacting to obtain the fluorinated styrene-acrylonitrile copolymer composition.

5. The preparation method according to claim 4, characterized in that, The preparation method comprises the following steps: (1) Mixing part of the styrene monomers, part of the acrylonitrile monomers, optionally part of the other copolymerizable monomers, component B, and a solvent uniformly, and reacting to obtain an intermediate; (2) Mixing the remaining styrene monomers, the remaining acrylonitrile monomers, fluorinated acrylate, optionally the remaining other copolymerizable monomers with the intermediate obtained in step (1), and reacting to obtain the fluorinated styrene-acrylonitrile copolymer composition; Preferably, based on the total mass of the styrene monomers being 100%, the mass of the part of styrene in step (1) is 20% - 80%; Preferably, based on the total mass of the acrylonitrile monomers being 100%, the mass of the part of acrylonitrile in step (1) is 20% - 80%; Preferably, based on the total mass of other copolymerizable monomers being 100%, the mass of the other copolymerizable monomers in the part described in step (1) is 0 to 100%.

6. The preparation method according to claim 5, characterized in that The solvent described in step (1) includes an organic solvent; Preferably, the organic solvent includes any one or a combination of at least two of ethylbenzene, toluene, or xylene; Preferably, after the reaction described in step (2), there are further steps of devolatilization, extrusion granulation, and drying.

7. A fluorine-containing ABS resin, characterized in that, The fluorine-containing ABS resin includes the fluorine-containing styrene-acrylonitrile copolymer composition as described in any one of claims 1-3 and an ABS high rubber powder.

8. The fluorine-containing ABS resin according to claim 7, wherein The fluorine-containing ABS resin includes the following components by weight: 60 to 85 parts of the fluorine-containing styrene-acrylonitrile copolymer composition as described in any one of claims 1-3 and 15 to 40 parts of an ABS high rubber powder.

9. An ABS composition, characterized in that, The ABS composition includes 60 to 85 parts of the fluorine-containing styrene-acrylonitrile copolymer composition as described in any one of claims 1-3, 15 to 40 parts of an ABS high rubber powder, and 0.01 to 150 parts of an auxiliary agent; Or it includes 100 parts of the fluorine-containing ABS resin as described in claim 7 or 8 and 0.01 to 150 parts of an auxiliary agent.

10. Use of any one of the fluorine-containing styrene-acrylonitrile copolymer composition as described in any one of claims 1-3, the fluorine-containing ABS resin as described in claim 7 or 8, or the ABS composition as described in claim 9 in automotive interior and exterior trim materials, household appliance housing materials, toy materials, food container materials, or medical supplies materials.

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