WO2022228143A1 - 一种无卤阻燃abs合金材料及其制备方法 - Google Patents

一种无卤阻燃abs合金材料及其制备方法 Download PDF

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WO2022228143A1
WO2022228143A1 PCT/CN2022/086947 CN2022086947W WO2022228143A1 WO 2022228143 A1 WO2022228143 A1 WO 2022228143A1 CN 2022086947 W CN2022086947 W CN 2022086947W WO 2022228143 A1 WO2022228143 A1 WO 2022228143A1
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halogen
alloy material
free flame
abs alloy
parts
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PCT/CN2022/086947
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English (en)
French (fr)
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秦旺平
付锦锋
杨霄云
叶南飚
陈平绪
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金发科技股份有限公司
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Publication of WO2022228143A1 publication Critical patent/WO2022228143A1/zh

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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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • 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
    • C08L25/06—Polystyrene
    • 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
    • C08L2201/22—Halogen free composition
    • 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 relates to the technical field of polymer materials, in particular to a halogen-free flame-retardant ABS alloy material and a preparation method thereof.
  • ABS resin is a terpolymer composed of acrylonitrile, styrene and butadiene. It has the high fluidity of styrene, the good toughness of butadiene, the heat resistance and solvent resistance of acrylonitrile, and has excellent processing properties. It has the advantages of good creep resistance and high dimensional stability, and is widely used in plastic products in household appliances, automotive products, electronic appliances and other fields.
  • ABS When the ABS material is used in the peripheral position in contact with the electric heat, in order to ensure fire safety, it needs to achieve a certain flame retardant performance.
  • ABS can be given better flame retardant performance by selectively adding a certain amount of flame retardant.
  • the research and application of brominated flame retardant ABS materials are very mature. During the injection molding production process, there is a certain degree of mold corrosiveness. The smoke generated during the combustion process is relatively large and has certain health hazards. The halogen-free flame retardant ABS is released during the combustion process. There are fewer harmful gases and can meet the higher requirements of environmental protection regulations, which belongs to the development trend of flame retardant materials in the future.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a halogen-free flame-retardant ABS alloy material and a preparation method thereof.
  • a halogen-free flame retardant ABS alloy material comprising the following components in parts by weight: 5-20 parts of ABS resin, 20-40 parts of polyphenylene ether resin, polystyrene 25-46 parts of resin, 12-25 parts of phosphate ester flame retardant and 2-8 parts of compatibilizer; the compatibilizer is styrene-(ethylene-butene)-styrene triblock copolymer, maleic At least one of acid anhydride grafted ABS and methyl methacrylate-butadiene-styrene copolymer.
  • the invention creatively proposes that the polyphenylene ether resin is alloyed with the ABS resin and the polystyrene resin for performance development, and the compatibility of the ABS resin with the polyphenylene ether and polystyrene resin is effectively solved by designing a compatibilizer with a specific chemical structure. It achieves better mechanical properties of the material, overcomes the major technical bottleneck in the development of ABS, polyphenylene ether and polystyrene alloys, makes the obtained alloy materials have high cost performance, and realizes halogen-free V-0 Flame retardant grade, this alloy material has excellent toughness, fluidity and dimensional stability, and has excellent comprehensive performance and mass production application value.
  • the compatibilizer is selected from at least styrene-(ethylene-butylene)-styrene triblock copolymer, maleic anhydride grafted ABS and methyl methacrylate-butadiene-styrene copolymer.
  • the compatibilizer is more preferably styrene-(ethylene-butylene)-styrene three Block copolymer with the best mechanical properties.
  • the ABS resin is composed of grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer, and the grafted polybutadiene rubber and grafted polystyrene-acrylonitrile copolymer are The weight ratio is (10 ⁇ 60):(40 ⁇ 90). At this ratio, the alloy system has good toughness, heat resistance, processing fluidity and mechanical properties.
  • the melt flow rate of the polyphenylene ether resin is 25-45 g/10min
  • the test temperature is 315°C
  • the load is 10kg.
  • the alloy material has good processability and heat resistance.
  • the polystyrene resin has a number average molecular weight of 4.3 ⁇ 10 3 to 5.6 ⁇ 10 3 g/mol. Under this property, the alloy material has good fluidity and mechanical rigidity.
  • R 1 , R 2 and R 3 are selected from H, C 6 H 5 , CH 3 and CH 3 CH 2 , and the chemical substituents at R 1 , R 2 and R 3 may be the same or different, and preferably the R 1 , R 2 and R 3 are the same, and more preferably, all of the R 1 , R 2 and R 3 are C 6 H 5 .
  • the halogen-free flame-retardant ABS alloy material further comprises 0.3-2 parts by weight of a processing aid.
  • the processing aid is at least one of a lubricant, an antioxidant and an anti-dripping agent.
  • the object of the present invention also is to provide a kind of preparation method of described halogen-free flame retardant ABS alloy material, described preparation method comprises the following steps:
  • each component is melted and plasticized, kneaded and mixed, and then extruded, drawn, cooled, pelletized, dried and packaged to obtain the halogen-free flame-retardant ABS alloy material;
  • the temperature of each section of the twin-screw extruder barrel from the feeding port to the head is: 90 °C in the first zone, 170 °C in the second zone, 190 °C in the third zone, 200 °C in the fourth zone, 200 °C in the fifth zone, and 200 °C in the sixth zone.
  • the screw speed is 300-500rpm
  • the length-diameter ratio of the twin-screw extruder is 40:1.
  • the present invention provides a halogen-free flame-retardant ABS alloy material
  • the halogen-free flame-retardant ABS alloy material of the present invention uses ABS resin, polyphenylene ether resin and polystyrene resin as resins
  • the alloying design and development of the matrix is carried out, the compatibility of the alloy system is solved through the compatibilizer, the performance defect caused by the difference in the polarity of the resin is overcome, the mechanical properties of the alloy material are greatly improved, and the halogen-free flame retardant performance is also improved.
  • the halogen-free flame-retardant ABS alloy material of the present invention has excellent comprehensive performance and halogen-free flame-retardant performance, and the alloy material has good industrial application value.
  • the invention also provides a preparation method of the halogen-free flame-retardant ABS alloy material.
  • each component is melted and plasticized, kneaded and mixed, and then extruded, drawn, cooled, pelletized, dried and packaged to obtain the halogen-free flame-retardant ABS alloy material;
  • the temperature of each section of the twin-screw extruder barrel from the feeding port to the head is: 90 °C in the first zone, 170 °C in the second zone, 190 °C in the third zone, 200 °C in the fourth zone, 200 °C in the fifth zone, and 200 °C in the sixth zone.
  • the screw speed is 400 rpm
  • the length-diameter ratio of the twin-screw extruder is 40:1.
  • Test items unit standard test Tensile Strength MPa ISO 527-2:2012 Izod notched impact strength kJ/m 2 ISO 180:2000 Flame retardant properties Class UL 94-2015
  • Polyphenylene ether resin Bluestar Chemical Company, the model is PPE LXR040, the melt flow rate is 35g/10min under the load of 10kg at 315°C;
  • Polyphenylene ether resin Bluestar Chemical Company, the model is PPE LXR050, the melt flow rate is 9g/10min under a load of 10kg at 315°C.
  • Polyphenylene ether resin Bluestar Chemical Company, the model is PPE LXR035, the melt flow rate is 75g/10min under a load of 10kg at 315°C.
  • Triphenyl phosphate Jiangsu Wansheng Company, model WSFR-TPP;
  • Resorcinol-bis(diphenyl phosphate) Jiangsu Wansheng Company, model WSFR-RDP;
  • Bisphenol A-bis(diphenyl phosphate) Jiangsu Wansheng Company, the model is WSFR-BDP-N2;
  • Polystyrene resin Foshan Total Company, model GP1441, number average molecular weight 5.1 ⁇ 10 3 g/mol;
  • Polystyrene resin Jiangsu Yashide, the model is EA3300, the number average molecular weight is 9.6 ⁇ 10 3 g/mol;
  • Styrene-(ethylene-butylene)-styrene triblock copolymer Huizhou Li Changrong Company, model SEBS7554;
  • Methyl methacrylate-butadiene-styrene copolymer Japan Zhongyuan, model M-521;
  • the processing aid is composed of the following components in parts by weight: 0.4 part of lubricant, 0.2 part of hindered phenol antioxidant, 0.2 part of phosphate ester antioxidant and 0.2 part of anti-dripping agent;
  • Hindered phenolic antioxidant SONOX 1010, Jinan Jiling Chemical
  • Phosphate ester antioxidant SONOX 168, Jinan Jiling Chemical
  • Anti-drip agent SN80-SA7, Guangzhou Entropy Energy Company.
  • the halogen-free flame retardant ABS alloy material of the present invention can achieve better mechanical properties (tensile strength above 35MPa, Izod notched impact strength above 16kJ/m 2 ) and better mechanical properties.
  • the addition of phosphate ester flame retardant can make the material meet the requirements of flame retardant performance while ensuring mechanical properties, especially the flame retardant performance of triphenyl phosphate is better; compared with other compatibilizers,
  • compatibilizer selects styrene-(ethylene-butylene)-styrene triblock copolymer, maleic anhydride grafted ABS or methyl methacrylate-butadiene-styrene copolymer, it can have better performance.
  • Mechanical properties and flame retardant properties among which the mechanical properties of the styrene-(ethylene-butylene)-styrene triblock copolymer are better.

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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

本发明公开了一种无卤阻燃ABS合金材料，包含以下重量份的组分：ABS树脂5～20份、聚苯醚树脂20～40份、磷酸酯阻燃剂12～25份、聚苯乙烯树脂25～45份和相容剂2～8份；所述相容剂为苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物、马来酸酐接枝ABS和甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物中的至少一种。本发明所述无卤阻燃ABS合金材料本发明通过将ABS树脂、聚苯醚树脂和聚苯乙烯树脂作为树脂基体进行合金化设计开发，通过相容剂解决了合金体系相容性，同时进行了无卤阻燃性能的开发，具有优异的综合性能及无卤阻燃性能，合金材料具有较好的产业化应用价值。本发明还公开了所述无卤阻燃ABS合金材料的制备方法。

Description

一种无卤阻燃ABS合金材料及其制备方法 技术领域
本发明涉及高分子材料技术领域，具体涉及一种无卤阻燃ABS合金材料及其制备方法。
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，具有苯乙烯的高流动性、丁二烯的良韧性、丙烯腈的耐热性和耐溶剂性，具有优良的加工性能、电绝缘性能、高光泽和电镀性能，同时具有耐蠕变性好、尺寸稳定性高等优点,在家用电器、汽车产品、电子电器等领域的塑料制品得到广泛应用。
ABS材料应用在与电热接触的周边位置时，为了确保防火安全性，需要达到一定的阻燃性能，一般通过选择性地添加一定量的阻燃剂可赋予ABS较好的阻燃性。溴系阻燃ABS材料的研究和应用非常成熟，注塑生产过程中具有一定的模具腐蚀性，在燃烧过程中产生的烟较大，具有一定健康危害性，无卤阻燃ABS在燃烧过程中释放有害气体较少，能够满足较高要求的环保法规，属于未来阻燃材料的发展趋势。
发明内容
本发明的目的在于克服现有技术存在的不足之处而提供一种无卤阻燃ABS合金材料及其制备方法。
为实现上述目的，本发明采取的技术方案为：一种无卤阻燃ABS合金材料，包含以下重量份的组分：ABS树脂5～20份、聚苯醚树脂20～40份、聚苯乙烯树脂25～46份、磷酸酯阻燃剂12～25份和相容剂2～8份；所述相容剂为苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物、马来酸酐接枝ABS和甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物中的至少一种。
本发明创造性提出聚苯醚树脂与ABS树脂和聚苯乙烯树脂合金化后进行性 能开发，通过设计特定化学结构的相容剂，有效解决了ABS树脂与聚苯醚和聚苯乙烯树脂的相容性，实现了材料较好的力学性能，克服了ABS与聚苯醚和聚苯乙烯合金开发存在的较大技术瓶颈问题，使得所得合金材料具有较高的性价比，并实现了无卤化V-0阻燃等级，这种合金材料具有优异的韧性、流动性和尺寸稳定性能，具有优异综合性能和量产应用价值。
发明人发现，相容剂选择苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物、马来酸酐接枝ABS和甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物中的至少一种时，可解决本发明合金组分极性的差异，提高相界面的分散均匀性，综合提升力学性能，所述相容剂更优选为苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物，力学性能最佳。
优选地，所述ABS树脂为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和接枝聚苯乙烯-丙烯腈共聚物的重量比为(10～60)：(40～90)。在此比例下，合金体系具有较好的韧性、耐热性、加工流动性及力学性能。
优选地，所述聚苯醚树脂的熔体流动速率为25～45g/10min，测试的温度为315℃，负荷10kg。此性能下合金材料具有较好的加工性能和耐热性。
优选地，所述聚苯乙烯树脂的数均分子量为4.3×10 3～5.6×10 3g/mol。此性能下合金材料具有较好流动性及力学刚性。
优选地，所述磷酸酯阻燃剂的结构式如式(I)所示：
Figure PCTCN2022086947-appb-000001
其中，R 1、R 2、R 3选自H、C 6H 5、CH 3和CH 3CH 2，R1、R2、R3处的化学取代基可以相同，可以不同，优选所述R 1、R 2、R 3相同，更优选所述R 1、R 2、R 3均为C 6H 5。
优选地，所述无卤阻燃ABS合金材料还包含0.3-2重量份的加工助剂。所述加工助剂为润滑剂、抗氧剂和抗滴落剂中的至少一种。
本发明的目的还在于提供一种所述的无卤阻燃ABS合金材料的制备方法，所述制备方法包括以下步骤：
(1)将各组分在高速混合机中混合均匀或通过计量喂料器进入双螺杆挤出机中；
(2)在双螺杆挤出机中各组分经熔融塑化、捏合混炼、然后进行挤出、拉条、冷却、切粒、干燥和包装，得所述无卤阻燃ABS合金材料；其中，双螺杆挤出机螺筒各段温度从下料口到机头分别为：一区90℃、二区170℃、三区190℃、四区200℃、五区200℃、六区200℃、七区190℃、八区190℃、九区190℃、机头210℃，螺杆转速为300-500rpm，双螺杆挤出机的长径比为40:1。
本发明的有益效果在于：本发明提供了一种无卤阻燃ABS合金材料，本发明所述无卤阻燃ABS合金材料本发明通过将ABS树脂、聚苯醚树脂和聚苯乙烯树脂作为树脂基体进行合金化设计开发，通过相容剂解决了合金体系相容性，克服了由于树脂极性的差异所造成的性能缺陷，大大提升了合金材料的力学性能，同时进行了无卤阻燃性能的开发，本发明所述无卤阻燃ABS合金材料具有优异的综合性能及无卤阻燃性能，合金材料具有较好的产业化应用价值。本发明还提供了所述无卤阻燃ABS合金材料的制备方法。
具体实施方式
为更好地说明本发明的目的、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。
本发明实施例和对比例中材料的制备方法为：
(1)将各组分在高速混合机中混合均匀或通过计量喂料器进入双螺杆挤出机中；
(2)在双螺杆挤出机中各组分经熔融塑化、捏合混炼、然后进行挤出、拉条、冷却、切粒、干燥和包装，得所述无卤阻燃ABS合金材料；其中，双螺杆挤出机螺筒各段温度从下料口到机头分别为：一区90℃、二区170℃、三区190℃、四区200℃、五区200℃、六区200℃、七区190℃、八区190℃、九区190℃、机头210℃，螺杆转速为400rpm，双螺杆挤出机的长径比为40:1。
实施例和对比例中各性能的具体评价方法如下：
表1各性能的测量标准
检测项目 单位 测试标准
拉伸强度 MPa ISO 527-2:2012
悬臂梁缺口冲击强度 kJ/m 2 ISO 180:2000
阻燃性能 Class UL 94-2015
实施例和对比例中各原料来源如下：
ABS树脂：
中国石化吉林石化公司，型号为ABS 0215A，其中接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物的重量比为18:82；
[根据细则26改正27.04.2022]　
中国台湾国乔公司，型号为ABS D-120A，其中接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物的重量比为28:72；
韩国锦湖公司，型号为ABS HR 181，其中接枝聚丁二烯橡胶和接枝聚苯乙烯-丙烯腈共聚物的重量比为60:40；
聚苯醚树脂：蓝星化工公司，型号为PPE LXR040，在315℃，负荷10kg的熔体流动速率为35g/10min；
聚苯醚树脂：蓝星化工公司，型号为PPE LXR050，在315℃，负荷10kg的熔体流动速率为9g/10min。
聚苯醚树脂：蓝星化工公司，型号为PPE LXR035，在315℃，负荷10kg的熔体流动速率为75g/10min。
磷酸三苯脂：江苏万盛公司，型号为WSFR-TPP；
间苯二酚-双(磷酸二苯酯)：江苏万盛公司，型号为WSFR-RDP；
双酚A-双(磷酸二苯酯):江苏万盛公司，型号为WSFR-BDP-N2；
聚苯乙烯树脂：佛山道达尔公司，型号为GP1441，数均分子量5.1×10 3g/mol；
[根据细则26改正27.04.2022]　
聚苯乙烯树脂：中国台湾奇美公司，型号为818K，数均分子量为7.6×10 3g/mol；
聚苯乙烯树脂：江苏雅士德，型号为EA3300，数均分子量为9.6×10 3g/mol；
苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物：惠州李长荣公司，型号为SEBS7554；
甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物：日本钟渊，型号为M-521；
马来酸酐接枝ABS:沈阳科通，型号为KT-2；
苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯：江苏佳易容，SAG-002；
加工助剂由以下重量份的组分组成：润滑剂0.4份、受阻酚类抗氧剂0.2份、磷酸酯类抗氧剂0.2份和抗滴落剂0.2份；
润滑剂：EBS B50，青岛赛诺化工有限公司；
受阻酚类抗氧剂：SONOX 1010，济南吉灵化工；
磷酸酯类抗氧剂：SONOX 168，济南吉灵化工；
抗滴落剂：SN80-SA7，广州熵能公司。
实施例和对比例的组分和测试结果见表2和3。
表2
Figure PCTCN2022086947-appb-000002
表3
Figure PCTCN2022086947-appb-000003
Figure PCTCN2022086947-appb-000004
从表2和表3可以看出，本发明所述无卤阻燃ABS合金材料能达到较好的力学性能(拉伸强度在35MPa以上，悬臂梁缺口冲击强度在16kJ/m 2以上)和较好的阻燃性能；磷酸酯阻燃剂的添加能够使材料在保证力学性能的同时满足阻燃性能的要求，尤其是磷酸三苯脂的阻燃性能更佳；相较于其他相容剂，相容剂选择苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物、马来酸酐接枝ABS或甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物时，可有较好的力学性能和阻燃性能，其中苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物的力学性能更佳。
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. 一种无卤阻燃ABS合金材料，其特征在于，包含以下重量份的组分：ABS树脂5～20份、聚苯醚树脂20～40份、聚苯乙烯树脂25～46份、磷酸酯阻燃剂12～25份和相容剂2～8份；所述相容剂为苯乙烯-(乙烯-丁烯)-苯乙烯三嵌段共聚物、马来酸酐接枝ABS和甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物中的至少一种。
  2. 如权利要求1所述的无卤阻燃ABS合金材料，其特征在于，所述ABS树脂为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和接枝聚苯乙烯-丙烯腈共聚物的重量比为(10～60)：(40～90)。
  3. 如权利要求1所述的无卤阻燃ABS合金材料，其特征在于，所述聚苯醚树脂的熔体流动速率为25～45g/10min，测试的温度为315℃，负荷10kg。
  4. 如权利要求1所述的无卤阻燃ABS合金材料，其特征在于，所述聚苯乙烯树脂的数均分子量为4.3×10 3～5.6×10 3g/mol。
  5. 如权利要求1所述的无卤阻燃ABS合金材料，其特征在于，所述磷酸酯阻燃剂的结构式如式(I)所示：
    Figure PCTCN2022086947-appb-100001
    其中，R 1、R 2、R 3选自H、C 6H 5、CH 3和CH 3CH 2。
  6. 如权利要求5所述的无卤阻燃ABS合金材料，其特征在于，所述R 1、 R 2、R 3相同。
  7. 如权利要求6所述的无卤阻燃ABS合金材料，其特征在于，所述R 1、R 2、R 3均为C 6H 5。
  8. 如权利要求1～7中任一项所述的无卤阻燃ABS合金材料，其特征在于，所述无卤阻燃ABS合金材料还包含0.3-2重量份的加工助剂。
  9. 如权利要求8所述的无卤阻燃ABS合金材料，其特征在于，所述加工助剂为润滑剂、抗氧剂和抗滴落剂中的至少一种。
  10. 如权利要求1～9中任一项所述的无卤阻燃ABS合金材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)将各组分在高速混合机中混合均匀或通过计量喂料器进入双螺杆挤出机中；
    (2)在双螺杆挤出机中各组分经熔融塑化、捏合混炼、然后进行挤出、拉条、冷却、切粒、干燥和包装，得所述无卤阻燃ABS合金材料；其中，双螺杆挤出机螺筒各段温度从下料口到机头分别为：一区90℃、二区170℃、三区190℃、四区200℃、五区200℃、六区200℃、七区190℃、八区190℃、九区190℃、机头210℃，螺杆转速为300-500rpm，双螺杆挤出机的长径比为40:1。
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