WO2021012189A1 - 一种abs/pok复合材料及其制备方法 - Google Patents

一种abs/pok复合材料及其制备方法 Download PDF

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WO2021012189A1
WO2021012189A1 PCT/CN2019/097333 CN2019097333W WO2021012189A1 WO 2021012189 A1 WO2021012189 A1 WO 2021012189A1 CN 2019097333 W CN2019097333 W CN 2019097333W WO 2021012189 A1 WO2021012189 A1 WO 2021012189A1
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abs
pok
composite material
zone
resin
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PCT/CN2019/097333
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English (en)
French (fr)
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秦旺平
叶南飚
黄险波
付锦锋
杨霄云
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金发科技股份有限公司
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Priority to PCT/CN2019/097333 priority Critical patent/WO2021012189A1/zh
Publication of WO2021012189A1 publication Critical patent/WO2021012189A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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 an ABS/POK 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.
  • ABS material has poor resistance to oil and organic solvents. It is prone to swelling and damage in non-polar oils or chemical solvents.
  • the unsaturated polybutadiene double bond in the structure is easy to age and change color and affect the appearance of the product. This performance defect is extremely The earth limits the application and promotion of ABS materials in some product fields. ABS materials are most sensitive to glacial acetic acid solvents. Once the parts are in contact, they will generally crack or break within 20 seconds. Therefore, ABS materials resistant to glacial acetic acid solvents are currently a technical bottleneck problem in the industry. Once solved, it can be satisfied. The medical, energy and other industries have great market prospects for the demand for solvent resistance of materials and expand the potential application market.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide an ABS/POK composite material.
  • the ABS/POK composite material has excellent high gloss, solvent resistance and weather resistance.
  • an ABS/POK composite material comprising the following components by weight: 20-77.8 parts of ABS resin, 15-60 parts of POK polyketone resin, and 5-30 parts of PETG resin .
  • the invention alloys POK polyketone resin with ABS, which solves the technical bottleneck problem of the compatibility of the resin system, greatly improves the mechanical properties of the material, PETG gives the material better gloss, and POK resin gives the material excellent Its weather resistance and solvent resistance make up for the shortcomings of the existing ABS alloy materials and have great industrial application value.
  • the melt flow rate of the POK polyketone resin under the test conditions of 240° C. and 2.16 kg is greater than 120 g/10 min.
  • the structural formula of the POK polyketone resin is shown in formula (1):
  • the mass percentage of 1,4-cyclohexanedimethanol (CHDM) in the PETG resin is less than 50%, otherwise, the alloy material developed using this resin has poor gloss and mechanical properties.
  • 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 ABS/POK 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, styrene-acrylonitrile- At least one of glycidyl methacrylate terpolymers.
  • a compatibilizer is ABS grafted with maleic anhydride, ABS grafted with methyl acrylate, styrene-acrylonitrile- At least one of 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 ABS/POK composite material further contains 0.2-1 parts by weight of processing aids.
  • the present invention also provides a method for preparing the ABS/POK 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 alloys POK polyketone resin with ABS, which solves the technical bottleneck problem of the compatibility of the resin system, greatly improves the mechanical properties of the material, PETG gives the material better gloss, and POK resin gives the material excellent Its weather resistance and solvent resistance make up for the shortcomings of the existing ABS alloy materials and have great industrial application value.
  • the preparation method of the ABS/POK composite material in the embodiment of the present invention is:
  • 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.
  • the present invention sets up Examples 1 to 8, and the components in specific Examples 1 to 5 are commercially available unless otherwise specified: Among them, ABS is commercially available ABS 8391; POK polyketone resin is commercially available POK M230A (100 ⁇ m ⁇ 15000, m>1, n>m+1); PETG is GN071 commercially available from Eastman, USA (the mass percentage of 1,4-cyclohexanedimethanol is less than 50%), processing aid Including antioxidants and lubricants. The weight ratio of specific antioxidants to lubricants is 1:1. The antioxidants are Irganox 1010 and Irganox 168 from BASF, and the lubricants are selected from N,N'-ethylene double hard.
  • Fatty acid amide (EBS); the compatibilizers in Examples 1 to 5 are ABS grafted maleic anhydride, ABS grafted methyl acrylate, styrene-acrylonitrile-glycidyl methacrylate terpolymer, benzene Ethylene-acrylonitrile-glycidyl methacrylate terpolymer, styrene-acrylonitrile-glycidyl methacrylate terpolymer, of which styrene-acrylonitrile-glycidyl methacrylate terpolymer
  • the average particle size is 40-350 ⁇ m (according to the ISO 13320:2009 standard, the sample is dispersed in water after ultrasonic treatment and tested with a laser particle size analyzer), the epoxy content is 5 ⁇ 0.2wt%, and the weight average molecular weight is 1.4 ⁇ 10 5 g/mol;
  • the ABS resin in Examples 1 to 5 is composed of grafted polybutadiene rubber and grafted
  • Example 6 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 The average particle size, epoxy content, and weight average molecular weight of the copolymer are different, and the other components and contents are the same as in Example 5.
  • the styrene-acrylonitrile-glycidyl methacrylate terpolymer in Example 8 The average particle size> 350 ⁇ m (according to the ISO 13320:2009 standard, the sample is dispersed in water after ultrasonic treatment, and then tested with a laser particle size analyzer), the epoxy content is 4 ⁇ 0.2wt%, and the weight average molecular weight is 2.5 ⁇ 10 5 g/mol .
  • the content of each component (in parts by weight) and performance test results in specific examples 1 to 8 are shown in Table 2:
  • the ABS/POK composite material of the present invention has excellent solvent resistance, weather resistance, gloss, and overall 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 /POK composite material has better comprehensive 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 At 4-6wt%, when the weight average molecular weight is 1.0 ⁇ 10 5 g/mol-3.0 ⁇ 10 5 g/mol, the ABS/POK composite material has more excellent comprehensive properties (at the same time it has better tensile strength and impact strength , Weather resistance).
  • the present invention sets experimental groups 1 to 6 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 8391;
  • POK polyketone resin POK M930A in experimental groups 1 to 5 and control groups 1 to 3 (melt index is> 120g/10min, test condition is 240°C/2.16kg), experimental group 6 is POK M330A (melt index is 40 ⁇ 120g/10min, the test condition is 240°C/2.16kg);
  • PETG resin is GN071 commercially available from Eastman, USA (the mass percentage of 1,4-cyclohexanedimethanol is less than 50%);
  • 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'-ethylenebisstearic acid amide (EBS), and the weight ratio of the content of the specific antioxidant and lubricant is 1 :1.
  • the increase of POK content in the experimental group 1 significantly prolongs the material in the ice
  • the cracking time under the condition of acetic acid improves the resistance to glacial acetic acid cracking of the material.
  • the test results of the melt flow rate of the material in experimental groups 3, 4, and 5 continue to increase. By recording the time of cracks on the surface of the sample After 30 minutes, no cracking occurs.
  • the material’s resistance to glacial acetic acid is greatly improved.
  • the chromatic aberration of the xenon lamp of the material is successively reduced, and the weather resistance is continuously improved.

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

Abstract

本发明公开了一种ABS/POK复合材料，包含以下重量份的成分：ABS树脂20-77.8份、POK聚酮树脂15-60份、PETG树脂5-30份。本发明创造性将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PETG赋予材料较好的光泽度，POK树脂赋予了材料优异的耐候性、耐溶剂性，弥补了现有ABS合金材料的不足，具有较大的产业化应用价值。同时，本发明还公开一种所述ABS/POK复合材料的制备方法。

Description

一种ABS/POK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ABS/POK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。
但是ABS材料耐油、耐有机溶剂性差，在非极性油品或化学溶剂中则易产生溶胀并出现破损，结构中不饱和聚丁二烯双键易老化变色影响产品外观，这种性能缺陷极大地限制了ABS材料在一些产品领域的应用和推广。ABS材料对于冰醋酸溶剂最为敏感，制件一旦接触到，一般在20秒以内会产生大裂纹以至于断裂，因此，耐冰醋酸溶剂的ABS材料目前属于行业的技术瓶颈问题，一旦解决就可以满足医疗，能源等行业对于材料耐溶剂性能的需求，拓展潜在应用市场，具有较大市场前景。
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ABS/POK复合材料。所述ABS/POK复合材料具有优异的高光泽、耐溶剂、耐候性能。
为实现上述目的，本发明采用的技术方案为：一种ABS/POK复合材料，包含以下重量份的成分：ABS树脂20-77.8份、POK聚酮树脂15-60份、PETG树 脂5-30份。
本发明将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，PETG赋予材料较好的光泽度，POK树脂赋予了材料优异的耐候性、耐溶剂性，弥补了现有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POK聚酮树脂在240℃、2.16kg测试条件下的熔体流动速率大于120g/10min。
优选地，所述POK聚酮树脂的结构式如式(1)所示：
Figure PCTCN2019097333-appb-000001
其中，100＜m＜15000，n≥m+1。
优选地，所述PETG树脂中，1,4-环己烷二甲醇(CHDM)的质量百分含量小于50％，否则，采用这种树脂开发的合金材料光泽度和力学性能较差。
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ABS/POK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 PCTCN2019097333-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ABS/POK复合材料，还包含0.2-1重量份的加工助剂。
同时，本发明还提供一种所述的ABS/POK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：
本发明将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，PETG赋予材料较好的光泽度，POK树脂赋予了材料优异的耐候性、耐溶剂性，弥补了现有ABS合金材料的不足， 具有较大的产业化应用价值。
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/POK复合材料的制备方法为：
(1)将ABS树脂、POK聚酮树脂、PETG树脂、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，所述性能的测试都是先将复合材料制备成测试样条后进行的测试：
表1各性能的测量标准
Figure PCTCN2019097333-appb-000003
本发明设置实施例1～8，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 8391；POK聚酮树脂为市售POK M230A(100＜m＜15000，m＞1，n＞m+1)；PETG为美国伊士曼市售GN071(1,4-环己烷二甲醇的质量百分含量小于50％)，加工助剂包括抗氧剂、润滑剂，具体抗氧剂、润滑剂的重量比为1:1，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)；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(按照ISO 13320:2009标准，将样品分散在水中超声处理后，采用激光粒度仪进行测试)，环氧含量为5±0.2wt％，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、环氧含量、重均分子量不同外，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(按照ISO 13320:2009标准，将样品分散在水中超声处理后，采用激光粒度仪进行测试)，环氧含量为4±0.2wt％，重均分子量2.5×10 5g/mol。具体实施例1～8中各成分含量(以重量份计)及性能测试结果如表2所示：
表2实施例1～8中各成分含量及性能测试结果
Figure PCTCN2019097333-appb-000004
Figure PCTCN2019097333-appb-000005
从表2可以看出，本发明ABS/POK复合材料具有优异的耐溶剂性、耐候、光泽度，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/POK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/POK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)。
此外，本发明设置实验组1～6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 8391；
POK聚酮树脂：实验组1～5及对照组1～3中为POK M930A(熔融指数为＞120g/10min，测试条件为240℃/2.16kg)、实验组6中为POK M330A(熔融指数为40～120g/10min，测试条件为240℃/2.16kg)；
PETG树脂为美国伊士曼市售GN071(1,4-环己烷二甲醇的质量百分含量小 于50％)；
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)，具体抗氧剂、润滑剂的含量的重量比为1:1。
具体实验组1～6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1～6及对照组1～3中各成分含量及各性能测试结果
Figure PCTCN2019097333-appb-000006
从表3可以看出，与对照组1～3相比，本发明实验组1～6中ABS/POK复合材料整体具有优异的光泽度、耐溶剂性和耐候性，整体具有优异综合力学性能和量产应用价值。将对照组1与对照组2对比发现，POK树脂提高了材料的耐冰醋酸性能和耐候性能，对照组2与对照组3对比发现，相容剂有效解决了材料的相容性，提升了材料的冲击强度；将对照组3与实验组1对比，PETG树脂 的添加，大大提升了材料的光泽度和耐候性，实验组1与实验组2相比，POK含量的增加明显延长了材料在冰醋酸条件下的开裂时间，提高了材料的耐冰醋酸开裂性能，实验组3、4、5相比实验组2，材料的熔体流动速率测试结果不断提高，通过记录样条表面产生裂纹的时间，30分钟后不发生开裂，材料的耐冰醋酸能力大大提高，同时材料的氙灯老化色差依次减小，耐候性不断提高；将实验组6与实验组5对比可知，当POK聚酮树脂的熔融指数＞120g/10min时，具有更好的拉伸强度，冲击强度，耐候性和光泽度，耐冰醋酸开裂时间大幅延长，材料的综合性能具有较大提高。
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 (9)

  1. 一种ABS/POK复合材料，其特征在于，包含以下重量份的成分：ABS树脂20-77.8份、POK聚酮树脂15-60份、PETG树脂5-30份。
  2. 如权利要求1所述的ABS/POK复合材料，其特征在于，所述POK聚酮树脂在240℃、2.16kg测试条件下的熔体流动速率大于120g/10min。
  3. 如权利要求1所述的ABS/POK复合材料，其特征在于，所述POK聚酮树脂的结构式如式(1)所示：
    Figure PCTCN2019097333-appb-100001
    其中，100＜m＜15000，n≥m+1。
  4. 如权利要求1所述的ABS/POK复合材料，其特征在于，所述PETG树脂中，1,4-环己烷二甲醇的质量百分含量小于50％。
  5. 如权利要求1所述的ABS/POK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)。
  6. 如权利要求1～5任一项所述的ABS/POK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。
  7. 如权利要求6所述的ABS/POK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 PCTCN2019097333-appb-100002
  8. 如权利要求1～5任一项所述的ABS/POK复合材料，其特征在于，还包含0.2-1重量份的加工助剂。
  9. 一种如权利要求1～8任一项所述的ABS/POK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。
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