WO2020173490A1 - 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 - Google Patents

一种高极性阻燃苯乙烯类组合物、制备方法及其应用 Download PDF

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WO2020173490A1
WO2020173490A1 PCT/CN2020/077075 CN2020077075W WO2020173490A1 WO 2020173490 A1 WO2020173490 A1 WO 2020173490A1 CN 2020077075 W CN2020077075 W CN 2020077075W WO 2020173490 A1 WO2020173490 A1 WO 2020173490A1
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flame
styrene
retardant
parts
polarity
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汪炉林
姜向新
肖华明
刘凯
黄池光
王林
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Kingfa Science and Technology Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34Silicon-containing compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/10Copolymers of styrene with conjugated dienes
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/14Copolymers of styrene with unsaturated esters
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the invention belongs to the field of polymer materials, and specifically relates to a high-polarity flame-retardant styrene composition suitable for glue-sealing lead-acid battery casings, a preparation method and application thereof.
  • Styrene resin is a terpolymer composed of styrene, butadiene, and acrylonitrile. It combines the high fluidity of styrene, the initial rubber properties of butadiene, and the chemical resistance of acrylonitrile. It has excellent processing Performance, low temperature resistance, electrical insulation, chemical resistance, high gloss, and excellent electroplating performance. At the same time, it has good creep resistance, high dimensional stability, and low mold shrinkage. It is used in military, automobile, and electronics Applications in electrical appliances and other fields are very extensive. But on the one hand, the oxygen index of styrene resin is only 18, which is a flammable material. Therefore, flame-retardant modification of styrene resin is a commonly used modification method of styrene resin.
  • styrene resin is a sea-island structure with styrene-acrylonitrile copolymer as the continuous phase and butadiene rubber as the dispersed phase.
  • the addition of about 15-25% of the flame retardant system partially destroyed the styrene blend.
  • the sea-island structure which in turn leads to a substantial decrease in the initial properties of the styrene matrix resin.
  • the content, particle size, and distribution of butadiene rubber can effectively control the initial properties of the styrene resin, while adjusting the initial properties of the styrene resin, the adhesive strength of the glue is greatly reduced.
  • the housing Due to the particularity of lead-acid batteries, in addition to UL94 V-0@1.5mm, the housing requires effective heating or glue welding for the battery slot and battery cover. Therefore, it is necessary to develop high-efficiency flame retardant and effective A flame-retardant styrene composition that improves its adhesion to glue is an inevitable choice.
  • the purpose of the present invention is to provide a highly polar flame-retardant styrenic composition, which has excellent flame retardancy, good impact resistance, and high adhesion to epoxy resin glue, which is particularly suitable Used to prepare plastic-sealed lead-acid battery shell materials.
  • a high-polarity flame-retardant styrenic composition including Including the following parts by weight
  • the styrenic resin is acrylonitrile-butadiene-styrene graft copolymer (ABS), acrylonitrile-styrene-acrylic acid terpolymer (ASA) or methyl methacrylate-butadiene- Styrene graft copolymer (MBS).
  • ABS acrylonitrile-butadiene-styrene graft copolymer
  • ASA acrylonitrile-styrene-acrylic acid terpolymer
  • MBS methyl methacrylate-butadiene- Styrene graft copolymer
  • the brominated flame retardant system is brominated imine, brominated polycarbonate, polybrominated styrene, brominated polystyrene, tris(tribromophenoxy) cyanurate, octabromoether, One or more of decabromodiphenyl ethane, brominated epoxy, tetrabromobisphenol A, tetrabromobisphenol A ether, etc. are combined with antimony trioxide, colloidal antimony pentoxide, sodium antimonate, trichloro One or several compound systems in antimony and antimony pentachloride.
  • the blended elastomer is one or more of acrylic rubber, silicone rubber, SBS, SEBS, grafted POE, nitrile rubber, fluorine rubber, butadiene rubber, styrene butadiene rubber and the like.
  • the modulus modifier is a linear expansion coefficient for one or more of a ⁇ l X 10_ powder material 6, such as kaolin, calcite, pyrophosphate, pyrophosphate tungstate, and the like.
  • the polar modifier is styrene maleimide copolymer, maleic anhydride grafted SEBS, maleic anhydride grafted styrene copolymer, maleic anhydride grafted AS copolymer, ethylene- One or more of butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer and the like.
  • the polar modifier is styrene maleimide copolymer, maleic anhydride grafted SEBS, One or more of maleic anhydride grafted styrene copolymer and maleic anhydride grafted AS copolymer; particularly preferred are styrene maleimide copolymer and maleic anhydride grafted SEBS One or two kinds of; the most preferred is maleic anhydride grafted SEBS o
  • the antioxidants include hindered phenolic primary antioxidants and phosphite secondary antioxidants.
  • the light stabilizers include one or more of benzophenones, benzotriazoles, triazines, substituted acrylonitriles, oxamides, and hindered amines.
  • the processing aid is one or a mixture of stearamide lubricants such as EBS, silicone oil and white mineral oil.
  • the above mixture is conveyed to the twin-screw extruder through a precisely metered feeding device.
  • the temperature of the screws in each section of the extruder is controlled between 170 ⁇ 230 ° C, and the aspect ratio of the twin-screw extruder is 20 ⁇ 40, The screw speed is 200-800 rpm.
  • the materials Under the shearing, mixing and conveying of the screw, the materials can be fully melted and compounded, and then extruded, granulated and dried to obtain a highly polar flame-retardant styrene composition particle;
  • the above-mentioned high-polarity flame-retardant styrene composition particles are added to an injection molding machine to be processed into the required splines.
  • the injection conditions are: barrel temperature 180-220 ° C, mold temperature 50-70 ° C, Injection pressure is 6-10MPa.
  • an application of the high-polarity flame-retardant styrenic composition is also provided, specifically it is used as a lead-acid battery shell material welded by epoxy resin glue.
  • the high-polarity flame-retardant styrene composition of the present invention prepares sample strips according to the standard, and performs the performance tests listed in Table 1 below.
  • the equipment used in the present invention includes:
  • the twin-screw extruder used to prepare the highly polar flame-retardant styrene composition is SHJ-30 produced by Nanjing Ruiya Polymer Equipment Co., Ltd.
  • the injection molding machine used to prepare the test strips of the high-polarity flame-retardant styrene composition is the B-920 model produced by Zhejiang Haitian Injection Molding Machine Co., Ltd.
  • the instrument used to test the melt flow rate is the ZR21452 melt flow rate meter produced by Meister Industrial Systems (China) Co., Ltd.
  • the impact testing machine used to test the impact strength is the T92 type produced by Tinius Olsenis, USA.
  • the universal testing machine for testing tensile strength and adhesion is H10K-S produced by Hounsfield.
  • the Vicat heat distortion tester used to test the heat distortion temperature is the 40-197 type produced by COESFELD in Germany.
  • the UL-94 vertical combustion instrument used to test the combustion performance is the HVUL-2 type produced by ATLAS in the United States.
  • the provided raw materials can be purchased from the market.
  • styrene resin is selected from Taiwan Taihua's styrene AG15A1
  • ASA resin is selected from Japan UMG ASA A600N;
  • the brominated flame retardant is FR-245 of Israel Dead Sea Bromine Company, and the 8010 of Albemarle, USA;
  • the antimony flame retardant is S-05N of Yunnan Muli Antimony Industry Co., Ltd.;
  • Acrylic rubber is selected from DuPont’s EA101, silicone rubber is from Japan’s Zhongyuan’s MR-01, SBS is from South Korea’s LG503N, butadiene rubber is from South Korea’s Kumho HR181;
  • Calcium pyrophosphate is selected from Nanjing Songguan, China, and kaolin is selected from US HG90;
  • Polar modifier adopts Taiwan Rubber's maleic anhydride grafted SEBS-7131, Nippon Electrochemical's styrene-maleimide copolymer MS-NB, and Shenyang Ketong's maleic anhydride grafted styrene copolymer KT-2, maleic anhydride grafted AS copolymer S601N of Japan UMG;
  • the antioxidants are Irganox 1010 and Irganox 168 made from Qiba refined;
  • the light stabilizer is selected from Qiba refined 770 and UV-P;
  • Example 1-4 Comparative Example 1-4 According to the parts by weight listed in Table 2, each component was added to a high-speed mixer for uniform mixing, and then the above mixture was fed into a twin-screw extruder for mixing and extrusion ⁇ Stretching, water cooling, pelletizing; Among them, the length to diameter ratio of the twin-screw extruder is 20-40; the screw barrel temperature is set as: the temperature of the first zone is 180°C, the temperature of the second zone is 190°C, and the temperature of the third zone is 200 °C, four zone temperature 210°C, five zone temperature 220°C, six zone temperature 220°C, seven zone temperature 220°C, eight zone temperature 220°C, nine zone temperature 220°C, ten zone temperature 220° C, the head temperature is 230°C; the screw speed is 200-800 revolutions/#
  • the high-polarity flame-retardant styrene composition particles prepared by the method described above are tested according to the standard preparation samples listed in Table 1. Record the
  • each component was added to a high-speed mixer according to the weight parts listed in Table 3 for uniform mixing, and then the above-mentioned mixture was fed into a twin-screw extruder for mixing, extruding, drawing, and Water cooling and pelletizing;
  • the length-to-diameter ratio of the twin-screw extruder is 20-40;
  • the temperature of the screw barrel is set as: 180°C in the first zone, 190°C in the second zone, 200°C in the third zone, and four Zone temperature 210°C, five zone temperature 220°C, six zone temperature 220°C, seven zone temperature 220°C, eight zone temperature 220°C, nine zone temperature 220°C, ten zone temperature 220°C, machine head
  • the temperature is 230°C;
  • the screw speed is 200-800 rpm/#
  • the high-polarity flame-retardant styrene composition prepared by the method described above is tested according to the standard preparation samples listed in Table 1 and the data is recorded

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明提供了一种适用于胶封铅酸蓄电池壳体的高极性阻燃苯乙烯类组合物、制备方法及其应用。所述高极性阻燃苯乙烯类组合物,包括以下重量份的组分:苯乙烯类树脂35-75份,溴系阻燃体系15-25份,共混弹性体10-40份,模量改性剂5-10份,极性改性剂0.1-5份,抗氧剂0.1-1份,光稳定剂0.1-1份和加工助剂0.1-2份。本发明还提供上述高极性阻燃苯乙烯类组合物的制备方法。本发明所述的高极性阻燃苯乙烯类组合物除了具有高韧性和高阻燃性,同时具有较高的极性。经过测试,其缺口冲击强度超过25kJ/m 2,阻燃性能达到UL94 V-0@1.5mm,同时采用双组份环氧树脂胶水粘接力均超过80kgf,特别适用于胶封铅酸蓄电池壳体材料。

Description

一种高极性阻燃苯乙烯类组合物、 制备方法及其应用 技术领域
本发明属于高分子材料领域, 具体涉及一种适用于胶封铅酸蓄电池壳体的高极性 阻燃苯乙烯类组合物、 制备方法及其应用。
背景技术
苯乙烯树脂是由苯乙烯、 丁二烯、 丙烯腈组成的三元共聚物, 集中了苯乙烯的高 流动性、 丁二烯的橡胶初性和丙烯腈的耐化学品特性, 具有优良的加工性能、 耐低温 性能、 电绝缘性能、 耐化学腐蚀性能及高光泽和优异的电镀性能, 同时具有耐蠕变性 好、 尺寸稳定性高、 成型收缩率小等优异特点, 在军工、 汽车、 电子电器等领域应用 非常广泛。 但一方面苯乙烯树脂的氧指数只有 18, 属于易燃材料。 因此, 对苯乙烯树 脂进行阻燃改性是目前常用的一种苯乙烯树脂改性方法。
另一方面苯乙烯树脂是苯乙烯 -丙烯腈共聚物作为连续相,丁二烯橡胶作为分散相 的海-岛结构, 15-25%左右的阻燃体系的加入部分破坏了苯乙烯共混物的海-岛结构, 进而导致苯乙烯基体树脂初性大幅降低。 虽然通过丁二烯橡胶的含量、 粒径大小及分 布可有效调控苯乙烯树脂的初性, 但在调控苯乙烯树脂初性的同时, 导致胶水粘接力 大幅下降。 由于铅酸蓄电池的特殊性, 壳体除了要求达到 UL94 V-0@1.5mm, 同时要 求电池槽和电池盖能进行有效的加热或胶水焊接, 因此有必要开发出高效阻燃的同 时, 可有效提高其和胶水粘接力的阻燃苯乙烯组合物是一项必然选择。
发明内容
针对现有技术的不足, 本发明的目的是提供一种高极性阻燃苯乙烯类组合物, 阻 燃性优异, 抗冲击性能好, 同时和环氧树脂胶水的粘结力高, 特别适用于制备胶封铅 酸蓄电池壳体材料。
在本发明的一个技术方案中, 提供了一种适用于高极性阻燃苯乙烯类组合物, 包 括以下重量份的组分
苯乙烯类树脂 35-65份
溴系阻燃体系 15-25份
共混弹性体 10-30份
模量改性剂 5-10份
极性改性剂 0.1-5份
抗氧剂 0.1-1份
光稳定剂 0.1-1份;
加工助剂 0.1-2份。
所述的苯乙烯类树脂为丙烯腈-丁二烯 -苯乙烯接枝共聚物 (ABS)、 丙烯腈 -苯乙 烯 -丙烯酸三元共聚物(ASA) 或甲基丙烯酸甲酯-丁二烯 -苯乙烯接枝共聚物(MBS)。
所述的溴系阻燃体系为溴化亚胺、溴化聚碳酸酯、聚溴化苯乙烯、溴化聚苯乙烯、 三 (三溴苯氧基) 三聚氰酸酯、 八溴醚、 十溴二苯乙烷、 溴化环氧、 四溴双酚 A、 四 溴双酚 A醚等中的一种或几种与三氧化二锑、 胶体五氧化二锑、 锑酸钠、 三氯化锑、 五氯化锑等中的一种或几种复配体系。
所述的共混弹性体为丙烯酸酯橡胶、硅橡胶、 SBS、 SEBS、接枝 POE、丁腈橡胶、 氟橡胶、 顺丁橡胶、 丁苯橡胶等中的一种或几种。
所述的模量改性剂为其线膨胀系数 a<l X 10_6的粉体材料, 如高岭土、 方解石、 焦磷酸盐、 焦钨酸盐等中的一种或几种。
所述的极性改性剂为苯乙烯马来酰亚胺共聚物、 马来酸酐接枝的 SEBS、 马来酸 酐接枝的苯乙烯共聚物、 马来酸酐接枝的 AS 共聚物、 乙烯 -丙烯酸丁酯 -甲基丙烯酸 缩水甘油酯共聚物、 乙烯 -丙烯酸甲酯 -甲基丙烯酸缩水甘油酯共聚物等中的一种或几 种。
优选地, 所述极性改性剂为苯乙烯马来酰亚胺共聚物、 马来酸酐接枝的 SEBS、 马来酸酐接枝的苯乙烯共聚物、 马来酸酐接枝的 AS共聚物中的一种或多种; 特别优 选的是苯乙烯马来酰亚胺共聚物、 马来酸酐接枝的 SEBS中的一种或两种; 最优选的 是马来酸酐接枝的 SEBSo
所述的抗氧剂包括受阻酚类主抗氧剂和亚磷酸酯类辅抗氧剂组成。
所述的光稳定剂包括二苯甲酮类、 苯并三唑类、 三嗪类、 取代丙烯腈类、 草酰胺 类、 受阻胺类中的一种或几种。
所述的加工助剂为硬脂酰胺类润滑剂如 EBS、硅油和白矿油中的一种或几种的混 合物。
在本发明的另一个技术方案中, 还提供了一种适用于胶封铅酸蓄电池壳体的高极 性阻燃苯乙烯类组合物的制备方法, 包括如下步骤:
a、 按比例将苯乙烯类树脂、 溴系阻燃体系、 共混弹性体、 模量改性剂、 极性改 性剂、 抗氧剂、 光稳定剂、 加工助剂加入高速混合机混合 10-60分钟;
b、 将上述混合物经过精密计量的送料装置输送到双螺杆挤出机中, 挤出机的各 段螺杆温度控制在 170〜 230°C之间, 双螺杆挤出机的长径比为 20〜 40 , 螺杆转速为 200-800转 /分钟, 在螺杆的剪切、 混炼及输送下, 物料得以充分熔化、 复合, 再经过 挤出造粒、 干燥得到高极性阻燃苯乙烯类组合物粒子;
c、 将上述高极性阻燃苯乙烯类组合物粒子加入到注塑机中加工成所需样条, 所 述注塑条件为: 料筒温度 180-220 °C, 模具温度 50〜 70 °C, 注塑压力 6-10MPa。
在本发明的另一个技术方案中, 还提供了一种所述的高极性阻燃苯乙烯类组合物 的应用, 具体是将其用于环氧树脂胶水焊接的铅酸蓄电池壳体材料。
本发明具有有益效果:
1) 本发明所述的高极性阻燃苯乙烯类组合物的缺口冲击强度达到 25kJ/m2以上 时, 阻燃达到 UL94V-0@1.5mm, 同时其和环氧树脂胶水的粘接力达到 80kgf以上。
2) 本发明所述的高极性阻燃苯乙烯类组合物制备方法简单易行, 加工容易, 成 本低廉, 非常适用于胶水粘接的铅酸蓄电池壳体材料。 具体实施方式
下面结合一些具体实施方式对本发明高极性阻燃苯乙烯类组合物及其制备方法做进 一步描述, 具体实施例为进一步详细说明本发明, 非限定本发明的保护范围。
本发明所述的高极性阻燃苯乙烯组合物按照标准制备样条, 并进行下表 1中所列出 的性能测试。
表 1 性能测试及其标准
Figure imgf000006_0001
本发明所用到的仪器设备有:
制备高极性阻燃苯乙烯类组合物所用的双螺杆挤出机是由南京瑞亚高聚物装备有限 公司生产的 SHJ-30。
制备高极性阻燃苯乙烯类组合物测试样条采用的注塑机是由浙江海天注塑机有限公 司生产的 B-920型。
测试熔体流动速率用的仪器是美斯特工业系统(中国)有限公司生产的 ZR21452熔 体流动速率仪。
测试冲击强度用的冲击实验机是美国 Tinius Olsenis公司生产的 T92型。
测试拉伸强度及粘接力用的万能试验机是 Hounsfield公司生产的 H10K-S。
测试热变形温度用的维卡热变形测试仪是德国 COESFELD生产的 40-197型。 测试燃烧性能使用的 UL-94垂直燃烧仪是美国 ATLAS生产的 HVUL-2型。
所有本发明提供的实施例中, 提供的原材料均可从市面采购获得。 其中,苯乙烯树脂选用台湾台化的苯乙烯 AG15A1, ASA树脂选用日本 UMG的 ASA A600N;
溴系阻燃剂选用以色列死海溴公司的 FR-245 , 美国雅宝公司的 8010; 锑系助阻燃 剂选用云南木利锑业有限公司的 S-05N;
丙烯酸酯橡胶选用美国杜邦的 EA101, 硅橡胶选用日本钟渊的 MR-01, SBS选用韩 国 LG的 LG503N, 丁二烯橡胶选用韩国锦湖的 HR181;
焦磷酸钙选用中国南京松冠生产的产品, 高岭土选用美国的 HG90;
极性改性剂采用台湾台橡的马来酸酐接枝 SEBS-7131, 日本电化的苯乙烯-马来酰亚 胺共聚物 MS-NB, 沈阳科通的马来酸酐接枝的苯乙烯共聚物 KT-2, 日本 UMG的马来 酸酐接枝的 AS共聚物 S601N;
抗氧剂选用气巴精化的 Irganox 1010和 Irganox 168;
光稳定剂选用气巴精化的 770和 UV-P;
其它未提及的加工助剂为市售的通用商品。
实施例 1-4、对比例 1-4按照表 2中所列的重量份将各组分加入高速混合机中进行均 匀混合, 然后将上述混合物送入双螺杆挤出机中混炼、挤出、 拉条、 水冷、 切粒; 其中, 双螺杆挤出机的长径比为 20-40; 螺筒温度设定为: 一区温度 180°C, 二区温度 190°C, 三区温度 200°C, 四区温度 210°C, 五区温度 220°C, 六区温度 220°C, 七区温度 220°C, 八区温度 220°C,九区温度 220°C,十区温度 220°C,机头温度 230°C;螺杆转速为 200-800 转 / # 述方法制得的高极性阻燃苯乙烯组合物粒子按照标准制备样条进行表 1中所列 出的各性能测试并记录数据于表 2中。
表 2 实施例 1-4以及对比例 1-4中的原料配比以及性能
Figure imgf000007_0001
Figure imgf000008_0001
从上表 2中, 实施例 1-4中可以看出, 制备得到的高极性阻燃苯乙烯组合物具备优 异的阻燃性能、 缺口冲击强度和粘结性能; 配方体系中不同极性改性剂均明显优于未添 加极性改性剂的粘接力, 但不同极性改性剂的表现效果不同, 综合看, SEBS7131 和 MS-NB表现出更优的综合效果。
进一步, 实施例 5-12按照表 3 中所列的重量份将各组分加入高速混合机中进行均 匀混合, 然后将上述混合物送入双螺杆挤出机中混炼、挤出、 拉条、 水冷、 切粒; 其中, 双螺杆挤出机的长径比为 20-40; 螺筒温度设定为: 一区温度 180°C, 二区温度 190°C, 三区温度 200°C, 四区温度 210°C, 五区温度 220°C, 六区温度 220°C, 七区温度 220°C, 八区温度 220°C,九区温度 220°C,十区温度 220°C,机头温度 230°C;螺杆转速为 200-800 转 / # 述方法制得的高极性阻燃苯乙烯组合物按照标准制备样条进行表 1中所列出的 各性能测试并记录数据于表 3中。
Figure imgf000008_0002
Figure imgf000009_0001
以上所述仅为本发明的实施例, 并非因此限制本发明的专利范围, 凡是利用本发明 说明书内容所作的等效结构或等效流程变换, 或直接或间接运用在其他相关的技术领 域, 均同理包括在本发明的专利保护范围内。

Claims

A18113508
WO 2020/173490 PCT/CN2020/077075
i . 一种高极性阻燃苯乙烯类组合物, 其特征在于, 按重量份数计, 包括如下组分: 苯乙烯类树脂 35-65份;
溴系阻燃体系 15-25份;
共混弹性体 10-30份;
模量改性剂 5-10份;
极性改性剂 0.1-5份;
抗氧剂 0.1-1份;
光稳定剂 0.1-1份;
加工助剂 0.1-2份。
2. 根据权利要求 1所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所述苯乙烯 类树脂为丙烯腈-丁二烯 -苯乙烯接枝共聚物 (苯乙烯)、 丙烯腈 -苯乙烯-丙烯酸三元共聚 物 (ASA) 或甲基丙烯酸甲酯-丁二稀 -苯乙烯接枝共聚物 (MBS)。
3. 根据权利要求 1-2任一项所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所述 溴系阻燃体系为溴化亚胺、 溴化聚碳酸酯、 聚溴化苯乙烯、 溴化聚苯乙烯、 三(三溴苯 氧基)三聚氰酸酯、 八溴醚、 十溴二苯乙烷、 溴化环氧、 四溴双酚 A、 四溴双酚 A醚中 的一种或几种与三氧化二锑、 胶体五氧化二锑、 锑酸钠、 三氯化锑、 五氯化锑中的一种 或几种复配体系。
4. 根据权利要求 1-3 任一项所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所 述共混弹性体为丙烯酸酯橡胶、 硅橡胶、 SBS、 SEBS、 接枝 POE、 丁腈橡胶、 氟橡胶、 顺丁橡胶、 丁苯橡胶中的一种或几种。
5. 根据权利要求 1-4任一项所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所 述模量改性剂为其线膨胀系数 a<l x l0_6的粉体材料, 包含高岭土、 方解石、 焦磷酸盐、 焦钨酸盐中的一种或几种。
6. 根据权利要求 1-5任一项所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所 述极性改性剂为苯乙烯马来酰亚胺共聚物、 马来酸酐接枝的 SEBS、 马来酸酐接枝的 苯乙烯共聚物、 马来酸酐接枝的 AS 共聚物、 乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油 酯共聚物、 乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物中的一种或几种; 优选地, 所述极性改性剂为苯乙烯马来酰亚胺共聚物、 马来酸酐接枝的 SEBS、 马来酸酐接枝 的苯乙烯共聚物、 马来酸酐接枝的 AS共聚物中的一种或多种; 特别优选的是苯乙烯 A18113508
WO 2020/173490 PCT/CN2020/077075 马来酰亚胺共聚物、 马来酸酐接枝的 SEBS中的一种或两种; 最优选的是马来酸酐接 枝的 SEBS o
7. 根据权利要求 1-6任一项所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所 述抗氧剂包括受阻酚类主抗氧剂和亚磷酸酯类辅抗氧剂组成。
8. 根据权利要求 1-7任一项所述的高极性阻燃苯乙烯类组合物, 其特征在于: 所 述光稳定剂包括二苯甲酮类、 苯并三唑类、 三嗪类、 取代丙烯腈类、 草酰胺类、 受阻胺 类中的一种或几种; 所述加工助剂为硬脂酰胺类润滑剂 EBS、硅油和白矿油中的一种或 几种。
9. 一种制备如权利要求 1-8中任一项所述的高极性阻燃苯乙烯类组合物的制备方 法, 其特征在于, 包括如下步骤:
a、 按比例将苯乙烯类树脂、 溴系阻燃体系、 共混弹性体、 模量改性剂、 极性改性 剂、 抗氧剂、 光稳定剂、 加工助剂加入高速混合机混合;
b、 将上述混合物经过精密计量的送料装置输送到双螺杆挤出机中, 在螺杆的剪切、 混炼及输送下, 物料得以充分熔化、 复合, 再经过挤出造粒、 干燥得到胶封铅酸蓄电池 壳体的高极性阻燃苯乙烯组合物粒子;
C、 将阻燃苯乙烯组合物粒子加入到注塑机中加工成所需样条, 备用。
10. 一种如权利要求 1至 8中任一项所述的高极性阻燃苯乙烯类组合物的应用, 其特征在于:所述高极性阻燃苯乙烯组合物应用于环氧树脂胶水焊接的铅酸蓄电池壳体 材料。
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CN107936888A (zh) * 2017-11-08 2018-04-20 天津金发新材料有限公司 一种阻燃abs复合物及其制备方法与应用
CN108219351A (zh) * 2017-12-28 2018-06-29 金发科技股份有限公司 低内应力、高抗冲阻燃abs组合物及其制备方法和应用
CN109897331A (zh) * 2019-02-28 2019-06-18 金发科技股份有限公司 一种高极性阻燃苯乙烯类组合物、制备方法及其应用

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