A fluorine-containing styrene-acrylonitrile copolymer composition, a method for preparing the same, and an application thereof

Abstract

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

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a fluorinated styrene-acrylonitrile copolymer composition, its preparation method, and its application. Background Technology

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS), as a general-purpose plastic, possesses excellent properties such as chemical resistance, abrasion resistance, and processability, and is widely used in automotive engineering, medical devices, and construction engineering. ABS can also be used in children's toys, such as building blocks, which need to simultaneously meet requirements such as safety, durability, suitable insertion and extraction force, and aesthetically pleasing colors. Currently, children's building block toys made of ABS material in China are prone to problems such as high insertion and extraction force, difficulty for children to insert and remove blocks, and excessive noise during insertion and removal.

[0003] CN115386177A discloses a high-gloss, scratch-resistant ABS material for toy manufacturing, its preparation method, and its application. The high-gloss, scratch-resistant ABS material for toy manufacturing comprises the following components by mass: 50-60 parts AS resin, 15-25 parts toughening high-strength rubber powder, 5-10 parts silicone additives, 10-20 parts TPEE, 0.2-0.4 parts light stabilizer, 0.2-0.4 parts antioxidant, and 0.2-0.6 parts lubricant. The AS resin has a modulus greater than 2400 MPa, and the toughening high-strength rubber powder is an acrylonitrile-butadiene-styrene copolymer, comprising a butadiene fragment content greater than or equal to 60%, an acrylonitrile fragment content of 10-14%, and a styrene fragment content of 26-30%. This technical solution involves adding TPEE, a linear block copolymer combining hard and soft segments, to ABS material. This alters the crystalline structure of the ABS material, transforming it from an amorphous to a crystalline state, thereby improving rigidity and toughness. In addition, a lubricating silicone additive is added, further enhancing the feel and scratch resistance. While this solution improves the lubricity of toys, the silicone additive is an external lubricant. If the amount added is not properly controlled, it can easily become excessive, gradually migrating to the surface and causing seepage and a greasy feel.

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

[0005] In addition, the compatibility of pigments can affect the color uniformity of the product, as well as its appearance and aesthetics. Therefore, the compatibility of pigments must be taken into account when preparing ABS materials.

[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 address the precipitation problem caused by adding external lubricants, in order to prepare ABS compositions with better mechanical and processing properties and lower insertion and extraction forces. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a fluorinated styrene-acrylonitrile copolymer composition, its preparation method, and its applications. The fluorinated styrene-acrylonitrile copolymer composition has low surface energy and good lubricity. ABS compositions made from this composition exhibit good mechanical and processing properties, low insertion and extraction forces, and can improve the problem of external lubricant precipitation.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a fluorinated styrene-acrylonitrile copolymer composition comprising, by weight percentage: component A 90% to 100% (91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, etc.) and component B 0% to 10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, etc.).

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

[0011] Component B includes 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, for example, 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; the molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition is 2.15 to 2.60, for example, 2.20, 2.25, 2.30, 2.35, 2.40, 2.45, 2.50, or 2.55.

[0013] In this invention, a fluorinated styrene-acrylonitrile copolymer is formed by introducing fluorinated acrylates. This copolymer has fluorinated side chains and contains CF bonds. The CF bond structure is tight and stable with high electronegativity, which reduces intermolecular attraction. The resulting fluorinated styrene-acrylonitrile copolymer composition has low surface energy and good lubricity. By controlling the weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition to be 80,000–150,000 g / mol and the molecular weight distribution to be 2.15–2.60, the resulting fluorinated styrene-acrylonitrile copolymer composition exhibits good mechanical properties, processing properties, and lubricity. When used to prepare ABS compositions, the resulting ABS compositions have inherent surface lubricity, low insertion and extraction forces, and good compatibility with pigments. No external lubricant is required, increasing the feel and auditory comfort during use and improving the problem of external lubricant precipitation.

[0014] In this 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 using gel permeation chromatography.

[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 monomers include acrylonitrile and / or methacrylonitrile.

[0017] Preferably, the fluorinated acrylate includes any one or a combination of at least two of the following: hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, pentafluorophenol acrylate, pentafluorophenol methacrylate, nonafluorohexyl acrylate, nonafluorohexyl methacrylate, or heptafluoroisopropyl acrylate, and more preferably hexafluorobutyl methacrylate.

[0018] In this invention, different fluorinated chain lengths in fluorinated acrylates affect the enrichment of fluorine atoms on the surface of injection molded parts, thus affecting lubricity. Although it is generally believed that fluorinated acrylates with more fluorine atoms have better hydrophobic effects, as the proportion of fluorinated acrylates gradually increases, the enrichment capacity of fluorine atoms during polymerization gradually exceeds the influence of the fluorinated chain length. Therefore, fluorinated styrene-acrylonitrile copolymer resins prepared from fluorinated acrylates with lower fluorinated chain lengths have better lubricity than those with higher fluorinated chain lengths. Furthermore, the steric hindrance of fluorinated groups in molecules with benzene rings is greater than that in molecules with straight chains, resulting in greater residual internal stress during injection molding. Therefore, the preferred fluorinated acrylate is 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 composed of the following monomers by mass percentage: 40%–80% styrene monomers (e.g., 45%, 50%, 55%, 60%, 65%, 70%, or 75%), 10%–40% acrylonitrile monomers (e.g., 15%, 20%, 25%, 30%, or 35%), 8%–20% fluorinated acrylates (9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or 19%), and 0%–10% other copolymerizable monomers (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%), the sum of the mass percentages of the monomers being 100%.

[0021] In this invention, the mass percentage of fluorinated acrylate is controlled to be 8% to 20% based on the total mass of monomers of 100%, which can effectively balance the insertion and extraction force and the colorant compatibility, so that the ABS composition containing the fluorinated styrene-acrylonitrile copolymer composition has both low insertion and extraction force and good colorant compatibility.

[0022] Preferably, the fluorinated styrene-acrylonitrile copolymer comprises random copolymer blocks of styrene monomers and acrylonitrile monomers, as well as random copolymer blocks of styrene monomers, acrylonitrile monomers and fluorinated acrylates.

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

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

[0025] Preferably, the processing aid includes any one or a combination of at least two of emulsifiers, molecular weight regulators, or oil-soluble initiators.

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

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

[0028] In this invention, the thiol preferably includes any one or a combination of at least two of n-dodecyl mercaptan, tert-dodecyl mercaptan, or 3-mercaptohexanol. The molecular weight regulator is preferably a fluorinated styrene-acrylonitrile copolymer composition obtained from n-dodecyl mercaptan or tert-dodecyl mercaptan, which is used to prepare ABS compositions. Its lubrication performance and colorant compatibility are not significantly affected. However, n-dodecyl mercaptan is a straight-chain alkyl mercaptan with a simpler molecular structure, making it more likely to react with fluorinated polymers. 3-mercaptohexanol, on the other hand, suffers from low chain transfer efficiency due to side reactions easily initiated by the hydroxyl group, as well as steric hindrance and stability issues, making it difficult to meet the requirements for precise molecular weight control in industrial polymerization. Therefore, n-dodecyl mercaptan is further preferred.

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

[0030] In this invention, the additive may be, for example, any one or a combination of at least two of the following: plasticizer, antistatic agent, light stabilizer, lubricant, foaming agent, tackifier, filler, surfactant, flame retardant, dye, pigment, antioxidant, hydrolytic stabilizer, heat stabilizer, anti-fading agent, or reinforcing agent.

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

[0032] In this invention, the light stabilizer can be any commonly used light stabilizer, such as compounds based on any one of benzophenone, benzotriazole, cinnamic acid, organophosphites or phosphonites, as well as sterically hindered amine compounds.

[0033] In this invention, the lubricant may be any one or a combination of at least two of the following: hydrocarbon compounds, fatty alcohol compounds, ketone compounds, carboxylic acid compounds, oxidized polyethylene wax, carboxylamine compounds, or carboxylic acid ester compounds.

[0034] For example, the hydrocarbon compound includes any one or a combination of at least two of the following: oil compounds, paraffin compounds, polyethylene wax compounds, or polypropylene wax compounds.

[0035] For example, the carboxylic acid compounds include carboxylic acid compounds having 6-30 (e.g., 9, 12, 15, 18, 21, 24 or 27 carbon atoms, etc.)

[0036] For example, the fatty acid compound having 6-30 (e.g., 9, 12, 15, 18, 21, 24 or 27 carbon atoms) includes linalic acid.

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

[0038] In this invention, the antioxidant can be a commonly used antioxidant, such as phenolic antioxidants and / or benzotriazole.

[0039] For example, the phenolic antioxidant includes any one or a combination of at least two of alkylated monohydric phenols, esters of β-(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid), or amides of β-(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid).

[0040] For example, the phenolic antioxidant includes any one or a combination of at least two of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[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 method comprising the following steps: mixing styrene monomers, acrylonitrile monomers, fluorinated acrylates, optionally other copolymerizable monomers and optionally component B, reacting to obtain the fluorinated styrene-acrylonitrile copolymer composition.

[0042] In this invention, fluorinated acrylates are added to the reaction system and a fluorinated styrene-acrylonitrile copolymer is generated by polymerization.

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

[0044] (1) Mix a portion of styrene monomers, a portion of acrylonitrile monomers, optionally a portion of other copolymerizable monomers, component B and solvent evenly, and react to obtain an intermediate.

[0045] (2) The remaining styrene monomers, the remaining acrylonitrile monomers, the fluorinated acrylate, and optionally other remaining copolymerizable monomers are mixed with the intermediate obtained in step (1) and reacted to obtain the fluorinated styrene-acrylonitrile copolymer composition.

[0046] Preferably, based on the total mass of styrene monomers as 100%, the mass of styrene in the portion described in step (1) is 20% to 80%, for example, 30%, 40%, 50%, 60% or 70%.

[0047] Preferably, based on the total mass of acrylonitrile monomers as 100%, the mass of acrylonitrile in the portion described in step (1) is 20% to 80%, for example, 30%, 40%, 50%, 60% or 70%.

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

[0049] In this invention, in order to concentrate the fluorinated acrylate at one end of the chain segment, it is preferable to use a two-step feeding method, adding the fluorinated acrylate in step (2) so that the prepared fluorinated styrene-acrylonitrile copolymer composition has a better effect on reducing insertion and extraction force.

[0050] Preferably, the mass of the molecular weight regulator is 0.1% to 1% of the total mass of styrene monomers, acrylonitrile monomers, fluorinated acrylates and other copolymerizable monomers, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%.

[0051] Preferably, the oil-soluble initiator is 0.1% to 1% of the total mass of styrene monomers, acrylonitrile monomers, fluorinated acrylates and other copolymerizable monomers, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%.

[0052] Preferably, the mass of the solvent is 5% to 12% of the total mass of styrene monomers, acrylonitrile monomers, fluorinated acrylates and other copolymerizable monomers, for example 6%, 7%, 8%, 9%, 10% or 11%.

[0053] Preferably, the reaction in step (1) is carried out with stirring in a reaction vessel at a temperature of 60–150°C (e.g., 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, or 140°C), and at a pressure of 0.2–0.8 MPa (e.g., 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). The reaction pressure is 0.70 MPa or 0.75 MPa, etc., and the reaction time is 0.5 to 4 hours (e.g., 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3.0 hours or 3.5 hours, etc.). The stirring speed is 10 to 300 r / min (e.g., 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 an organic solvent.

[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 vessel at a temperature of 90–150°C (e.g., 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, or 145°C, etc.) and a pressure of 0.2–0.8 MPa (e.g., 0.25 MPa, 0.30 MPa, 0.35 MPa, 0.40 MPa, 0.45 MPa, 0.50 MPa, 0.55 MPa, 0.6 MPa). The reaction pressure is 0 MPa, 0.65 MPa, 0.70 MPa or 0.75 MPa, etc., the reaction time is 0.5 to 4 hours (e.g., 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3.0 hours or 3.5 hours, etc.), and the stirring speed is 10 to 300 r / min (e.g., 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 vessel includes a batch reactor.

[0058] Preferably, step (2) further includes devolatilization, extrusion granulation and drying steps after the reaction.

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

[0060] Thirdly, the present invention provides a fluorinated ABS resin, the fluorinated ABS resin comprising the fluorinated styrene-acrylonitrile copolymer composition as described in the first aspect and ABS high-adhesion powder.

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

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

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

[0064] In this invention, the fluorinated styrene-acrylonitrile copolymer composition can be compounded and extruded with ABS high-rubber powder to obtain fluorinated ABS resin, which has good lubrication, low insertion and extraction force, and can improve the problem of external lubricant precipitation.

[0065] Fourthly, the present invention provides an ABS composition comprising 60 to 85 parts (e.g., 63, 66, 69, 72, 75, 78, 81, or 84 parts, etc.) of the fluorinated styrene-acrylonitrile copolymer composition as described in the first aspect, 15 to 40 parts (e.g., 18, 21, 24, 27, 30, 33, 36, or 39 parts, etc.) of ABS high-resin powder, and 0.01 to 150 parts (e.g., 20, 40, 60, 80, 100, 120, or 140 parts, etc.) of additives.

[0066] Alternatively, it may include 100 parts of fluorinated ABS resin as described in the third aspect and 0.01 to 150 parts of additives (e.g., 20 parts, 40 parts, 60 parts, 80 parts, 100 parts, 120 parts, or 140 parts, etc.).

[0067] Preferably, the additives include any one or a combination of at least two of flame retardants, antioxidants, lubricants, colorants, or antistatic agents.

[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 antioxidants 1010, 168, 1076, or 618.

[0070] Preferably, the lubricant in the ABS composition includes any one or a combination of at least two of ethylene bis-stearamide (lubricant EBS), zinc stearate, glyceryl 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 maleimide copolymers.

[0073] Fifthly, the present invention provides the application of any one of the following: 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, appliance housing materials, toy materials, food container materials, or medical supplies materials, and more preferably, in toy building blocks.

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

[0075] In this invention, a fluorinated styrene-acrylonitrile copolymer composition is formed by introducing fluorinated acrylates, and the weight-average molecular weight and molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition are controlled within a specific range. This results in a low surface energy, self-lubricating properties, and good mechanical and processing properties. When used to prepare ABS compositions, the resulting ABS compositions have low insertion and extraction forces, reducing noise during insertion and extraction, increasing the comfort of touch and hearing during use, and exhibiting good colorant compatibility. They can be used to prepare children's toy products with uniform and beautiful colors. Detailed Implementation

[0076] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

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

[0078] n-Dodecyl mercaptan: manufactured by Phillips Corporation of the United States, its structure is shown below:

[0079]

[0080] tert-dodecyl mercaptan has the following structure:

[0081]

[0082] Example 1

[0083] This embodiment provides a fluorinated styrene-acrylonitrile copolymer composition and its preparation method. The raw materials for preparing the fluorinated styrene-acrylonitrile copolymer composition include the following components by weight: 60 parts styrene, 27 parts acrylonitrile, 5 parts fluorinated acrylate, 0.15 parts molecular weight regulator (n-dodecyl mercaptan), 0.1 parts oil-soluble initiator (benzoyl peroxide), and 8 parts 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 parts by weight of molecular weight regulator (n-dodecyl mercaptan), 0.1 parts by weight of oil-soluble initiator (benzoyl peroxide) and 8 parts by weight of solvent (ethylbenzene) evenly, add to a batch reactor, stir, the reaction temperature is 80℃, the reaction pressure is 0.3MPa, the stirring speed is 70r / min, the reaction time is 2h, and the intermediate is obtained;

[0086] (2) 30 parts by weight of styrene, 17 parts by weight of acrylonitrile, and 5 parts by weight of fluorinated acrylate (hexafluorobutyl methacrylate) were premixed evenly and added dropwise to a batch reactor to mix with the intermediate obtained in step (1). The temperature of the batch reactor was 120°C, the pressure was 0.3 MPa, the stirring speed was 70 r / min, and the reaction time was 2 h. Deviation was carried out in a devolatilizer, and extrusion granulation was performed using a twin-screw extruder. The twin-screw extruder had a total of 6 temperature zones, and the temperatures of zones 1 to 6 were 200°C, 220°C, 240°C, 210°C, 230°C, and 220°C, respectively. Then, the mixture was 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 was 130,000, and the molecular weight distribution was 2.20.

[0087] Examples 2-13 and Comparative Examples 1-5 used the same preparation method as Example 1, except for the added raw materials, their content, and process parameters. The content of the raw materials is expressed in parts by weight, as shown in Tables 1, 2, and 3.

[0088] Table 1

[0089]

[0090]

[0091] In Table 1, " / " indicates that the ingredient was not added.

[0092] Table 2

[0093]

[0094]

[0095] In Table 2, " / " indicates that the ingredient was not added.

[0096] Table 3

[0097]

[0098]

[0099] In Table 3, " / " indicates that the ingredient was not added.

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

[0101] Application Example 1

[0102] This application example provides an ABS composition, which is prepared 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 granulated by extrusion using a twin-screw extruder at an extrusion temperature of 240°C to obtain the ABS composition.

[0103] Application Examples 2-13

[0104] Application Examples 2 to 13 each 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 instead of the fluorinated styrene-acrylonitrile copolymer composition obtained in Example 1, while the other conditions are the same as in Application Example 1.

[0105] Application Example 14

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

[0107] Application Example 15

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

[0109] Comparative Application Examples 1-5

[0110] Comparative Application Examples 1 to 5 each provide an ABS composition, which differs from Application Example 1 only in that the styrene-acrylonitrile copolymer resin obtained in Comparative Examples 1 to 5 is used instead of the fluorinated styrene-acrylonitrile copolymer composition obtained in Example 1. Otherwise, they are the same as Application Example 1.

[0111] The following performance tests were performed on the ABS compositions provided in corresponding use cases 1-15 and comparative application examples 1-5:

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

[0113] (2) Colorant compatibility: The ABS composition and yellow colorant (brand name organic pigment yellow H2R, manufacturer Clariant) were injection molded at a weight ratio of 1:0.0003 to obtain a color swatch. The chromaticity values ​​a, b, and c were measured using a colorimeter, where b represents the yellow-blue value of the object, with positive values ​​for yellow and negative values ​​for blue. Four points were taken at different locations on the color swatch, and their b values ​​were measured and recorded as b1, b2, b3, and b4. The mean M and variance s were calculated. 2 The specific formula is shown below:

[0114]

[0115] If s 2 If ≤0.2, then the colorant compatibility is considered good; if s 2 A value greater than 0.2 indicates poor colorant compatibility.

[0116] The test results are shown in Table 4 below.

[0117] Table 4

[0118]

[0119]

[0120] In Table 4, " / " indicates that the test was not performed.

[0121] As shown in Table 4, the insertion and extraction forces of the ABS compositions provided in Application Examples 1-15 are 20-34 N, and the colorant compatibility is s. 2 ≤0.2.

[0122] By comparing Examples 4-8, it can be seen that, taking the total mass of styrene monomers, acrylonitrile monomers, fluorinated acrylates and other copolymerizable monomers as 100%, controlling the mass of fluorinated acrylates at 8%-20% can balance the insertion and extraction forces and the compatibility of pigments.

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

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

[0125] Compared with Application Example 6, if no fluorinated acrylate is added (compared to Application Example 1), the insertion and extraction force increases and the stain resistance decreases.

[0126] Compared with Application Example 6, if the weight-average molecular weight of the fluorostyrene-acrylonitrile copolymer composition used is too large (compared to Application Example 2), the melt viscosity of the fluorostyrene-acrylonitrile copolymer composition is high, making it difficult to disperse the pigments in the ABS composition, resulting in agglomeration or uneven distribution and reduced pigment compatibility; if the weight-average molecular weight of the fluorostyrene-acrylonitrile copolymer composition used is too small (compared to Application Example 3), the fluorostyrene-acrylonitrile copolymer composition has high fluidity, resulting in pigment interface migration and reduced pigment compatibility.

[0127] Compared with Application Example 6, if the molecular weight distribution of the fluorostyrene-acrylonitrile copolymer composition used is too large (compared to Application Example 4), the insertion and extraction forces of the prepared ABS composition increase, and the colorant compatibility decreases. The inventors speculate that this may be due to uneven melt flow, increased surface roughness of the injection molded part, leading to increased insertion and extraction forces. In addition, the high fluidity of low molecular weight segments in an excessively large molecular weight distribution leads to colorant migration and local aggregation, while high molecular weight segments hinder colorant dispersion, further forming uneven hue regions, resulting in decreased colorant compatibility. If the molecular weight distribution of the fluorostyrene-acrylonitrile copolymer composition used is too small (compared to Application Example 3), the lack of lubrication from low molecular weight components on the surface increases the coefficient of friction, resulting in increased insertion and extraction forces of the prepared ABS composition. The smaller molecular weight distribution also results in high melt viscosity during injection molding, making it difficult for colorant to disperse and prone to agglomeration, leading to uneven hue and decreased colorant compatibility.

[0128] The applicant declares that this invention illustrates a fluorinated styrene-acrylonitrile copolymer composition, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A fluorinated styrene-acrylonitrile copolymer composition, characterized in that, The fluorinated styrene-acrylonitrile copolymer composition comprises, by weight percentage: component A 90%~100% and component B 0~10%; Component A includes a fluorinated styrene-acrylonitrile copolymer, which is mainly composed of the following monomers by mass percentage: 40%~80% styrene monomers, 10%~40% acrylonitrile monomers, 1%~35% fluorinated acrylates, and 0~10% other copolymerizable monomers; Component B includes an additive; The weight-average molecular weight of the fluorinated styrene-acrylonitrile copolymer composition is 80,000 to 150,000 g / mol; the molecular weight distribution of the fluorinated styrene-acrylonitrile copolymer composition is 2.15 to 2.

60.

2. The fluorinated styrene-acrylonitrile copolymer composition according to claim 1, characterized in that, The styrene monomers include any one or a combination of at least two of styrene, α-methylstyrene, or p-methylstyrene.

3. The fluorinated styrene-acrylonitrile copolymer composition according to claim 1, characterized in that, The acrylonitrile monomers include acrylonitrile and / or methacrylonitrile.

4. The fluorinated styrene-acrylonitrile copolymer composition according to claim 1, characterized in that, The fluorinated acrylates include any one or a combination of at least two of the following: hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, pentafluorophenol acrylate, pentafluorophenol methacrylate, nonafluorohexyl acrylate, nonafluorohexyl methacrylate, or heptafluoroisopropyl acrylate.

5. The fluorinated styrene-acrylonitrile copolymer composition according to claim 1, characterized in that, The fluorinated acrylate is hexafluorobutyl methacrylate.

6. The fluorinated styrene-acrylonitrile copolymer composition according to claim 1, characterized in that, 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, phenylmaleimide, maleic anhydride, acrylamide, or vinyl methyl ether.

7. The fluorinated styrene-acrylonitrile copolymer composition according to claim 1, characterized in that, The fluorinated styrene-acrylonitrile copolymer is mainly composed of the following monomers by mass percentage: 40%~80% styrene monomers, 10%~40% acrylonitrile monomers, 8%~20% fluorinated acrylates, and 0~10% other copolymerizable monomers.

8. A method for preparing a fluorinated styrene-acrylonitrile copolymer composition according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: mixing styrene monomers, acrylonitrile monomers, fluorinated acrylates, optionally other copolymerizable monomers and optionally component B, reacting them to obtain the fluorinated styrene-acrylonitrile copolymer composition.

9. The preparation method according to claim 8, characterized in that, The preparation method includes the following steps: (1) Mix a portion of styrene monomers, a portion of acrylonitrile monomers, optionally a portion of other copolymerizable monomers, component B and solvent evenly, and react to obtain an intermediate; (2) The remaining styrene monomers, the remaining acrylonitrile monomers, the fluorinated acrylate, and optionally other remaining copolymerizable monomers are mixed with the intermediate obtained in step (1) and reacted to obtain the fluorinated styrene-acrylonitrile copolymer composition.

10. The preparation method according to claim 9, characterized in that, Based on the total mass of styrene monomers being 100%, the mass of styrene monomers in step (1) is 20% to 80%.

11. The preparation method according to claim 9, characterized in that, Based on the total mass of acrylonitrile monomers being 100%, the mass of acrylonitrile monomers in step (1) is 20% to 80%.

12. The preparation method according to claim 9, characterized in that, With the total mass of other copolymerizable monomers being 100%, the mass of other copolymerizable monomers in the part described in step (1) is 0~100%.

13. The preparation method according to claim 9, characterized in that, The solvent in step (1) includes organic solvents.

14. The preparation method according to claim 13, characterized in that, The organic solvent includes any one or a combination of at least two of ethylbenzene, toluene, or xylene.

15. The preparation method according to claim 13, characterized in that, Step (2) further includes devolatilization, extrusion granulation and drying steps after the reaction.

16. A fluorinated ABS resin, characterized in that, The fluorinated ABS resin includes the fluorinated styrene-acrylonitrile copolymer composition as described in any one of claims 1-7 and ABS high-adhesion powder.

17. The fluorinated ABS resin according to claim 16, characterized in that, The fluorinated ABS resin comprises the following components in parts by weight: The composition of the fluorinated styrene-acrylonitrile copolymer as described in any one of claims 1-7, comprising 60-85 parts and 15-40 parts of ABS high-resin powder.

18. An ABS composition, characterized in that, The ABS composition comprises the following components in parts by weight: The composition of fluorinated styrene-acrylonitrile copolymer as described in any one of claims 1-7, comprising 60-85 parts, 15-40 parts, and 0.01-150 parts of additives; Or it may include the following components by weight: 100 parts of the fluorinated ABS resin and 0.01 to 150 parts of the additives as described in claim 16 or 17.

19. The use of any one of the fluorinated styrene-acrylonitrile copolymer compositions as described in any one of claims 1-7, the fluorinated ABS resin as described in claim 16 or 17, or the ABS composition as described in claim 18 in automotive interior and exterior trim materials, appliance housing materials, toy materials, food container materials, or medical supplies materials.

Images