WO2020108204A1 - 一种abs复合材料 - Google Patents

一种abs复合材料 Download PDF

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Publication number
WO2020108204A1
WO2020108204A1 PCT/CN2019/113851 CN2019113851W WO2020108204A1 WO 2020108204 A1 WO2020108204 A1 WO 2020108204A1 CN 2019113851 W CN2019113851 W CN 2019113851W WO 2020108204 A1 WO2020108204 A1 WO 2020108204A1
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parts
composite material
flame retardant
abs
abs composite
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French (fr)
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王亮
叶南飚
邹声文
秦旺平
付锦锋
杜荣华
刘凯
杨霄云
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Kingfa Science and Technology Co Ltd
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • 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
    • 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

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to an ABS composite material.
  • ABS resin is a yellowish solid with a density of about 1.04g/cm 3. Because it organically unifies the properties of three different materials, acrylonitrile, butadiene, and styrene, it has moldability, rigidity, toughness, and comprehensive performance. Excellent and widely used. ABS is suitable for household appliances, such as TV housings, refrigerator linings, vacuum cleaners, etc., as well as plastic products for instruments, telephones, and the automotive industry.
  • Flame retardant ABS is one of the important directions of ABS modification. It is developed in response to the shortcoming of ordinary ABS resin that is easy to burn.
  • the flame retardant grade increases from HB, V-2, V-1, V-0, 5VB to 5VA.
  • the 5V test requires the sample to be burned five times for 5 seconds, and the afterflame or afterflame is extinguished within 30 seconds. The dripping cannot ignite cotton.
  • 5VA also requires that the sample is not allowed to burn through. The thinner the spline, the more Not easy to reach.
  • Patents CN200810066901 and CN201611212463 disclose PVC/ABS alloys, which can achieve high flame retardant grades, but due to poor thermal stability of PVC, the processing window is very narrow, which limits its application.
  • Patent CN201480014209 discloses a filled polycarbonate composition, the flame retardant is bisphenol A-bis (diphenyl phosphate) compounded with a large amount of polytetrafluoroethylene, wollastonite particles, alumina particles or glass fibers And its mixture is filled, but the highest can only be 2.3mm 5VA.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide an ABS composite material.
  • the technical solution adopted by the present invention is: an ABS composite material comprising the following parts by weight of components: ABS resin 34-78 parts, SAN resin 0-20 parts, toughening agent 0-10 parts, resistance 12-20 parts of fuel, 3-6 parts of flame retardant synergist, 3-15 parts of inorganic filler, 0.1-0.5 parts of anti-dripping agent, and 0-2 parts of auxiliary; the average long diameter of the inorganic filler Ratio ⁇ 5:1.
  • AS resin uses high-viscosity SAN resin and inorganic filler with aspect ratio ⁇ 5:1.
  • the inorganic filler cannot be combusted.
  • the inorganic filler with this aspect ratio can be staggered together to play the role of skeleton support.
  • the material is not easy to burn through.
  • the ABS composite material prepared by the above formula: 1. High flame retardant grade, up to 1.8mm5VA grade; 2. Good overall performance, balanced strength and notch impact performance; 3. Good appearance, high gloss; 4. Good thermal stability and wide processing window.
  • the ABS composite material of the present invention can be used in the field of electronic appliances with high performance and flame retardant requirements.
  • the inorganic filler is at least one of talc powder, inorganic salt whiskers, marble powder, mica powder, calcium metasilicate, kaolin and montmorillonite.
  • the inorganic salt whiskers are calcium sulfate whiskers and/or basic magnesium sulfate whiskers.
  • the average aspect ratio of the inorganic filler is ⁇ 10:1, and D50 ⁇ 8 ⁇ m.
  • the flame retardant is tetrabromobisphenol A, tris(tribromophenoxy)triazine, brominated epoxy, decabromodiphenylethane, brominated At least one of polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate, and brominated polyacrylate.
  • the flame retardant may be a halogen flame retardant, preferably a bromine flame retardant; more preferably the above bromine flame retardant.
  • the flame retardant is a mixture of tris(tribromophenoxy)triazine and brominated epoxy or decabromodiphenylethane.
  • the flame retardant is tri(tribromophenoxy)triazine compounded with brominated epoxy or decabromodiphenylethane, the flame retardant effect is better than other types of flame retardants.
  • the weight percentage of acrylonitrile is 15 to 30%
  • the weight percentage of butadiene is 20 to 40%
  • the weight of styrene is 30 to 65%.
  • the ABS resin may be ABS resin produced by a one-step polymerization process with a core-shell structure, or two steps of acrylonitrile-styrene copolymer (AS resin, SAN) blended with ABS rubber powder graft-polymerized by an emulsion method ABS resin produced by the process; commercially available ABS resin can be used as the matrix resin, or a certain amount and ratio of the blend of ABS grafted rubber powder and SAN can be used as the matrix resin, but the composition of the ABS resin matrix needs to meet Only in this way can a better flame retardant effect be achieved.
  • AS resin, SAN acrylonitrile-styrene copolymer
  • ABS resin graft-polymerized by an emulsion method ABS resin produced by the process
  • commercially available ABS resin can be used as the matrix resin, or a certain amount and ratio of the blend of ABS grafted rubber powder and SAN can be used as the matrix resin, but the composition of the ABS resin matrix needs to meet Only in this way can a
  • the weight percentage of the butadiene in the ABS resin is 28 to 35%. After repeated experiments and researches by the inventors, it is found that under the same amount of ABS resin, when the weight percentage of butadiene in the ABS resin is 28 to 35%, a better flame retardant effect can be achieved, and the resistance The impact performance is good, the combustion is not easy to drip (5VA), and the performance and appearance are more balanced.
  • the toughening agent is ABS grafted rubber powder, chlorinated polyethylene, silicone rubber, styrene-butadiene-styrene block copolymer, oil-extended SBS , SEBS, nitrile rubber, EPDM, cis-butadiene rubber, natural rubber, styrene-butadiene rubber, acrylic resin, methyl methacrylate-butadiene-styrene copolymer, styrene butyl acrylate binary At least one of graft-modified ethylene-propylene rubber, ethylene-acrylate copolymer, EAA, ethylene-acrylate copolymer, and EVA.
  • the toughening agent is at least one of linear or star SBS and linear or star SEBS.
  • the above-mentioned toughening agent when used, it can complement each other with the inorganic filler, which can more effectively increase the viscosity of the material in the molten state and help to improve the flame retardant level.
  • the ABS composite material of the present invention contains the following parts by weight of components: ABS resin 34-78 parts, SAN resin 0-20 parts, toughener 0-10 parts, flame retardant 12 to 20 parts of agent, 3 to 6 parts of flame retardant synergist, 3 to 15 parts of inorganic filler, 0.1 to 0.5 parts of anti-drip agent and 0 to 2 parts of auxiliary.
  • the ABS composite material includes the following parts by weight of components: ABS resin 34-78 parts, SAN resin 3-20 parts, toughener 1-10 parts, flame retardant 12 to 20 parts of agent, 3 to 6 parts of flame retardant synergist, 3 to 15 parts of inorganic filler, 0.1 to 0.5 parts of anti-drip agent and 0 to 2 parts of auxiliary.
  • the flame retardant synergist includes antimony compound, polysiloxane and inorganic powder, and the weight percentage of the antimony compound in the flame retardant synergist The content is 20 ⁇ 80%;
  • the antimony compound is at least one of antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, antimony phosphite, antimony polyphosphate and complex antimony;
  • the polysiloxane is methyl polysiloxane, phenyl polysiloxane, vinyl polysiloxane, amido polysiloxane, epoxy polysiloxane, isobutyl polysiloxane , At least one of styryl polysiloxane and cyclic structure polysiloxane;
  • the inorganic powder is at least one of talc powder, magnesium carbonate, barium sulfate, marble powder, mica powder, natural silica, wollastonite powder, kaolin, sepiolite, whiskers, montmorillonite and feldspar powder.
  • the flame retardant synergist is more preferably the flame retardant synergist in CN20121045503.8.
  • the weight average molecular weight is 1 ⁇ 10 5 to 1.5 ⁇ 10 5 g/mol.
  • the anti-dripping agent is polytetrafluoroethylene;
  • the auxiliary agent includes at least one of an antioxidant, a lubricant, a weathering agent, and a colorant.
  • the antioxidant includes a hindered phenolic antioxidant and a phosphite antioxidant
  • the lubricant includes an amide lubricant and a stearate lubricant , At least one of ester lubricants and silicone lubricants
  • the weathering agent includes at least one of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers and hindered amine light stabilizers Species.
  • the colorant includes at least one of a pigment type, a dye type, and other colorants with special aesthetic effects.
  • the invention also provides a method for preparing the ABS composite material, including the following steps:
  • the above mixture is transported to the twin-screw extruder through a precision metering feeding device.
  • the screw temperature of each section of the extruder is controlled between 180 and 220°C, and the length-diameter ratio of the twin-screw extruder is 30 to 45.
  • the screw speed is 200-800 rpm, under the shearing, mixing and conveying of the screw, the material can be fully melted and compounded, and then extruded, granulated and dried to obtain ABS composite material.
  • the beneficial effect of the present invention is that the present invention provides an ABS composite material.
  • the ABS composite material of the present invention : 1. High flame retardant grade, up to 1.8mm5VA grade; 2. Good overall performance, balanced strength and notch impact performance; 3. Good appearance, high gloss; 4. Thermal stability Good performance and wide processing window.
  • PA-747S and PA-757 of Chimei Industries of Taiwan are used as the ABS resin; the weight percentage of butadiene in PA-747S is 28-35%, butadiene in PA-757 The weight percentage of olefin is less than 20%;
  • SAN resin is selected from D-168 of Zhenjiang Chimei Chemical Co., Ltd. and SAN 350 of Kumho Chemical Co., Ltd.; D-168 is a high-viscosity SAN, and the weight average molecular weight of D-168 is 1.4 ⁇ 10 5 g/mol; It is a common SAN. The weight average molecular weight of SAN-350 is 0.85 ⁇ 10 5 g/mol.
  • the toughening agent is the irregular spherical high-rubber powder ABS 60P of Taiwan Guoqiao Petrochemical Co., Ltd., and the linear SBS and star SEBS of China Petrochemical Corporation Baling Branch; the flame retardant is the Israeli Dead Sea Bromine Company.
  • the agent is prepared by the following method: mix 60 grams of talc powder, 15 grams of dimethyl polysiloxane, and 25 grams of antimony trioxide in a high-mixer for 20 minutes to prepare it, and record it as KF-1;
  • the average aspect ratio of HTPUltra5L is ⁇ 5:1, the average aspect ratio of basic magnesium sulfate whiskers is ⁇ 5:1, the average aspect ratio of precipitated barium sulfate is about 1:1;
  • the anti-dripping agent is Guangzhou Entropy SN80-SA7;
  • the produced antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 1:2.
  • the lubricant is ethylene bisstearic acid amide (EBS) provided by Beijing Shidafeng Trading Co., Ltd.
  • the preparation method of the ABS composite material of the embodiment and the comparative example is the same, specifically: firstly, the raw materials are added into a high-speed mixer for uniform mixing, and then the above mixture is sent into a twin-screw extruder for kneading, extrusion, drawing, Water cooling and pelletizing; among them, the length-to-diameter ratio of the twin screw extruder is 40:1; the barrel temperature is set to: the temperature in the first zone is 80 °C, the temperature in the second zone is 160 °C, the temperature in the third zone is 200 °C, and the temperature in the fourth zone is 200 °C, five zone temperature 200 °C, six zone temperature 200 °C, seven zone temperature 200 °C, eight zone temperature 200 °C, nine zone temperature 200 °C, ten zone temperature 200 °C, head temperature 220 °C; screw speed is 300 rpm Minutes to get ABS composite material.
  • ABS composite material formulations of Examples 16 to 22 differ from Example 7 only in the types of flame retardants.
  • the ABS composite material formulations of Examples 16 to 22 are shown in Table 3.
  • Examples 22 to 23 The ABS composite formulations of Examples 22 to 23 differ from Example 6 only in the types of tougheners. The types of Examples 22 to 23 are shown in Table 4.
  • ABS composite materials prepared in the above examples and comparative examples are first injected into standard test strips according to the standard size, and then each performance test is performed according to the test standards shown in Table 5 above; each example and comparative test The performance test data of this kind are shown in Table 6-9.
  • the tensile strength is greater than 38MPa
  • the bending strength is greater than 56MPa
  • the IZOD notch impact strength is greater than 12kJ/m 2 and the gloss is greater than 80
  • the comprehensive mechanical properties of the material are better
  • the impact strength is the most critical factor.
  • the ABS composite material of the present invention has better flame retardancy and better impact resistance. From the comparison between Example 7 and Comparative Example 1, it can be seen that the flame retardant effect and mechanical properties of butadiene with a weight percentage of 28 to 35% are better than that of ABS resin with a lower butadiene content.
  • Example 7 and Comparative Example 2 It can be seen from the comparison between Example 7 and Comparative Example 2 that the high-viscosity SAN resin has a higher flame retardant grade than the ordinary SAN resin. It can be seen from the comparison between Example 7 and Comparative Example 3 that the flame retardant effect of using KF-1 is better than the general flame retardant synergist. It can be seen from the comparison between Example 7 and Comparative Example 4 that when the aspect ratio of the inorganic filler is greater than 5:1, the flame retardant effect is better. As can be seen from the comparison of Examples 4 to 9, as the content of the inorganic filler increases, the content of the ABS resin decreases, the flame retardant grade of the ABS composite increases, and the tensile strength, bending strength, and notch impact strength decrease.
  • the content of the inorganic filler is greater than 12 parts by weight, the increase in the flame retardant grade is not obvious, and the toughness decreases, so the content of the inorganic filler is preferably 8 to 12 parts by weight. It can be seen from the results of Examples 5, 7, 10 to 13 that as the content of the high-viscosity SAN resin increases, the impact strength decreases, but the tensile strength and bending strength increase. When the high-viscosity SAN resin is greater than When it is 3 parts by weight, it can meet the balance of impact performance and strength. It can be seen from the comparison between Example 7 and Examples 14 and 15 that the toughening agent can improve the problem of reduction in impact strength caused by the high-viscosity SAN resin.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

一种ABS复合材料，包含以下重量份的组分：ABS树脂34～78份、SAN树脂0～20份、增韧剂0～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份；所述无机填充物的平均长径比≥5:1。所述ABS复合材料：1、阻燃等级高，最高可以达到1.8mm5VA等级；2、综合性能好，能达到强度和缺口冲击性能均衡；3、外观好，光泽度高；4、热稳定性好，加工窗口宽。

Description

一种ABS复合材料 技术领域
本发明涉及工程塑料技术领域，具体涉及一种ABS复合材料。
背景技术
ABS树脂是微黄色固体，密度约为1.04g/cm 3，由于它将丙烯腈、丁二烯、苯乙烯三种不同材料的性能有机地统一起来，兼具成型性、刚性、韧性，综合性能优良，应用广泛。ABS适用于家用电器制品，如电视机外壳、冰箱内衬、吸尘器等，以及仪表、电话、汽车工业用塑料制品。
阻燃ABS是ABS改性的重要方向之一，它是针对普通ABS树脂容易燃烧这一缺点而开发的。阻燃等级由HB、V-2、V-1、V-0、5VB向5VA逐级递增。其中5V测试要求对样品进行五次5秒的燃烧测试后，余焰或余燃在30秒内熄灭，滴落不可引燃棉花，5VA还要求样品不允许被烧穿，样条越薄，越不容易达到。
常规改性方式，如专利CN201310225994、CN201310430476公开了阻燃ABS和阻燃PC/ASA合金，溴系或磷系阻燃，但达到阻燃效果的样条厚度较大，一般在3.0mm以上。
专利CN200810066901、CN201611212463公开了PVC/ABS合金，可以达到高阻燃等级，但由于PVC热稳定性较差，加工窗口很窄，限制了其应用。
专利CN201210470130、CN201310743041公开了高阻燃等级的ABS及其合金，但由于玻纤/碳纤的加入，导致其外观不佳。
专利CN201480014209公开了一种填充的聚碳酸酯组合物，阻燃剂为双酚A一双(二苯基磷酸酯)复配大量的聚四氟乙烯，以硅灰石颗粒、氧化铝颗粒或者玻璃纤维及其混合物为填充，但最高只能做到2.3mm 5VA。
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ABS复合材料。
为实现上述目的，本发明采取的技术方案为：一种ABS复合材料，包含以下重量份的组分：ABS树脂34～78份、SAN树脂0～20份、增韧剂0～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份；所述无机填充物的平均长径比≥5:1。
AS树脂选用高粘的SAN树脂，选用长径比≥5:1的无机填充物，无机填充物不能燃烧，该长径比的无机填充物能交错搭在一起，起到骨架支撑的作用，使材料不易烧穿。采用上述配方制得的ABS复合材料：1、阻燃等级高，最高可以达到1.8mm5VA等级；2、综合性能好，能达到强度和缺口冲击性能均衡；3、外观好，光泽度高；4、热稳定性好，加工窗口宽。本发明所述ABS复合材料可用于性能和阻燃等级要求较高的电子电器领域。
作为本发明所述ABS复合材料的优选实施方式，所述无机填充物为滑石粉、无机盐晶须、云石粉、云母粉、偏硅酸钙、高岭土和蒙脱石中的至少一种。
作为本发明所述ABS复合材料的优选实施方式，所述无机盐晶须为硫酸钙晶须和/或碱式硫酸镁晶须。
作为本发明所述ABS复合材料的优选实施方式，所述无机填充物的平均长径比≥10:1，D50≤8μm。
作为本发明所述ABS复合材料的优选实施方式，所述阻燃剂为四溴双酚A、三(三溴苯氧基)三嗪、溴化环氧、十溴二苯乙烷、溴化聚酰亚胺、溴化聚苯乙烯、聚溴化苯乙烯、溴化聚碳酸酯和溴化聚丙烯酸酯中的至少一种。
所述阻燃剂可以为卤系阻燃剂，优选为溴系阻燃剂；更优选为上述溴系阻燃剂。
作为本发明所述ABS复合材料的优选实施方式，所述阻燃剂为三(三溴苯 氧基)三嗪与溴化环氧或十溴二苯乙烷的混合物。当阻燃剂为三(三溴苯氧基)三嗪与溴化环氧或十溴二苯乙烷复配时，阻燃效果相比采用其他种类的阻燃剂较好。
作为本发明所述ABS复合材料的更优选实施方式，所述三(三溴苯氧基)三嗪与溴化环氧或十溴二苯乙烷的重量之比为：三(三溴苯氧基)三嗪：溴化环氧或十溴二苯乙烷＝1:4～4:1。经发明人多次反复实验得出，当阻燃剂尤其是当采用上述配比复配时，阻燃效果更佳。
作为本发明所述ABS复合材料的优选实施方式，所述ABS树脂中，丙烯腈的重量百分含量为15～30％，丁二烯的重量百分含量为20～40％，苯乙烯的重量百分含量为30～65％。
所述ABS树脂可以选用具有核壳结构的一步法聚合工艺生产的ABS树脂，也可以选用乳液法接枝聚合的ABS胶粉掺混丙烯腈-苯乙烯共聚物(AS树脂，SAN)的两步法工艺生产的ABS树脂；可以选用市售的ABS树脂作为基体树脂，也可以选用一定量和比例的ABS接枝胶粉与SAN的掺混物作为基体树脂，但ABS树脂基体的组成均需要满足上述才能达到较好的阻燃效果。
作为本发明所述ABS复合材料的优选实施方式，所述丁二烯在所述ABS树脂中的重量百分含量为28～35％。经发明人多次反复实验研究得出，在同样的ABS树脂添加量下，当ABS树脂中的丁二烯重量百分含量为28～35％时，能达到更好的阻燃效果，且抗冲击性能好，燃烧不易滴落(5VA)，性能和外观较均衡。
作为本发明所述ABS复合材料的优选实施方式，所述增韧剂为ABS接枝胶粉、氯化聚乙烯、硅橡胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物、充油SBS、SEBS、丁睛橡胶、三元乙丙橡胶、顺丁橡胶、天然橡胶、丁苯橡胶、丙烯酸系树脂、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、苯乙烯丙烯酸丁酯二元接枝改性乙丙胶、乙烯-丙烯酸脂共聚物、EAA、乙烯-丙烯酸盐共聚物和EVA中的至少一种。
作为本发明所述ABS复合材料的优选实施方式，所述增韧剂为线型或星型SBS和线型或星型SEBS中的至少一种。尤其是采用上述增韧剂时，能与无机 填充材料相互补充，能更有效地提高材料在熔融状态下的粘度，有利于提高阻燃等级。
作为本发明所述ABS复合材料的优选实施方式，所述ABS复合材料包含以下重量份的组分：ABS树脂34～78份、SAN树脂0～20份、增韧剂0～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份。
作为本发明所述ABS复合材料的优选实施方式，所述ABS复合材料包含以下重量份的组分：ABS树脂34～78份、SAN树脂3～20份、增韧剂1～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份。
作为本发明所述ABS复合材料的优选实施方式，所述阻燃协效剂包括锑化合物、聚硅氧烷和无机粉体，所述锑化合物在所述阻燃协效剂中的重量百分含量为20～80％；
所述锑化合物为三氧化二锑、胶体五氧化二锑、锑酸钠、三氯化锑、五氯化锑、亚磷酸锑、多聚磷酸锑和络合锑中的至少一种；
所述聚硅氧烷为甲基聚硅氧烷、苯基聚硅氧烷、乙烯基聚硅氧烷、酰胺基聚硅氧烷、环氧基聚硅氧烷、异丁基聚硅氧烷、苯乙烯基聚硅氧烷和环状结构聚硅氧烷中的至少一种；
所述无机粉体为滑石粉、碳酸镁、硫酸钡、云石粉、云母粉、天然硅石、硅灰石粉、高岭土、海泡石、晶须、蒙脱石和长石粉中的至少一种。
阻燃协效剂更优选采用CN20121045503.8中的阻燃协效剂。
作为本发明所述ABS复合材料的优选实施方式，所述SAN树脂中，重均分子量为1×10 5～1.5×10 5g/mol。
作为本发明所述ABS复合材料的优选实施方式，所述抗滴落剂为聚四氟乙烯；所述助剂包括抗氧剂、润滑剂、耐候剂和着色剂中的至少一种。
作为本发明所述ABS复合材料的优选实施方式，所述抗氧化剂包括受阻酚类抗氧剂和亚磷酸酯类抗氧剂；所述润滑剂包括酰胺类润滑剂、硬脂酸盐类润滑剂、酯类润滑剂和硅酮类润滑剂中的至少一种；所述耐候剂包括二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂中的至少一种。所述着色剂包括颜料型、染料型和其他具有特殊美学效果的着色剂中的至少一种。
本发明还提供了所述ABS复合材料的制备方法，包括如下步骤：
a、将各组分原料按配比在高速混合机充分混合5～10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180～220℃之间，双螺杆挤出机的长径比为30～45，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ABS复合材料。
本发明的有益效果在于：本发明提供了一种ABS复合材料。本发明所述ABS复合材料：1、阻燃等级高，最高可以达到1.8mm5VA等级；2、综合性能好，能达到强度和缺口冲击性能均衡；3、外观好，光泽度高；4、热稳定性好，加工窗口宽。
具体实施方式
实施例和对比例的原料中，ABS树脂选用台湾奇美实业的PA-747S和PA-757；PA-747S中的丁二烯的重量百分含量为28～35％，PA-757中的丁二烯的重量百分含量小于20％；
SAN树脂选用镇江奇美化工有限公司的D-168以及韩国锦湖化学株式会社的SAN 350；D-168为高粘SAN，D-168的重均分子量为1.4×10 5g/mol；SAN-350是普通SAN，SAN-350的重均分子量为0.85×10 5g/mol。
增韧剂选用台湾国乔石油化学股份有限公司的不规则球型高胶粉ABS 60P，以及中国石油化工股份有限公司巴陵分公司的线性SBS和星型SEBS；阻燃剂选用以色列死海溴公司的三(三溴苯氧基)三嗪FR-245和韩国宇进的溴化环氧 CXB-714C；阻燃协效剂选用三氧化二锑，由华昌锑业公司生产；阻燃协效剂采用以下方法制得：将滑石粉60克，二甲基聚硅氧烷15克，三氧化二锑25克，在高混机中混和20分钟，即可制得，记为KF-1；无机填充物选用意大利依米发比(IMIFABI)滑石粉HTPUltra5L、营口威斯克化学有限公司的碱式硫酸镁晶须HTPUltra5L的滑石粉和广州市黄埔天泰化轻有限公司沉淀硫酸钡AB-3000N1，HTPUltra5L的平均长径比≥5:1，碱式硫酸镁晶须的平均长径比≥5:1，沉淀硫酸钡的平均长径比约为1:1；抗滴落剂选用广州熵能公司的SN80-SA7；助剂为抗氧剂和润滑剂，其中，抗氧剂和润滑剂的重量之比为：抗氧剂：润滑剂＝3:5，抗氧剂选用上海汽巴精化公司生产的抗氧剂1010和抗氧剂168按重量比1:2复配而成的混合物，润滑剂选用北京实达丰商贸有限公司提供的乙撑双硬脂酸酰胺(EBS)。
实施例和对比例的ABS复合材料的制备方法相同，具体为：首先将原料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40:1；螺筒温度设定为：一区温度80℃，二区温度160℃，三区温度200℃，四区温度200℃，五区温度200℃，六区温度200℃，七区温度200℃，八区温度200℃，九区温度200℃，十区温度200℃，机头温度220℃；螺杆转速为300转/分钟，即得ABS复合材料。
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。
实施例1～9
实施例1～9的ABS复合材料配方见表1。
表1 实施例1～9的ABS复合材料配方
Figure PCTCN2019113851-appb-000001
Figure PCTCN2019113851-appb-000002
“-”表示不添加。
实施例10～15和对比例1～4
实施例10～15和对比例1～4的ABS复合材料配方见表2。
表2 实施例10～15和对比例1～4的ABS复合材料配方
Figure PCTCN2019113851-appb-000003
Figure PCTCN2019113851-appb-000004
实施例16～22
实施例16～22的ABS复合材料配方与实施例7的不同之处仅在于阻燃剂的种类的不同，实施例16～22的ABS复合材料配方见表3。
表3 实施例16～22的ABS复合材料配方
Figure PCTCN2019113851-appb-000005
实施例22～23实施例22～23的ABS复合材料配方与实施例6的不同之处仅在于增韧剂的种类的不同，实施例22～23的种类见表4。
表4 实施例22～23的增韧剂种类
实施例 增韧剂种类
实施例22 线型SBS
实施例23 星型SEBS
实施例24
产品性能测试方法见表5。
表5 性能测试方法
性能指标 测试条件 测试方法
拉伸强度 50mm/min ISO 527
弯曲强度 2mm/min ISO 178
IZOD缺口冲击强度 23℃ ISO 180
阻燃等级测试 1.8-3.0mm UL94
光泽度 60° ASTM D523
将上述各实施例和对比例所制得的ABS复合材料先按标准尺寸注塑成测试用的标准样条，然后按上述表5所示的测试标准进行各性能测试；各实施例和对比例试样的性能测试数据见表6～9所示。
表6 实施例1～9的试样的性能测试数据
Figure PCTCN2019113851-appb-000006
Figure PCTCN2019113851-appb-000007
表7 实施例10～15和对比例1～4的试样的性能测试数据
Figure PCTCN2019113851-appb-000008
一般而言，拉伸强度大于38MPa，弯曲强度大于56MPa，IZOD缺口冲击强度大于12kJ/m 2，光泽度大于80时，材料的综合力学性能较优，其中冲击强度为最关键的因素。从表6、7的数据可以看出，本发明所述ABS复合材料的阻燃性能较好，并具有较好的抗冲击强度。从实施例7和对比例1的比较可以看出，采用丁二烯的重量百分含量为28～35％的阻燃效果和力学性能优于较低丁二烯含量的ABS树脂。从实施例7和对比例2的比较可以看出，采用高粘SAN树脂比普通的SAN树脂的阻燃等级更高。从实施例7和对比例3的比较可以看出，采用KF-1的阻燃效果比一般的阻燃协效剂更好。从实施例7和对比例4的比较可以看出，当无机填充物的长径比大于5:1时，阻燃效果更佳。从实施例4～9的比较可以看出，随着无机填充物含量的增加，ABS树脂含量的降低，ABS复合材料的阻燃等级增加，拉伸强度、弯曲强度和缺口冲击强度有所下降，当无机填充物的含量大于12重量份时，阻燃等级增加不明显，韧性下降，因此优选无机填充物的含量为8～12重量份。从实施例5、7、10～13的结果可以看出，随着高粘SAN树脂含量的增加，抗冲击强度有所下降，但是拉伸强度和弯曲强 度有所上升，当高粘SAN树脂大于3重量份时，能满足冲击性能和强度的平衡。实施例7和实施例14、15的比较可以看出，增韧剂能改善高粘SAN树脂带来的抗冲击强度下降问题。
表8 实施例16～22试样的性能测试数据
Figure PCTCN2019113851-appb-000009
从表6、8中实施例7、16～22的比较可以看出，当三(三溴苯氧基)三嗪与溴化环氧复配作为阻燃剂时能的阻燃效果较好，尤其是当三(三溴苯氧基)三嗪与溴化环氧的重量之比为：三(三溴苯氧基)三嗪：溴化环氧＝1:4～4:1时，阻燃效果更好。发明人采用同样的方法对三(三溴苯氧基)三嗪与十溴二苯乙烷复配做了相关试验，结果表明当三(三溴苯氧基)三嗪与十溴二苯乙烷复配作为阻燃剂时能的阻燃效果较好，尤其是当三(三溴苯氧基)三嗪与十溴二苯乙烷的重量之比为：三(三溴苯氧基)三嗪：十溴二苯乙烷＝1:4～4:1时，阻燃效果更好。
表9 实施例22～23试样的性能测试数据
Figure PCTCN2019113851-appb-000010
Figure PCTCN2019113851-appb-000011
从表6、9中实施例6、22、23的比较可以看出，当增韧剂由球形的高胶粉更换为线型或星型SBS或SEBS时，复合材料的阻燃效果更好。
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ABS复合材料，其特征在于，包含以下重量份的组分：ABS树脂34～78份、SAN树脂0～20份、增韧剂0～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份；所述无机填充物的平均长径比≥5:1。
  2. 如权利要求1所述ABS复合材料，其特征在于，所述无机填充物为滑石粉、无机盐晶须、云石粉、云母粉、偏硅酸钙、高岭土和蒙脱石中的至少一种。
  3. 如权利要求1所述ABS复合材料，其特征在于，所述无机填充物的平均长径比≥10:1，D50≤8μm。
  4. 如权利要求1所述ABS复合材料，其特征在于，所述阻燃剂为四溴双酚A、三(三溴苯氧基)三嗪、溴化环氧、十溴二苯乙烷、溴化聚酰亚胺、溴化聚苯乙烯、聚溴化苯乙烯、溴化聚碳酸酯和溴化聚丙烯酸酯中的至少一种；所述阻燃剂为三(三溴苯氧基)三嗪与溴化环氧或十溴二苯乙烷的混合物；更优选地，所述三(三溴苯氧基)三嗪与溴化环氧或十溴二苯乙烷的重量之比为：三(三溴苯氧基)三嗪：溴化环氧或十溴二苯乙烷＝1:4～4:1。
  5. 如权利要求1所述ABS复合材料，其特征在于，所述ABS树脂中，丙烯腈的重量百分含量为15～30％，丁二烯的重量百分含量为20～40％，苯乙烯的重量百分含量为30～65％；优选地，所述丁二烯在所述ABS树脂中的重量百分含量为28～35％。
  6. 如权利要求1所述ABS复合材料，其特征在于，所述增韧剂为ABS接枝胶粉、氯化聚乙烯、硅橡胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物、充油SBS、SEBS、丁睛橡胶、三元乙丙橡胶、顺丁橡胶、天然橡胶、丁苯橡胶、丙烯酸系树脂、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物、苯乙烯丙烯酸丁酯二元接枝改性乙丙胶、乙烯-丙烯酸脂共聚物、EAA、乙烯-丙烯酸盐共聚物和EVA中的至少一种；优选地，所述增韧剂为线型或星型SBS和线型或星型SEBS中的至少一种。
  7. 如权利要求1所述ABS复合材料，其特征在于，包含以下重量份的组分：ABS树脂34～78份、SAN树脂0～20份、增韧剂0～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份；优选地，所述ABS复合材料包含以下重量份的组分：ABS树脂34～78份、SAN树脂3～20份、增韧剂1～10份、阻燃剂12～20份、阻燃协效剂3～6份、无机填充物3～15份、抗滴落剂0.1～0.5份和助剂0～2份。
  8. 如权利要求1所述ABS复合材料，其特征在于，所述阻燃协效剂包括锑化合物、聚硅氧烷和无机粉体，所述锑化合物在所述阻燃协效剂中的重量百分含量为20～80％；
    所述锑化合物为三氧化二锑、胶体五氧化二锑、锑酸钠、三氯化锑、五氯化锑、亚磷酸锑、多聚磷酸锑和络合锑中的至少一种；
    所述聚硅氧烷为甲基聚硅氧烷、苯基聚硅氧烷、乙烯基聚硅氧烷、酰胺基聚硅氧烷、环氧基聚硅氧烷、异丁基聚硅氧烷、苯乙烯基聚硅氧烷和环状结构聚硅氧烷中的至少一种；
    所述无机粉体为滑石粉、碳酸镁、硫酸钡、云石粉、云母粉、天然硅石、硅灰石粉、高岭土、海泡石、晶须、蒙脱石和长石粉中的至少一种。
  9. 如权利要求1所述ABS复合材料，其特征在于，所述SAN树脂中，重均分子量为1×10 5～1.5×10 5g/mol。
  10. 如权利要求1所述ABS复合材料，其特征在于，所述抗滴落剂为聚四氟乙烯；所述助剂包括抗氧剂、润滑剂、耐候剂和着色剂中的至少一种；优选地，所述抗氧化剂包括受阻酚类抗氧剂和亚磷酸酯类抗氧剂；所述润滑剂包括酰胺类润滑剂、硬脂酸盐类润滑剂、酯类润滑剂和硅酮类润滑剂中的至少一种；所述耐候剂包括二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂和受阻胺类光稳定剂中的至少一种。
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CN118878929A (zh) * 2024-08-13 2024-11-01 深圳金大全科技有限公司 一种abs阻燃增韧剂及其制备方法和应用
CN119371757A (zh) * 2024-10-28 2025-01-28 金发科技股份有限公司 一种as组合物及其制备方法和应用
CN120005347A (zh) * 2025-04-22 2025-05-16 陕西聚能塑胶有限公司 一种高透明阻燃abs复合材料及其制备方法

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