WO2021012187A1 - 一种高性能阻燃abs复合材料及其制备方法 - Google Patents

一种高性能阻燃abs复合材料及其制备方法 Download PDF

Info

Publication number
WO2021012187A1
WO2021012187A1 PCT/CN2019/097323 CN2019097323W WO2021012187A1 WO 2021012187 A1 WO2021012187 A1 WO 2021012187A1 CN 2019097323 W CN2019097323 W CN 2019097323W WO 2021012187 A1 WO2021012187 A1 WO 2021012187A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite material
abs composite
retardant
zone
flame
Prior art date
Application number
PCT/CN2019/097323
Other languages
English (en)
French (fr)
Inventor
秦旺平
黄险波
叶南飚
付锦锋
杨霄云
Original Assignee
金发科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Priority to PCT/CN2019/097323 priority Critical patent/WO2021012187A1/zh
Publication of WO2021012187A1 publication Critical patent/WO2021012187A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the invention belongs to the technical field of ABS composite materials, and specifically relates to a high-performance flame-retardant ABS composite material and a preparation method thereof.
  • ABS resin is a terpolymer composed of styrene, butadiene and acrylonitrile. It has the high fluidity of styrene, the toughness of butadiene and the chemical resistance of acrylonitrile. It has excellent processing performance and resistance to chemicals. Low temperature performance, electrical insulation performance, high gloss and excellent electroplating performance. At the same time, it has excellent characteristics such as good creep resistance, high dimensional stability, and low molding shrinkage. It is used in plastic products in the fields of home appliances, automobiles, electronic appliances, etc. Very extensive.
  • the oxygen index of ABS resin is only 18%
  • the glow-wire ignition temperature is only about 700°C
  • the vertical combustion can only reach HB level. It is difficult to pass the needle flame test. These performance defects make it more difficult to apply to some electrical appliances with higher safety requirements. Only by improving the performance of the product and developing a new flame-retardant technology to give the material higher flame-retardant performance can it meet the performance requirements of oxygen index, glow wire, and needle flame testing in product applications.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a high-performance flame-retardant ABS composite material.
  • the ABS composite material has excellent heat resistance, weather resistance, solvent resistance, and abrasion resistance.
  • the technical solution adopted by the present invention is: a high-performance flame-retardant ABS composite material, comprising the following components by weight: 28-73 parts of ABS resin, 5-50 parts of POK polyketone resin, and the POK polyketone
  • the melt index of the ketone resin under the test conditions of 240°C and 2.16kg is greater than 120g/10min.
  • the structural formula of the POK polyketone resin is shown in formula (1):
  • the invention creatively alloys the POK polyketone resin with a specific structure with ABS, which solves the technical bottleneck problem of the compatibility of the resin system and greatly improves the mechanical properties of the material.
  • the material is given Excellent weather resistance, solvent resistance, heat resistance, etc., make up for the shortcomings of existing flame-retardant ABS alloy materials, and have greater industrial application value.
  • the high-performance flame-retardant ABS composite material further contains the following components by weight: 35-70 parts of ABS resin and 15-50 parts of POK polyketone resin.
  • the ABS resin is composed of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer, and the weight of the grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer is The ratio is (5 ⁇ 80): (20 ⁇ 95).
  • ABS resin can be synthesized by bulk method or emulsion method, and can also be obtained by blending grafted polybutadiene rubber and acrylonitrile-polystyrene copolymer.
  • the high-performance flame-retardant ABS composite material further comprises the following components by weight: 13-17 parts of bromine-based flame retardant, and 3-7 parts of antimony-based flame retardant.
  • the brominated flame retardant is decabromodiphenyl ethane, brominated epoxy resin, brominated polystyrene, tetrabromobisphenol A and tris(tribromophenyl) triazine, brominated ethylene At least one of amines;
  • the antimony flame retardant is at least one of antimony trioxide, antimony pentoxide, sodium antimonate, and antimony phosphate.
  • the high-performance flame-retardant ABS composite material further contains 2-8 parts by weight of a compatibilizer, and the compatibilizer is ABS grafted with maleic anhydride, ABS grafted with methyl acrylate, and styrene-propylene. At least one of nitrile-glycidyl methacrylate terpolymers.
  • the compatibilizer is a styrene-acrylonitrile-glycidyl methacrylate terpolymer
  • the average particle size of the styrene-acrylonitrile-glycidyl methacrylate terpolymer is 40. -350 ⁇ m, epoxy content 4-6wt%, weight average molecular weight 1.0 ⁇ 10 5 g/mol-3.0 ⁇ 10 5 g/mol, structural formula is shown in formula (2):
  • the high-performance flame-retardant ABS composite material further contains 0.2-2 parts by weight of processing aids.
  • the high-performance flame-retardant ABS composite material further contains 0.1-1 parts by weight of a weathering agent, and the weathering agent is a combination of a benzotriazole light stabilizer and a hindered amine light stabilizer.
  • the benzotriazole-based light stabilizer is at least one of compound A and compound B.
  • the structural formula of compound A is as shown in formula (3), and the structural formula of compound B is as shown in formula (4). ); the structural formula of the hindered amine light stabilizer is shown in formula (5):
  • the present invention also provides a method for preparing the high-performance flame-retardant ABS composite material, the method is:
  • the preparation method of the present invention has simple and continuous flow, high production efficiency and stable product quality.
  • the invention creatively alloys the POK polyketone resin with a specific structure with ABS, which effectively solves the technical bottleneck problem of the compatibility of the conventional two resins, and prepares a high-performance alloy material with better heat resistance , Solvent resistance, weather resistance, abrasion resistance, etc., and the specific structure of POK polyketone itself can reduce the amount of flame retardant.
  • It is a new type of green polymer, making the prepared alloy material unique Green and environmentally friendly, it has great originality in technology and simple production process, which is convenient for industrialization and mass production.
  • the ingredients in the formula are fully melted and plasticized, kneaded and mixed, extruded through the head, drawn, cooled, pelletized, dried, and packaged.
  • the new high-performance flame-retardant ABS composite material is obtained; among them, the temperature of each section of the twin-screw extruder from the feeding port to the die is: the temperature of the first zone is 80°C, the temperature of the second zone is 160°C, and the temperature of the third zone is 180°C.
  • screw speed is preferably 320 rpm, double The length to diameter ratio of the screw extruder is 40:1.
  • Test items unit Executive standard Tensile Strength MPa ISO527 Izod notched impact strength kJ/m 2 ISO180 Flame retardant performance Class UL 94 Heat distortion temperature °C IEC60695.2-12 Weather resistance % ISO 4893-2/200h
  • Examples 1 to 10 and specific Examples 1 to 5 are commercially available unless otherwise specified.
  • ABS is commercially available ABS PA-757K
  • POK polyketone resin is commercially available POK M930A (100 ⁇ m ⁇ 15000, n ⁇ m+1, melting index is>120g/10min)
  • brominated flame retardant is decabromodiphenylethane, STYTEX 8010, product of Albemarle Bromine is selected
  • antimony flame retardant The agent is selected from Changde Chenzhou product Sb 2 O 3 ; the processing aids include antioxidants, lubricants and anti-dripping agents.
  • the specific weight ratio of the content of antioxidants, lubricants and anti-dripping agents is 1:1: 0.5, where the antioxidants are Irganox 1010 and Irganox 168 of BASF, the lubricant is N,N'-ethylenebisstearylamide (EBS), the anti-dripping agent is X-010, and the weathering agent is TINUVIN 234 (Benzotriazole light stabilizer) and UV-770 (hindered amine light stabilizer);
  • the compatibilizers in Examples 1 to 5 are ABS grafted maleic anhydride, ABS grafted methyl acrylate, Styrene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer , Where the average particle size of the styrene-acrylonitrile-glycid
  • Example 6 Except that the weight ratio of grafted polybutadiene rubber to grafted polystyrene-acrylonitrile copolymer is different from that of Example 5 in Examples 6 and 7, the other components and contents are the same as Example 5.
  • the weight ratios of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer in 7 are 2:98 and 85:15 respectively; in Example 8, styrene-acrylonitrile-glycidyl methacrylate three Except that the average particle size, density, and epoxy content of the copolymer are different, the other components and contents are the same as in Example 5.
  • Example 8 The average of the styrene-acrylonitrile-glycidyl methacrylate terpolymer in Example 8 Particle size> 350 ⁇ m, epoxy content 4 ⁇ 0.2wt%, weight average molecular weight 2.5 ⁇ 10 5 g/mol;
  • Examples 9 and 10 are the same as those in Example 5 except for the selection of weathering agents.
  • 10 weathering agents are TINUVIN 234 (benzotriazole light stabilizer), UV-770 (hindered amine light stabilizer).
  • Table 2 The content and performance test results of each component in specific examples 1 to 10 are shown in Table 2:
  • the ABS composite material of the present invention has excellent heat resistance, solvent resistance, weather resistance, and flame retardancy, and has excellent comprehensive mechanical properties and mass production application value as a whole. Comparing Examples 6 and 7 with Example 5, it is found that when the weight ratio of grafted polybutadiene rubber to grafted polystyrene-acrylonitrile copolymer is (5-80): (20-95), ABS The composite material has better overall performance; comparing Example 8 with Example 5, it is found that when the average particle size of the styrene-acrylonitrile-glycidyl methacrylate terpolymer is 40-350 ⁇ m, the epoxy content is 4- At 6wt%, when the weight average molecular weight is 1.0 ⁇ 10 5 g/mol-3.0 ⁇ 10 5 g/mol, the ABS composite material has more excellent comprehensive properties (at the same time it has better tensile strength, impact strength, and weather resistance) Comparing Examples 9, 10 with Example 5, it is found that when the weathering agent is a combination
  • the present invention sets up experimental groups 1 to 7 and control groups 1 to 3.
  • the experimental group and control group of the present invention use the following raw materials, but are not limited to these raw materials:
  • ABS resin composed of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer, the weight ratio of grafted polybutadiene rubber to grafted polystyrene-acrylonitrile copolymer is (5 ⁇ 80): (20 ⁇ 95), such as ABS PA-757K;
  • POK polyketone resin POK M930A (melt index is> 120g/10min, test condition is 240°C/2.16kg), POK M330A (melt index is 40 ⁇ 120g/10min, test condition is 240°C/2.16kg);
  • Brominated flame retardant Decabromodiphenyl ethane, selected from Albemarle’s bromine product STYTEX 8010;
  • Antimony flame retardant selected from Changde Chenzhou product Sb 2 O 3 ;
  • Jiayirong SAG-002 styrene-acrylonitrile-glycidyl methacrylate terpolymer, average particle size of 40-350 ⁇ m, epoxy content of 5 ⁇ 0.2wt%, the weight average molecular weight is 1.4 ⁇ 10 5 g/mol
  • the antioxidants are Irganox 1010 and Irganox 168 from BASF
  • the lubricant is selected from N,N'-ethylenebisstearylamide (EBS)
  • the anti-dripping agent X-010 of polytetrafluoroethylene the specific anti-oxidant
  • the weight ratio of the oxygen agent, lubricant, and anti-dripping agent is 1:1:0.5.
  • Weathering agent a combination of TINUVIN 234 (benzotriazole light stabilizer) and UV-770 (hindered amine light stabilizer).
  • Table 3 The content of each component and the test results of each performance in the experimental group 1-7 and the control group 1-3

Landscapes

  • 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

本发明公开了一种高性能阻燃ABS复合材料，包含以下重量份的成分：ABS树脂28-73份、POK聚酮树脂5-50份，所述POK聚酮树脂在240℃、2.16kg测试条件下的熔融指数大于120g/10min。本发明创造性将特定结构的POK聚酮树脂与ABS合金化，很好的解决了树脂体系的相容性技术瓶颈问题，大大提升了材料的力学性能，同时由于POK树脂自身的优点，赋予了材料优异的耐候性、耐溶剂性、耐热性等特点，弥补了现有阻燃ABS合金材料的不足，具有较大的产业化应用价值。同时，本发明还提供一种所述高性能阻燃ABS复合材料的制备方法。

Description

一种高性能阻燃ABS复合材料及其制备方法 技术领域
本发明属于ABS复合材料技术领域，具体涉及一种高性能阻燃ABS复合材料及其制备方法。
背景技术
ABS树脂是由苯乙烯、丁二烯、丙烯腈组成的三元共聚物，具有苯乙烯的高流动性、丁二烯的韧性和丙烯腈的耐化学药品腐蚀特性，具有优良的加工性能、耐低温性能、电绝缘性能、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,在家电、汽车、电子电器等领域的塑料制品中应用非常广泛。
ABS树脂的氧指数只有18％，灼热丝起燃温度只有700℃左右，垂直燃烧只能达到HB级，难以通过针焰测试，这些性能缺陷导致其较难应用于一些具有较高安规要求的电器产品，只有通过性能提升，开发一种新的阻燃技术，赋予材料较高的阻燃性能，才能满足产品应用中的氧指数、灼热丝、针焰测试等性能要求。
发明内容
基于此，本发明的目的在于克服上述现有技术的不足之处而提供一种高性能阻燃ABS复合材料。所述ABS复合材料具有优异的耐热性、耐候性、耐溶剂性、耐磨性。
为实现上述目的，本发明采用的技术方案为：一种高性能阻燃ABS复合材料，包含以下重量份的成分：ABS树脂28-73份、POK聚酮树脂5-50份，所述POK聚酮树脂在240℃、2.16kg测试条件下的熔融指数大于120g/10min，所述POK聚酮树脂的结构式如式(1)所示：
Figure PCTCN2019097323-appb-000001
其中，100＜m＜15000，n≥m+1。
本发明创造性将特定结构的POK聚酮树脂与ABS合金化，很好的解决了树脂体系的相容性技术瓶颈问题，大大提升了材料的力学性能，同时由于POK树脂自身的优点，赋予了材料优异的耐候性、耐溶剂性、耐热性等特点，弥补了现有阻燃ABS合金材料的不足，具有较大的产业化应用价值。
优选地，所述的高性能阻燃ABS复合材料，还包含以下重量份的成分：ABS树脂35-70份、POK聚酮树脂15-50份。
优选地，所述ABS树脂由接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物组成，所述接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比为(5～80)：(20～95)。ABS树脂可以由本体法或者乳液法合成，也可由接枝聚丁二烯橡胶与丙烯腈-聚苯乙烯共聚物共混而得。
优选地，所述的高性能阻燃ABS复合材料，还包含以下重量份的成分：溴系阻燃剂13-17份、锑系阻燃剂3-7份。
更优选地，所述溴系阻燃剂为十溴二苯乙烷、溴化环氧树脂、溴化聚苯乙烯、四溴双酚A及三(三溴苯基)三嗪、溴化亚胺中的至少一种；所述锑系阻燃剂为三氧化二锑、五氧化二锑、锑酸钠、磷酸锑中的至少一种。
优选地，所述的高性能阻燃ABS复合材料，还包含2-8重量份的相容剂，所述相容剂为ABS接枝马来酸酐、ABS接枝丙烯酸甲酯、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物中的至少一种。
更优选地，所述相容剂为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物，所述苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物的平均粒度为40-350μm，环氧含量为4-6wt％，重均分子量1.0×10 5g/mol-3.0×10 5g/mol，结构 式如式(2)所示：
Figure PCTCN2019097323-appb-000002
粒度较小易产生团聚，粒度过大增容效果降低，环氧含量与增容效率相关，分子量大小与力学性能相关。
优选地，所述的高性能阻燃ABS复合材料，还包含0.2-2重量份的加工助剂。
优选地，所述的高性能阻燃ABS复合材料，还包含0.1-1重量份的耐候剂，所述耐候剂为苯并三唑类光稳定剂、受阻胺类光稳定剂的复配。
更优选地，所述苯并三唑类光稳定剂为化合物A、化合物B中的至少一种，所述化合物A的结构式如式(3)所示，所述化合物B的结构式如式(4)所示；所述受阻胺类光稳定剂的结构式如式(5)所示：
Figure PCTCN2019097323-appb-000003
同时，本发明还提供一种所述的高性能阻燃ABS复合材料的制备方法，所述方法为：
(1)将各成分在高速搅拌混料机中混合均匀或单独通过计量喂料器进入双螺杆挤出机中；
(2)在双螺杆挤出机的输送、混合和剪切作用下，配方中各成分充分熔融 塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥、包装，得到所述新型环保阻燃ABS复合材料；其中，双螺杆挤出机的各段螺杆温度从加料口到机头分别为：一区80℃、二区160℃、三区180℃、四区230℃、五区230℃、六区230℃、七区220℃、八区220℃、九区220℃、机头230℃，螺杆转速为300-400rpm，双螺杆挤出机的长径比为40:1。
本发明上述制备方法流程简单、连续，生产效率高，产品品质稳定。
相对于现有技术，本发明的有益效果为：
本发明创造性将特定结构的POK聚酮树脂与ABS合金化，有效地解决了常规两种树脂的相容性技术瓶颈问题，制备了一种高性能化的合金材料，具有较好的耐热性、耐溶剂性能、耐候性能、耐磨性能等，并且特定结构的POK聚酮自身的易成炭性可以降低阻燃剂的用量，其属于一种新型绿色聚合物，使得制备的合金材料具有独特绿色环保特性，技术方面具有很大的独创性，生产工艺简单，便于工业化大规模量产。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
本发明实施例中ABS复合材料的制备方法为：
(1)将ABS树脂、POK聚酮树脂、溴系阻燃剂、锑系阻燃剂、相容剂以及加工助剂按比例进行高速搅拌混料机混合均匀或单独通过计量喂料器进入双螺杆挤出机中；
(2)在双螺杆挤出机的输送、混合和剪切作用下，配方中各成分充分熔融塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥、包装，得到所述新型高性能阻燃ABS复合材料；其中，双螺杆挤出机的各段螺杆温度从加料口到机头分别为：一区温度80℃、二区温度160℃、三区温度180℃、四区温度230℃、五区温度230℃、六区温度230℃、七区温度220℃、八区温度220℃、九区温度220℃、机头温度230℃，螺杆转速优选为320rpm，双螺杆挤出机的长径比为40:1。
实施例中各性能的具体评价方法如表1所示：
表1 各性能的测量标准
检测项目 单位 执行标准
拉伸强度 MPa ISO527
悬臂梁缺口冲击强度 kJ/m 2 ISO180
阻燃性能 Class UL 94
热变形温度 ℃ IEC60695.2-12
耐候性 ％ ISO 4893-2/200h
本发明设置实施例1～10，具体实施例1～5中的各成分，如无具体说明，均为市售可得：其中，ABS为市售ABS PA-757K；POK聚酮树脂为市售POK M930A(100＜m＜15000，n≥m+1，熔融指数为＞120g/10min)；溴系阻燃剂为十溴二苯乙烷，选用雅宝溴的产品STYTEX 8010；锑系阻燃剂选自常德辰州产品Sb 2O 3；加工助剂包括抗氧剂、润滑剂和抗滴落剂，具体抗氧剂、润滑剂、抗滴落剂的含量的重量比为1:1:0.5，其中抗氧剂选用巴斯夫的Irganox 1010和Irganox 168，润滑剂选自N,N'-亚乙基双硬脂酰胺(EBS)，抗滴落剂选自X-010，耐候剂为TINUVIN 234(苯并三唑类光稳定剂)和UV-770(受阻胺类光稳定剂)组合；实施例1～5中的相容剂分别为ABS接枝马来酸酐、ABS接枝丙烯酸甲酯、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物，其中苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物的平均粒度为40-350μm，环氧含量为5±0.2wt％时，重均分子量为1.4×10 5g/mol；实施例1～5中的ABS树脂由接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物组成，所述接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比依次为：5：95、80：20、40：60、50：50、28：72。
实施例6、7中除接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比与实施例5不同外，其他成分及含量均与实施例5相同，实施例6、7中接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比分别为2：98、85：15；实施例8中苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物的平均粒度、密度、环氧含量不同外，其他成分及含量均与实施例5相同，具体实施例8中的苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物的平均粒度＞350μm，环氧含量为 4±0.2wt％，重均分子量2.5×10 5g/mol；实施例9、10中除耐候剂选择不同外，其他均与实施例5中相同，实施例9、10中耐候剂分别为TINUVIN 234(苯并三唑类光稳定剂)、UV-770(受阻胺类光稳定剂)。具体实施例1～10中各成分含量及性能测试结果如表2所示：
表2 实施例1～10中各成分含量及性能测试结果
Figure PCTCN2019097323-appb-000004
从表2可以看出，本发明ABS复合材料具有优异的耐热性、耐溶剂性和耐候、阻燃性能，整体具有优异综合力学性能和量产应用价值。将实施例6、7与实施例5对比发现，当接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比为(5～80)：(20～95)时，ABS复合材料具有更好综合性能；将实施例8与实 施例5对比发现，当苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物中平均粒度为40-350μm，环氧含量为4-6wt％时，重均分子量为1.0×10 5g/mol-3.0×10 5g/mol时，ABS复合材料具有更加优异的综合性能(同时具有较好的拉伸强度、冲击强度、耐候性)；将实施例9、10与实施例5对比发现，当耐候剂选择TINUVIN234(苯并三唑类光稳定剂)和UV-770(受阻胺类光稳定剂)的复配时，本发明所述ABS复合材料具有更好的耐候性，氙灯老化后色差较小。
此外，本发明设置实验组1～7及对照组1～3，具体本发明的实验组及对照组采用如下原料，但不仅限于这些原料：
ABS树脂：由接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物组成，所述接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比为(5～80)：(20～95)，如ABS PA-757K；
POK聚酮树脂：POK M930A(熔融指数为＞120g/10min，测试条件为240℃/2.16kg)、POK M330A(熔融指数为40～120g/10min，测试条件为240℃/2.16kg)；
溴系阻燃剂：十溴二苯乙烷，选用雅宝的溴的产品STYTEX 8010；
锑系阻燃剂：选自常德辰州产品Sb 2O 3；
相容剂：佳易容SAG-002(苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物，平均粒度为40-350μm，环氧含量为5±0.2wt％时，重均分子量为1.4×10 5g/mol)；
加工助剂：抗氧剂选用巴斯夫的Irganox 1010和Irganox 168，润滑剂选自N,N'-亚乙基双硬脂酰胺(EBS)，聚四氟乙烯抗滴落剂X-010，具体抗氧剂、润滑剂、抗滴落剂的含量的重量比为1:1:0.5。
耐候剂：TINUVIN 234(苯并三唑类光稳定剂)和UV-770(受阻胺类光稳定剂)的复配。
具体实验组1～7及对照组1～3中各成分含量及各性能测试结果如表3所示：
表3 实验组1～7及对照组1～3中各成分含量及各性能测试结果
Figure PCTCN2019097323-appb-000005
Figure PCTCN2019097323-appb-000006
从表3可以看出，将实验组1与对照组1～2对比可知，本发明特定POK聚酮树脂的加入，可提高热变形温度和耐候性；将实验组2与对照组3相比，POK聚酮树脂的加入，可以提高材料的耐候性，而且由于POK聚酮树脂自身具有较好的成炭性，含量的增加可以提高阻燃等级。将实验组5、6、7与实验组4比较，随着POK聚酮树脂含量的进一步增加，材料的耐热性和耐候性均进一步提高；将实验组3与实验组4比较，本发明所述相容剂苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物提高了体系的冲击性能，满足了材料应用方面的韧性需求。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种高性能阻燃ABS复合材料，其特征在于，包含以下重量份的成分：ABS树脂28-73份、POK聚酮树脂5-50份，所述POK聚酮树脂在240℃、2.16kg测试条件下的熔融指数大于120g/10min，所述POK聚酮树脂的结构式如式(1)所示：
    Figure PCTCN2019097323-appb-100001
    其中，100＜m＜15000，n≥m+1。
  2. 如权利要求1所述的高性能阻燃ABS复合材料，其特征在于，所述ABS树脂由接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物组成，所述接枝聚丁二烯橡胶与接枝聚苯乙烯-丙烯腈共聚物的重量比为(5～80)：(20～95)。
  3. 如权利要求1或2所述的高性能阻燃ABS复合材料，其特征在于，还包含以下重量份的成分：溴系阻燃剂13-17份、锑系阻燃剂3-7份。
  4. 如权利要求3所述的高性能阻燃ABS复合材料，其特征在于，所述溴系阻燃剂为十溴二苯乙烷、溴化环氧树脂、溴化聚苯乙烯、四溴双酚A及三(三溴苯基)三嗪、溴化亚胺中的至少一种；所述锑系阻燃剂为三氧化二锑、五氧化二锑、锑酸钠、磷酸锑中的至少一种。
  5. 如权利要求1或2所述的高性能阻燃ABS复合材料，其特征在于，还包含2-8重量份的相容剂，所述相容剂为ABS接枝马来酸酐、ABS接枝丙烯酸甲酯、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物中的至少一种。
  6. 如权利要求5所述的高性能阻燃ABS复合材料，其特征在于，所述相容剂为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物，所述苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯三元共聚物的平均粒度为40-350μm，环氧含量为4-6wt％，重均分子量1.0×10 5g/mol-3.0×10 5g/mol，结构式如式(2)所示：
    Figure PCTCN2019097323-appb-100002
  7. 如权利要求1～3任一项所述的高性能阻燃ABS复合材料，其特征在于，还包含0.2-2重量份的加工助剂。
  8. 如权利要求1～3任一项所述的高性能阻燃ABS复合材料，其特征在于，还包含0.1-1重量份的耐候剂，所述耐候剂为苯并三唑类光稳定剂、受阻胺类光稳定剂的复配。
  9. 如权利要求8所述的高性能阻燃ABS复合材料，其特征在于，所述苯并三唑类光稳定剂为化合物A、化合物B中的至少一种，所述化合物A的结构式如式(3)所示，所述化合物B的结构式如式(4)所示；所述受阻胺类光稳定剂的结构式如式(5)所示：
    Figure PCTCN2019097323-appb-100003
  10. 一种如权利要求1～9任一项所述的高性能阻燃ABS复合材料的制备方法，其特征在于，所述方法为：
    (1)将各成分在高速搅拌混料机中混合均匀或单独通过计量喂料器进入双螺杆挤出机中；
    (2)在双螺杆挤出机的输送、混合和剪切作用下，配方中各成分充分熔融塑化、捏合混炼、经机头挤出、拉条、冷却、切粒、干燥、包装，得到所述高 性能阻燃ABS复合材料；其中，双螺杆挤出机的各段螺杆温度从加料口到机头分别为：一区80℃、二区160℃、三区180℃、四区230℃、五区230℃、六区230℃、七区220℃、八区220℃、九区220℃、机头230℃，螺杆转速为300-400rpm，双螺杆挤出机的长径比为40:1。
PCT/CN2019/097323 2019-07-23 2019-07-23 一种高性能阻燃abs复合材料及其制备方法 WO2021012187A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/097323 WO2021012187A1 (zh) 2019-07-23 2019-07-23 一种高性能阻燃abs复合材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/097323 WO2021012187A1 (zh) 2019-07-23 2019-07-23 一种高性能阻燃abs复合材料及其制备方法

Publications (1)

Publication Number Publication Date
WO2021012187A1 true WO2021012187A1 (zh) 2021-01-28

Family

ID=74192940

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/097323 WO2021012187A1 (zh) 2019-07-23 2019-07-23 一种高性能阻燃abs复合材料及其制备方法

Country Status (1)

Country Link
WO (1) WO2021012187A1 (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900789A (en) * 1988-12-22 1990-02-13 Shell Oil Company Polymer blend of carbon monoxide/olefin copolymer and conjugated alkadiene
CN107903567A (zh) * 2017-11-20 2018-04-13 广东聚石化学股份有限公司 一种阻燃abs/pok合金及其制备方法
CN108641269A (zh) * 2018-03-28 2018-10-12 广东聚石化学股份有限公司 一种耐溶剂耐候阻燃abs/pok合金及其制备方法
CN110343382A (zh) * 2019-07-23 2019-10-18 金发科技股份有限公司 一种高性能阻燃abs复合材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900789A (en) * 1988-12-22 1990-02-13 Shell Oil Company Polymer blend of carbon monoxide/olefin copolymer and conjugated alkadiene
CN107903567A (zh) * 2017-11-20 2018-04-13 广东聚石化学股份有限公司 一种阻燃abs/pok合金及其制备方法
CN108641269A (zh) * 2018-03-28 2018-10-12 广东聚石化学股份有限公司 一种耐溶剂耐候阻燃abs/pok合金及其制备方法
CN110343382A (zh) * 2019-07-23 2019-10-18 金发科技股份有限公司 一种高性能阻燃abs复合材料及其制备方法

Similar Documents

Publication Publication Date Title
CN101503570B (zh) 一种用于薄壁制品的玻璃纤维增强环保阻燃尼龙合金及其制备方法
CN110343382A (zh) 一种高性能阻燃abs复合材料及其制备方法
CN106751678A (zh) 一种低气味、低散发、阻燃pc/abs复合材料及其制备方法
CN103374214A (zh) 一种高抗冲、绿色环保阻燃pc/abs合金材料及其制备工艺
CN104403258A (zh) 一种阻燃增强abs复合材料及其制备方法
CN113248901B (zh) 一种无卤阻燃abs合金材料及其制备方法
CN104629184A (zh) 一种含聚丁烯合金的复合材料及其制备方法
CN107541049B (zh) 一种石墨烯协同连续玻纤增强无卤阻燃耐候ppo/hips合金材料及其制备方法
WO2020253483A1 (zh) 一种环保阻燃abs复合材料及其制备方法
CN101974216A (zh) 一种无卤阻燃pc/abs合金
CN101486824B (zh) 耐低温的环保阻燃高抗冲聚苯乙烯组合物制备方法
WO2013057841A1 (ja) 難燃剤マスターバッチ及びそれを使用したスチレン系難燃性樹脂組成物の製造方法
CN107418197B (zh) 一种导热尼龙工程塑料及其制备方法
CN102719082B (zh) 一种聚苯醚/abs合金及其制备方法
CN104817838A (zh) 一种高韧性无卤阻燃pc/abs合金反光材料及其制备方法
CN106349675B (zh) 一种耐水解、耐低温pc/abs复合材料及其制备方法
CN104448672A (zh) 一种抗氧化、高流动、无卤阻燃abs及其制备工艺
CN115109350B (zh) 一种高性阻燃hips材料及其制备方法和应用
WO2021012187A1 (zh) 一种高性能阻燃abs复合材料及其制备方法
CN103073854A (zh) 一种聚酯组合物、制备方法及其应用
CN102775681A (zh) 高温耐析出无卤阻燃聚丙烯组合物及其制备方法
CN103937094A (zh) 一种抗打螺钉爆裂增强聚丙烯材料、其制备方法及其应用
CN101333318A (zh) 无析出聚丙烯阻燃母料及其制备方法
CN110760177B (zh) 导电聚苯醚/高抗冲聚苯乙烯组合物及其制备方法
CN110684313B (zh) 一种陶瓷/abs超强超韧复合材料及在电气领域的应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19939034

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19939034

Country of ref document: EP

Kind code of ref document: A1