WO2020253483A1 - 一种环保阻燃abs复合材料及其制备方法 - Google Patents

一种环保阻燃abs复合材料及其制备方法 Download PDF

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WO2020253483A1
WO2020253483A1 PCT/CN2020/092622 CN2020092622W WO2020253483A1 WO 2020253483 A1 WO2020253483 A1 WO 2020253483A1 CN 2020092622 W CN2020092622 W CN 2020092622W WO 2020253483 A1 WO2020253483 A1 WO 2020253483A1
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composite material
abs
retardant
environmentally friendly
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秦旺平
黄险波
叶南飚
付锦锋
杨霄云
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Kingfa Science and Technology Co Ltd
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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C08K2003/2282—Antimonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • the invention belongs to the technical field of ABS composite materials, and specifically relates to an environmentally friendly flame-retardant ABS composite material and a preparation method thereof.
  • ABS resin is a terpolymer composed of acrylonitrile, styrene and butadiene.
  • This material has the high fluidity of styrene, the toughness of butadiene, the solvent resistance and heat resistance of acrylonitrile, and it has excellent The processing performance, low temperature resistance, electrical insulation performance, high gloss and excellent electroplating performance. At the same time, it has the advantages of good creep resistance, high dimensional stability, and low molding shrinkage. It is used in the fields of home appliances, automobiles, electronic appliances, etc. Plastic products are widely used.
  • ABS material When the ABS material is applied to the peripheral position where the electrical product is in contact with the electric heating, in order to ensure the fire safety, the material needs to have high flame retardant performance, but the oxygen index of ABS is only 18%, which is a flammable material and cannot meet the requirements of industrial applications .
  • bromine antimony flame retardant can give ABS better flame retardancy, but the mechanical properties of the material are general, and cannot meet the technical requirements of materials for special applications.
  • the purpose of the present invention is to overcome the above shortcomings of the prior art and provide an environmentally friendly flame-retardant ABS composite material.
  • the technical solution adopted by the present invention is: an environmentally friendly flame-retardant ABS composite material, comprising the following components by weight: 50-88 parts of ABS resin, 3-40 parts of polyolefin resin, and 2-8 parts of compatibilizer
  • the compatibilizer is at least one of ABS grafted maleic anhydride, ABS grafted polyethylene, ABS grafted methyl methacrylate, and ethylene butyl acrylate copolymer.
  • the invention creatively proposes to develop the alloying properties of polyolefin resin and ABS resin.
  • a compatibilizer with a specific chemical structure, the compatibility of ABS resin and polyolefin resin is effectively solved, and the material has better mechanical properties and overcomes
  • the major technical bottleneck problems in the development of polyolefin and ABS alloys have made the resulting composite materials more cost-effective.
  • This alloy material has excellent low temperature toughness, solvent resistance and weather resistance, and has excellent comprehensive performance and mass production. Value.
  • 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). Under this ratio, ABS resin has better toughness, heat resistance, processing fluidity and mechanical properties.
  • the polyolefin resin is chlorinated polyethylene or polyvinyl chloride produced by a hydrochloric acid phase suspension method, and the mass percentage of chlorine in the polyolefin resin is 30-40%. Under this ratio, the thermal stability and fluidity of the material are better, and the mechanical properties are relatively excellent.
  • the environmentally friendly flame-retardant ABS composite material further comprises the following components by weight: 7-17 parts of bromine-based flame retardant and 3-6 parts of antimony-based flame retardant.
  • the brominated flame retardant is decabromodiphenyl ethane, decabromodiphenyl ether, brominated epoxy resin, brominated polystyrene, tetrabromobisphenol A, tris(tribromophenyl) At least one of triazines;
  • the antimony flame retardant is at least one of antimony trioxide, antimony pentoxide, antimonate, and antimony phosphate.
  • the environmentally friendly flame-retardant ABS composite material further contains 0.1-3 parts by weight of a heat stabilizer, and the heat stabilizer is methyl tin mercaptan, butyl tin, calcium zinc stabilizer, methyl tin maleate At least one of them.
  • a heat stabilizer is methyl tin mercaptan, butyl tin, calcium zinc stabilizer, methyl tin maleate At least one of them.
  • the heat stabilizer is methyl tin maleate.
  • butyl tin is easily decomposed to produce dibutyl tin, which is a substance that can disrupt the endocrine function of organisms.
  • the REACH regulations have imposed a limited use requirement on it; methyl tin mercaptan one
  • the smell is large, on the other hand, it will affect the overall color of the material; the thermal stability of calcium and zinc stabilizer is not high, and the amount of addition is large; and methyl tin maleate due to its special chemical structure, it is very effective for chlorine in the material forming process.
  • the thermal decomposition of chemical polyethylene has higher efficiency, and has the advantages of small addition amount and low odor.
  • the methyl tin maleate is obtained by mixing monomethyl tin maleate and dimethyl tin maleate, and the mass percentage of tin in the methyl tin maleate It is 30-50%. Within this range, it has good initial thermal stability and inhibits degradation and discoloration.
  • the thermal stabilizer is an environmentally friendly and highly efficient thermal stabilizer, which has good thermal stability efficiency, improves the problem of poor thermal stability during the processing of the ABS/polyolefin alloy, and achieves better processing performance of the material.
  • the structural formula of the dimethyl tin maleate is as shown in formula (1), and the structural formula of the monomethyl tin maleate is as shown in formula (2):
  • R1 and R2 can be a hydrogen group, an alkyl group, an alkoxy group, a carboxyl group, a carbonyl group, an ester group, and a methyl group is preferred.
  • the environmentally friendly flame-retardant ABS composite material further contains 0.3-2 parts by weight of processing aids.
  • the present invention also discloses a preparation method of the environmentally friendly flame-retardant ABS composite material, the method is:
  • the invention improves the toughness and weather resistance of the material by alloying ABS with polyolefin resin, and greatly compensates for the lack of performance of flame-retardant ABS materials.
  • compatibilizer and thermal stability system the material processing and application are solved Defects make the material have better industrial application value.
  • Examples 1 to 11 and Specific Examples 1 to 5 are as shown in Table 2. Unless otherwise specified, they are all commercially available. Examples 6 and 7 except for grafted polybutylene The weight ratio of the diene rubber to the grafted polystyrene-acrylonitrile copolymer is different from that in Example 5. The other components and contents are the same as in Example 5. In Examples 6 and 7, the grafted polybutadiene rubber and grafted The weight ratio of the branched polystyrene-acrylonitrile copolymer is 2:98 and 85:15 respectively; in Examples 8 and 9, except for the chlorine content in the polyolefin resin, the other components and contents are the same as in Example 5.
  • Example 8 and 9 the chlorine content in the polyolefin resin is 25% and 45%, respectively; in Examples 10 and 11, except for the different tin content in methyl tin maleate, the others are the same as in Example 5.
  • the tin content in methyl tin maleate in Examples 10 and 11 are 25% and 55% respectively:
  • the ABS composite material of the present invention has excellent low temperature toughness, solvent resistance, weather resistance, and flame retardant properties, and has excellent comprehensive mechanical properties and mass production application value. 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 comprehensive properties; comparing Examples 8, 9 and Example 5, it is found that when the mass percentage of chlorine in the polyolefin resin is 30-40%, the ABS composite material has more excellent comprehensive mechanical properties; Comparing Examples 10 and 11 with Example 5, it is found that when the mass percentage of tin in methyl tin maleate is 30-50%, the ABS composite material of the present invention has better thermal stability and thermal stability. The residual color difference ⁇ E is small.
  • 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-757;
  • Polyolefin resin chlorinated polyethylene or polyvinyl chloride produced by the hydrochloric acid phase suspension method, the mass percentage of chlorine in the polyolefin resin is 30-40%, such as CPE-135A.
  • Bromine-based flame retardants select Israeli Dead Sea bromine products
  • Antimony flame retardant selected from Changde Chenzhou products
  • Compatibilizer selected from ABS grafted methyl methacrylate
  • Heat stabilizer selected from methyl tin maleate with a tin content of 42%; the heat stabilizers for experimental groups 2-5 and control group 2 of this application are all methyl tin maleate, methyl tin maleate can It is monomethyl tin maleate, dimethyl tin maleate, or a mixture of the two.
  • the antioxidants are Ciba refined Irganox 1010 and Irganox 168
  • the lubricant is selected from N,N'-ethylenebisstearic acid amide (EBS), polytetrafluoroethylene anti-dripping agent X-010 .
  • Table 4 The content of each component and the results of each performance test in the experimental group 1-7 and the control group 1-3

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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

一种环保阻燃ABS复合材料，包含以下重量份的成分：ABS树脂50-88份、聚烯烃树脂3-40份、相容剂2-8份，所述相容剂为ABS接枝马来酸酐、ABS接枝聚乙烯、ABS接枝甲基丙烯酸甲酯、乙烯丙烯酸丁酯共聚物中的至少一种。通过将ABS与聚烯烃树脂合金化，提升了材料的韧性和耐候性，大大弥补了阻燃ABS材料性能的不足，通过相容剂和热稳定体系的开发，解决了材料的加工和应用缺陷，使得材料具有较好的产业化应用价值。同时，还提供一种所述环保阻燃ABS复合材料的制备方法。

Description

一种环保阻燃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，具体涉及一种环保阻燃ABS复合材料及其制备方法。
背景技术
ABS树脂是由丙烯腈、苯乙烯、丁二烯组成的三元共聚物，这种材料具有苯乙烯的高流动性、丁二烯的韧性、丙烯腈的耐溶剂性和耐热性，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、成型收缩率小等优点,在家电、汽车、电子电器等领域的塑料制品应用非常广泛。
ABS材料应用在电器产品与电热接触的周边位置时，为了保证防火安全性，需要材料具有较高的阻燃性能高，但是ABS的氧指数只有18％，属于易燃材料，无法达到工业应用要求。我们通过选择性地添加一定量的溴锑阻燃剂虽然可赋予ABS较好阻燃性，但是材料的力学性能一般，无法满足特殊应用环境材料的技术要求。
阻燃ABS材料体系中通过添加某些聚烯烃树脂来提高材料韧性，同时赋予材料一定的耐候性，但是二者的加工温度差异导致聚烯烃树脂在加工过程中易分解变色，影响产品应用和制件外观；而且ABS与聚烯烃相容性较差，在生产使用中常会出现分层起皮等缺陷。鉴于目前研究的基本情况，在维持ABS聚烯烃合金系材料优良的阻燃性能和物理性能的前提下，仍需开发一种具有较好热稳性，能够解决材料成型外观缺陷的组合物。
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环保 阻燃ABS复合材料。
为实现上述目的，本发明采用的技术方案为：一种环保阻燃ABS复合材料，包含以下重量份的成分：ABS树脂50-88份、聚烯烃树脂3-40份、相容剂2-8份，所述相容剂为ABS接枝马来酸酐、ABS接枝聚乙烯、ABS接枝甲基丙烯酸甲酯、乙烯丙烯酸丁酯共聚物中的至少一种。
本发明创造性提出聚烯烃树脂与ABS树脂进行合金化性能开发，通过设计特定化学结构的相容剂，有效解决了ABS树脂和聚烯烃树脂的相容性，实现了材料较好的力学性能，克服了聚烯烃和ABS的合金开发存在的较大技术瓶颈问题，使得所得复合材料具有较高的性价比，这种合金材料具有优异的低温韧性、耐溶剂性和耐候性能，具有优异综合性能和量产应用价值。
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)。在此比例下，ABS树脂具有较好的韧性，耐热性，加工流动性及力学性能。
优选地，所述聚烯烃树脂为采用盐酸相悬浮法生产的氯化聚乙烯或聚氯乙烯，所述聚烯烃树脂中氯的质量百分含量为30-40％。在此比例下，材料的热稳定性和流动性较好，力学性能比较优异。
优选地，所述的环保阻燃ABS复合材料，还包含以下重量份的成分：溴系阻燃剂7-17份、锑系阻燃剂3-6份。
更优选地，所述溴系阻燃剂为十溴二苯乙烷、十溴二苯醚、溴化环氧树脂、溴化聚苯乙烯、四溴双酚A、三(三溴苯基)三嗪中的至少一种；所述锑系阻燃剂为三氧化二锑、五氧化二锑、锑酸盐、磷酸锑中的至少一种。
优选地，所述的环保阻燃ABS复合材料，还包含0.1-3重量份的热稳定剂，所述热稳定剂为硫醇甲基锡、丁基锡、钙锌稳定剂、马来酸甲基锡中的至少一种。
更优选地，所述热稳定剂为马来酸甲基锡。相对而言，在所使用的热稳定剂中，丁基锡容易分解产生二丁基锡，是一种能够扰乱生物内分泌作用的物质，REACH法规中已经对其进行了限量使用的要求；硫醇甲基锡一方面气味较大，另一方面会影响材料整体颜色；钙锌稳定剂热稳定效率不高，添加量较大；而马来酸甲基锡由于其特殊的化学结构，在材料成形过程中对于氯化聚乙烯的热分解具有较高的效率、并且具有添加量小，气味较低的优势。
更优选地，所述马来酸甲基锡由顺丁烯二酸一甲基锡和顺丁烯二酸二甲基锡混合而得，所述马来酸甲基锡中锡的质量百分含量为30-50％，在此范围内，具有较好的初期热稳定性及抑制降解变色作用。所述热稳定剂为环保型高效率的热稳定剂，具有较好的热稳定效率，提高了ABS/聚烯烃合金加工过程中热稳定性差的问题，实现了材料较好的加工性能。
更优选地，所述顺丁烯二酸二甲基锡的结构式如式(1)所示，所述顺丁烯二酸一甲基锡的结构式如式(2)所示：
Figure PCTCN2020092622-appb-000001
其中，R1和R2可以为氢基、烷基、烷氧基、羧基、羰基、酯基，优选甲基。
优选地，所述的环保阻燃ABS复合材料，还包含0.3-2重量份的加工助剂。
同时，本发明还公开一种所述的环保阻燃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190℃、五区190℃、六区190℃、七区180℃、八区180℃、九区180℃、机头200℃，螺杆转速为300-400rpm，双螺杆挤出机的长径比为40:1。
相对于现有技术，本发明的有益效果为：
本发明通过将ABS与聚烯烃树脂合金化，提升了材料的韧性和耐候性，大大弥补了阻燃ABS材料性能的不足，通过相容剂和热稳定体系的开发，解决了材料的加工和应用缺陷，使得材料具有较好的产业化应用价值。
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、聚烯烃树脂、溴系阻燃剂、锑系阻燃剂、相容剂和加工助剂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190℃、五区190℃、六区190℃、七区180℃、八区180℃、九区180℃、机头200℃，螺杆转速为300-400rpm，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下：
阻燃ABS材料在成型时由于制件尺寸较大，成型周期较长，点浇口剪切较 强，导致材料降解产生异色纹等外观缺陷，因此以200℃注塑方板的颜色作为底色，在220℃热滞留5min后注塑方板与200℃计算色差及b值变化，比较ΔE的大小进行评价；具体各性能的测量标准如表1所示：
表1各性能的测量标准
Figure PCTCN2020092622-appb-000002
本发明设置实施例1～11，具体实施例1～5中的各成分，具体如表2所示，如无具体说明，均为市售可得，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、9中除聚烯烃树脂中氯含量不同外，其他成分及含量均与实施例5相同，具体实施例8、9中，聚烯烃树脂中氯含量分别为25％、45％；实施例10、11中除马来酸甲基锡中锡含量不同外，其他均与实施例5中相同，实施例10、11中马来酸甲基锡中的锡含量分别为25％、55％：
表2实施例1～5中的各成分选择
Figure PCTCN2020092622-appb-000003
Figure PCTCN2020092622-appb-000004
具体实施例1～11中各成分含量及性能测试结果如表3所示：
表3实施例1～11中各成分含量及性能测试结果
Figure PCTCN2020092622-appb-000005
Figure PCTCN2020092622-appb-000006
从表3可以看出，本发明所述ABS复合材料具有优异的低温韧性、耐溶剂性和耐候、阻燃性能，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、9与实施例5对比发现，当聚烯烃树脂中氯的质量百分含量为30-40％时，ABS复合材料具有更加优异的综合力学性能；将实施例10、11与实施例5对比发现，当马来酸甲基锡中锡的质量百分含量为30-50％时，本发明所述ABS复合材料具有更好的热稳定性，热滞留色差ΔE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-757；
聚烯烃树脂：采用盐酸相悬浮法生产的氯化聚乙烯或聚氯乙烯，所述聚烯烃树脂中氯的质量百分含量为30-40％，如CPE-135A。
溴系系阻燃剂：选用以色列死海溴的产品；
锑系阻燃剂：选自常德辰州产品；
相容剂：选自ABS接枝甲基丙烯酸甲酯；
热稳定剂：选自马来酸甲基锡，锡含量为42％；本申请实验组2～5及对照组2的热稳定剂均为马来酸甲基锡，马来酸甲基锡可以是马来酸一甲基锡，也可以是马来酸二甲基锡，也可以是二者的混合物。
加工助剂：抗氧剂选用汽巴精化的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4所示：
表4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 PCTCN2020092622-appb-000007
从表4可以看出，将对照组1与对照组3对比可知，聚烯烃树脂的加入，可提高材料的耐候性与韧性；将实验组1与对照组3相比，相容剂的加入，可以有效提升材料的冲击性能，解决制件的起皮问题；将实验组2、3与实验组6对比，本申请中的热稳定剂马来酸甲基锡具有较好的颜色稳定性，其中马来酸一甲基锡和马来酸一甲基锡混合后，颜色稳定性更好，可以很好的降低热滞留色差；将实验组2与对照组2相比，在同样阻燃剂含量，没有聚烯烃树脂条件下材料只能达到V-2阻燃等级，但是材料的耐候性色差较小，耐候性较好。
结合表3及表4可以看出，本发明配方中，正是在聚烯烃树脂、相容剂、热稳定剂的共同作用下，才最终达到了本申请ABS复合材料优异的低温韧性、耐溶剂性和耐候、阻燃性能等综合性能及量产应用价值。
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. 一种环保阻燃ABS复合材料，其特征在于，包含以下重量份的成分：ABS树脂50-88份、聚烯烃树脂3-40份、相容剂2-8份，所述相容剂为ABS接枝马来酸酐、ABS接枝聚乙烯、ABS接枝甲基丙烯酸甲酯、乙烯丙烯酸丁酯共聚物中的至少一种。
  2. 如权利要求1所述的环保阻燃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所述的环保阻燃ABS复合材料，其特征在于，所述聚烯烃树脂为采用盐酸相悬浮法生产的氯化聚乙烯或聚氯乙烯，所述聚烯烃树脂中氯的质量百分含量为30-40％。
  4. 如权利要求1～3任一项所述的环保阻燃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7-17份、锑系阻燃剂3-6份。
  5. 如权利要求4所述的环保阻燃ABS复合材料，其特征在于，所述溴系阻燃剂为十溴二苯乙烷、十溴二苯醚、溴化环氧树脂、溴化聚苯乙烯、四溴双酚A、三(三溴苯基)三嗪中的至少一种；所述锑系阻燃剂为三氧化二锑、五氧化二锑、锑酸盐、磷酸锑中的至少一种。
  6. 如权利要求1～3任一项所述的环保阻燃ABS复合材料，其特征在于，还包含0.1-3重量份的热稳定剂，所述热稳定剂为硫醇甲基锡、丁基锡、钙锌稳定剂、马来酸甲基锡中的至少一种。
  7. 如权利要求6所述的环保阻燃ABS复合材料，其特征在于，所述热稳定剂为马来酸甲基锡。
  8. 如权利要求7所述的环保阻燃ABS复合材料，其特征在于，所述马来酸甲基锡由顺丁烯二酸一甲基锡和顺丁烯二酸二甲基锡混合而得，所述马来酸甲基锡中锡的质量百分含量为30-50％。
  9. 如权利要求1～3任一项所述的环保阻燃ABS复合材料，其特征在于，还包含0.3-2重量份的加工助剂。
  10. 一种如权利要求1～9任一项所述的环保阻燃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190℃、五区190℃、六区190℃、七区180℃、八区180℃、九区180℃、机头200℃，螺杆转速为300-400rpm，双螺杆挤出机的长径比为40:1。
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