WO2020114316A1 - 一种abs组合物及一种abs组合物的制备方法 - Google Patents
一种abs组合物及一种abs组合物的制备方法 Download PDFInfo
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- WO2020114316A1 WO2020114316A1 PCT/CN2019/121706 CN2019121706W WO2020114316A1 WO 2020114316 A1 WO2020114316 A1 WO 2020114316A1 CN 2019121706 W CN2019121706 W CN 2019121706W WO 2020114316 A1 WO2020114316 A1 WO 2020114316A1
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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
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- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- 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
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the invention relates to the technical field of new polymer materials, in particular to an ABS composition and a preparation method of the ABS composition.
- ABS resin Acrylonitrile-butadiene-styrene copolymer resin
- its performance is between engineering plastics and general-purpose plastics, and its comprehensive mechanical properties and processing performance are excellent. It is widely used in many fields such as electrical, electronic, mechanical, and construction. Applications.
- ABS resin due to the limitations of its polymer structure and composition, ABS resin also has many defects and deficiencies, such as fatigue resistance, can only reach HB-level flame retardancy.
- the object of the present invention is to provide an ABS composition having advantages such as excellent flame retardancy, excellent fatigue resistance, and low-temperature bending retention rate.
- Another object of the present invention is to provide a method for preparing an ABS composition.
- An ABS composition based on parts by weight, includes the following components:
- ABS resin 70 copies 70 copies of ABS resin
- the flame retardant is selected from the group consisting of brominated flame retardants-antimony-containing compound flame retardant synergists or brominated flame retardants-antimony-containing compound flame retardant synergists and (nitrogen-based One or more of a flame retardant, a phosphorus flame retardant, a phosphorus-nitrogen flame retardant, and a metal hydroxide).
- the flame retardant is selected from the group consisting of brominated flame retardants-antimony-containing compound flame retardant synergists or brominated flame retardants-antimony-containing compound flame retardant synergists and (nitrogen-based One or more of a flame retardant, a phosphorus flame retardant, a phosphorus-nitrogen flame retardant, and a metal hydroxide).
- the flame retardant is selected from the group consisting of bromine flame retardant-antimony compound flame retardant synergist and (nitrogen flame retardant, phosphorus flame retardant, phosphorus-nitrogen flame retardant) , One or more of metal hydroxides) re-compounds;
- Brominated flame retardant-antimony compound flame retardant synergist compound and (nitrogen flame retardant, phosphorus flame retardant, phosphorus-nitrogen flame retardant, one or more of metal hydroxide Species) can be: brominated flame retardant, antimony-containing compound flame retardant synergist, phosphorus-nitrogen flame retardant, nitrogen flame retardant, metal hydroxide compound; brominated flame retardant Flame retardant, antimony compound flame retardant synergist, phosphorus-nitrogen flame retardant, metal hydroxide compound; bromine flame retardant, antimony compound flame retardant synergist, nitrogen flame retardant, metal Compounding of hydroxides; compounding of bromine-based flame retardants, flame retardant synergists containing antimony compounds, metal hydroxides; compounding of bromine-based flame retardants, flame retardant synergists containing antimony compounds, phosphorus-nitrogen-based resistance Compounding of fuel and nitrogen flame retardant; etc. formula.
- the brominated flame retardant is selected from tetrabromobisphenol A, brominated triazine, brominated epoxy, decabromodiphenylethane, decabromobiphenyl ether, brominated polyimide, brominated polyphenylene At least one of ethylene, polybrominated styrene, brominated polycarbonate, and brominated polyacrylate;
- the phosphorus-based flame retardant is selected from at least one of bisphenol A bis (diphenyl phosphate), resorcinol (diphenyl phosphate), and triphenyl phosphate;
- the phosphorus-nitrogen flame retardant is selected from at least one of ammonium orthophosphate, ammonium pyrophosphate, ammonium polyphosphate, melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate salt;
- the antimony-containing compound flame retardant synergist is selected from at least one of antimony trioxide, antimony pentoxide, alkali metal salts of antimony acid, and alkaline earth metal salts of antimony acid;
- the metal hydroxide flame retardant is selected from at least one of magnesium hydroxide and aluminum hydroxide;
- the nitrogen flame retardant is selected from at least one of amine salt flame retardants and ammonium salt flame retardants; the amine salt flame retardant is selected from at least one melamine salt flame retardant
- the melamine salt flame retardant is selected from at least one of melamine cyanurate and melamine hydrobromide;
- the ammonium salt flame retardant is selected from ammonium sulfate, aluminum ammonium sulfate, magnesium ammonium sulfate, Ammonium zinc sulfate, calcium ammonium sulfate, iron ammonium sulfate, ammonium bisulfate, ammonium pyrosulfate, ammonium chloride, ammonium bromide, ammonium formate, ammonium acetate, ammonium propionate, ammonium isopropionate, ammonium benzoate, ammonium phenylacetate , Ammonium phthalate, ammonium isophthalate, ammonium terephthalate,
- the particle size of the phosphorus-nitrogen flame retardant is less than or equal to 10 microns; the particle size of the amine salt flame retardant is less than or equal to 10 microns; the flame retardant synergist of the antimony-containing compound The particle size is less than or equal to 10 microns; the particle size of the metal hydroxide flame retardant is less than or equal to 10 microns.
- These flame retardants are filler-type flame retardants, and the particle size hardly changes during the preparation process. If the particle size is too large, it will easily affect the fatigue resistance and low-temperature bending retention rate of the product.
- the polymer with a weight average molecular weight of 4 million to 9 million is selected from ethylene polymers with a weight average molecular weight of 4 million to 9 million; the ethylene polymer with a weight average molecular weight of 4 million to 9 million is selected from a heavy weight Polyethylene with an average molecular weight of 4 million to 9 million, polyvinyl chloride with a weight average molecular weight of 4 million to 9 million, polyvinylidene chloride with a weight average molecular weight of 4 million to 9 million, and weight average molecular weight of 4 million to 9 million Of polyvinylidene fluoride, polytetrafluoroethylene with a weight average molecular weight of 4 million to 9 million, polysiloxane with a weight average molecular weight of 4 million to 9 million, or ethylene, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene At least one of the two or three monomers has a weight average molecular weight of 4 to 9 million.
- the ethylene-based polymer is coated with a thermoplastic resin
- the thermoplastic resin is at least one selected from the group consisting of silicone resin, acrylate resin, and acrylonitrile-styrene copolymer; thermoplastic resin and ethylene
- the weight ratio of the polymer is 1:9-1:1.
- the toughening agent is selected from at least one of polybutadiene grafted acrylonitrile-styrene copolymer and chlorinated polyethylene;
- the content of acrylonitrile is 2-20%, the content of butadiene is 50-80%, and the content of styrene is 18-30%;
- the weight average molecular weight of the chlorinated polyethylene is 100,000-500,000, and the chlorine content is 20-45%.
- the chlorine content of the chlorinated polyethylene is 20-35%.
- inorganic filler In terms of parts by weight, it also includes 0-20 parts of inorganic filler; the inorganic filler is selected from at least one of sheet-like inorganic filler, powdery inorganic filler, and fibrous inorganic filler;
- the flaky inorganic filler is selected from at least one of talc powder and mica powder;
- the fibrous inorganic filler is selected from at least one of wollastonite, potassium titanate whisker, magnesium sulfate whisker, and glass fiber ;
- the powdered inorganic filler is at least one selected from barium sulfate, sepiolite, vermiculite;
- the dosage of the inorganic filler may be 0 parts, 2 parts, 5 parts, 10 parts, 13 parts, 18 parts, and the like.
- the particle size distribution range of the flaky inorganic filler and powdery inorganic filler is 0.05-50 microns.
- the particle size distribution range of the flaky inorganic filler and powdery inorganic filler is 0.5-30 microns.
- the lubricant is selected from at least one of stearate lubricants, fatty acid lubricants, and stearate lubricants ;
- the stearate lubricants are selected from at least one of calcium stearate, magnesium stearate, and zinc stearate;
- the fatty acid lubricants are selected from fatty acids, fatty acid derivatives, fatty acids At least one ester;
- the stearate lubricant is at least one selected from pentaerythritol stearate;
- the lubricant is at least one selected from fatty acid lubricants and stearate lubricants.
- the preferred fatty acid lubricants and stearate lubricants are very effective.
- the content of acrylonitrile in the ABS resin is 11-36%, the content of butadiene is 8-36%, and the content of styrene is 28-80%.
- auxiliaries are at least one selected from heat stabilizers, weathering agents, antioxidants, and colorants.
- a preparation method of ABS composition includes the following steps: Weigh ABS resin, flame retardant, polymer with a weight average molecular weight of 4 million to 9 million, toughener, inorganic filler, and additives into high-speed mixing In the feeder, the mixing is uniform. After adding the uniformly mixed materials to the twin-screw extruder, the screw temperature is 180-240°C, the screw speed is 200-800 rpm, and the ABS composition is obtained by extrusion granulation.
- the flame retardant ABS composition is obtained while improving the fatigue resistance and low-temperature bending retention rate of the material; further, The compound flame retardant is used, and the flame retardant performance is excellent, and when the phosphate flame retardant, amine salt flame retardant, antimony-containing compound flame retardant synergist, metal hydroxide and other filler flame retardants are used At the time, the particle size range was screened to reduce the impact of flame retardants on the fatigue resistance and low-temperature bending retention rate of the material; the addition of lubricants can further greatly improve the fatigue resistance and low-temperature bending retention rate of the material.
- the sources of raw materials used in the present invention are as follows:
- ABS resin acrylonitrile content is 24%, butadiene content is 12%, styrene content is 64%;
- Brominated triazine brominated flame retardant
- Antimony trioxide A particle size less than 10 microns
- Antimony trioxide B particle size less than 20 microns greater than 10 microns;
- Ammonium polyphosphate salt particle size less than 10 microns
- Magnesium hydroxide particle size less than 10 microns
- Ethylene polymer A ultra-high molecular weight polytetrafluoroethylene with a weight average molecular weight of 7 million;
- Ethylene polymer C ultra-high molecular weight polytetrafluoroethylene with a weight average molecular weight of 3 million;
- the particle size distribution range is 1-20 microns
- Talc powder B The particle size distribution range is 30-50 microns
- Talc C The particle size distribution range is 51-60 microns
- Toughener A chlorinated polyethylene with a weight average molecular weight of 250,000 and a chlorine content of 30%;
- Toughener B chlorinated polyethylene with a weight average molecular weight of 250,000 and a chlorine content of 40%;
- Toughener C polybutadiene grafted acrylonitrile-styrene copolymer, acrylonitrile content is 12%, butadiene content is 60%, styrene content is 28%;
- Lubricant A fatty acid ester lubricant, PETS;
- Lubricant B stearate lubricant, zinc stearate
- ABS composition Preparation method of ABS composition: Weigh ABS resin, flame retardant, polymer with a weight average molecular weight of 4 million to 9 million, toughening agent, inorganic filler, lubricant, and additives in proportion
- the mixing is uniform.
- the screw temperature is 180-240°C
- the screw speed is 200-800 rpm
- the ABS composition is obtained by extrusion granulation.
- Comparative Example 1 and Examples 1-5 that adding a polymer with a weight average molecular weight of 4 million to 9 million can improve the flame retardant performance, fatigue resistance, and low-temperature bending retention rate of the product; when the weight average molecular weight is 4 million to 9 million polymer dosage reaches 1 part, fatigue resistance, low temperature bending retention rate increases significantly, GWIT temperature rises, when the amount of ethylene polymer exceeds 5 parts, fatigue resistance, low temperature bending retention rate instead Slightly dropped.
- Example 3 It can be seen from Example 3 and Example 6 that the vinyl polymer coated with SA resin has excellent fatigue resistance and low-temperature bending retention rate.
- Example 3 and Example 7 it can be seen from Example 3 and Example 7 that when the particle size of the filler-type flame retardant is less than 10 ⁇ m, the fatigue resistance is better at low-temperature bending retention.
- Example 3 and Examples 8-9 that the fatty acid ester lubricant improves the fatigue resistance and low-temperature bending retention rate of the product higher, without the addition of lubricant, the fatigue resistance and low-temperature bending retention rate The decline is larger.
- Example 3 and Example 10/11 It can be seen from Example 3 and Example 10/11 that if the particle size of talc powder is small, the effect on fatigue resistance and low-temperature bending retention rate is small.
- Example 3 and Examples 12-13 that the addition of toughening agents can increase fatigue resistance and low-temperature bending retention rate; examples of chlorinated polyethylene as a toughening agent fatigue resistance and low-temperature bending retention rate Better; chlorinated polyethylene with a chlorine content of 20-35% has the best effect in enhancing fatigue resistance and low-temperature bending retention.
- Example 3 It can be seen from Example 3 and Example 14 that the toughening agent can improve the fatigue resistance and low-temperature bending retention rate of the product.
- Example 3 and Examples 15-18 the flame retardant performance of the preferred compound flame retardant is better than the commonly used bromine antimony flame retardant, and although the preferred compound flame retardant is filled The amount of flame retardant added is large, but the fatigue resistance is close to or even better than that of Example 3, and the low-temperature bending retention rate is also maintained at a relatively high level.
- Example 1 without adding a polymer having a weight average molecular weight of 4 million to 9 million, flame retardant performance is reduced, fatigue resistance and low-temperature bending retention rate are poor.
- Example 3 It can be seen from Example 3 and Comparative Examples 1-2 that the molecular weight of the ethylene-based polymer is only 3 million, and the improvement in flame retardancy, fatigue resistance, and low-temperature bending retention rate is small.
- Example 3/11 and Comparative Example 1 polymers with a weight average molecular weight of 4 million to 9 million have a greater impact on the fatigue resistance of the product, while lubricants have a greater impact on the low temperature bending retention rate of the product , The two cooperate, can get very good fatigue resistance and low temperature bending retention rate.
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Abstract
本发明公开了一种ABS组合物，按重量份计，包括以下组分：ABS树脂70份；阻燃剂10-40份；重均分子量为400万-900万的聚合物0.05-8份；所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物、溴系阻燃剂-含锑化合物阻燃协效剂的复配物和氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种的再复配物。本发明的ABS组合物具有耐疲劳性能、低温弯折保持率、阻燃性能好等优点。并且，本发明还公开了一种ABS组合物的制备方法。
Description
本发明涉及新型高分子材料技术领域，特别是涉及一种ABS组合物及一种ABS组合物的制备方法。
近年来，人们对电子电气、建筑等相关领域使用材料的安全性的关注越来越多，相关的法律法规也在逐渐完善，对材料的要求也越来越严格。另外，塑料注塑制品的薄壁化已然成为工业界的重要趋势。这些都对应用材料提出了越来越高的要求。同时，很多厂家为了提高产品的竞争力，不断提高产品的附加值，提出以阻燃材料替代非阻燃材料，高耐候、高耐疲劳性能等也都是相关产品重要的附加功能。
丙烯腈-丁二烯-苯乙烯共聚树脂，即ABS树脂，其性能介于工程塑料和通用塑料之间，综合机械性能和加工成型性能优异，在电子电气、机械、建筑等很多领域都有广泛的应用。但是，受其聚合物结构和组成成份的限制，ABS树脂也存在很多缺陷和不足，如不耐疲劳、只能达到HB级阻燃等。
以ABS树脂为基体，加入一定量和一定配比的溴系阻燃剂和含锑化合物阻燃协效剂，可以制备不同垂直燃烧等级的阻燃ABS。如中国专利CN 102391608中，发明人使用10-25％的环保溴系阻燃剂(十溴二苯乙烷和溴化环氧，单独使用或按照一定比例组合使用)，复配2-8％的阻燃协效剂(含锑化合物的复配型阻燃协效剂)制备出了垂直燃烧等级达到1.6-3.0mm UL94V-0级别的阻燃ABS；中国专利CN 103289293中，作者使用10-25％环保溴系阻燃剂三(三-溴苯基)氰尿酸酯，复配0-1％锑系阻燃协效剂和1-5％磷系阻燃协效剂，可以制备出垂直燃烧等级达到1.5-3.0mm V-2等级以上，甚至1.5-3.0mm V-0等级的阻燃ABS材料。但是，以上专利均未对ABS组合物的耐疲劳性能进行优化和考察。
发明内容
本发明的目的在于，提供一种ABS组合物，具有优秀的阻燃性能、优秀的耐疲劳性能和低温弯折保持率等优点。
本发明的另一目的在于，提供一种ABS组合物的制备方法。
本发明是通过以下技术方案实现的：
一种ABS组合物，按重量份计，包括以下组分：
ABS树脂 70份；
阻燃剂 10-40份；
重均分子量为400万-900万的聚合物 0.05-8份；
所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物或者溴系阻燃剂-含锑化合物阻燃协效剂的复配物和(氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种)的再复配物。
优选的，按重量份计，包括以下组分：
ABS树脂 70份；
阻燃剂 15-35份；
重均分子量为400万-900万的聚合物 1-5份；
所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物或者溴系阻燃剂-含锑化合物阻燃协效剂的复配物和(氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种)的再复配物。
优选的，所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物和(氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种)的再复配物；
溴系阻燃剂-含锑化合物阻燃协效剂的复配物和(氮系阻燃剂、磷系阻燃剂、磷-氮系阻 燃剂、金属氢氧化物中的一种或多种)的再复配物可以是：溴系阻燃剂、含锑化合物阻燃协效剂、磷-氮系阻燃剂、氮系阻燃剂、金属氢氧化物的复配；溴系阻燃剂、含锑化合物阻燃协效剂、磷-氮系阻燃剂、金属氢氧化物的复配；溴系阻燃剂、含锑化合物阻燃协效剂、氮系阻燃剂、金属氢氧化物的复配；溴系阻燃剂、含锑化合物阻燃协效剂、金属氢氧化物的复配；溴系阻燃剂、含锑化合物阻燃协效剂、磷-氮系阻燃剂、氮系阻燃剂的复配；等配方。
所述的溴系阻燃剂选自四溴双酚A、溴代三嗪、溴化环氧、十溴二苯乙烷、十溴联苯醚、溴化聚酰亚胺、溴化聚苯乙烯、聚溴化苯乙烯、溴化聚碳酸酯、溴化聚丙烯酸酯中的至少一种；
所述的磷系阻燃剂选自双酚A双(磷酸二苯酯)、间苯二酚(二苯基磷酸酯)、磷酸三苯酯中的至少一种；
所述的磷-氮系阻燃剂选自正磷酸铵盐、焦磷酸铵盐、聚磷酸铵盐、正磷酸三聚氰胺盐、焦磷酸三聚氰胺盐、聚磷酸三聚氰胺盐中的至少一种；
所述的含锑化合物阻燃协效剂选自三氧化二锑、五氧化二锑、锑酸的碱金属盐、锑酸的碱土金属盐中的至少一种；
所述的金属氢氧化物阻燃剂选自氢氧化镁、氢氧化铝中的至少一种；
所述的氮系阻燃剂选自胺盐类阻燃剂、铵盐类阻燃剂中的至少一种；所述的胺盐类阻燃剂选自三聚氰胺盐阻燃剂中的至少一种；所述的三聚氰胺盐阻燃剂选自三聚氰胺氰尿酸盐、三聚氰胺氢溴酸盐中的至少一种；所述的铵盐类阻燃剂选自硫酸铵、硫酸铵铝、硫酸铵镁、硫酸铵锌、硫酸铵钙、硫酸铵铁、硫酸氢铵、焦硫酸铵、氯化铵、溴化铵、甲酸铵、乙酸铵、丙酸铵、异丙酸铵、苯甲酸铵、苯乙酸铵、邻苯二甲酸铵、间苯二甲酸铵、对苯二甲酸铵、苯丙酸铵、2-甲基苯乙酸铵、3-甲基苯乙酸铵、4-甲基苯乙酸铵、2-乙基苯甲酸铵、3-乙基苯甲酸铵、4-乙基苯甲酸铵中的至少一种。
优选的，所述的磷-氮系阻燃剂的粒径小于等于10微米；所述的胺盐类阻燃剂的粒径小于等于10微米；所述的含锑化合物阻燃协效剂的粒径小于等于10微米；所述的金属氢氧化物阻燃剂的粒径小于等于10微米。这些阻燃剂为填料型阻燃剂，在制备过程中粒径几乎不发生变化，粒径过大，容易影响产品的耐疲劳性能和低温弯折保持率。
所述的重均分子量为400万-900万的聚合物选自重均分子量为400万-900万的乙烯类聚合物；所述的重均分子量为400万-900万的乙烯类聚合物选自重均分子量为400万-900万的聚乙烯、重均分子量为400万-900万的聚氯乙烯、重均分子量为400万-900万的聚偏氯乙烯、重均分子量为400万-900万的聚偏氟乙烯、重均分子量为400万-900万的聚四氟乙烯、重均分子量为400万-900万的聚硅氧烷、或者乙烯、偏氯乙烯、偏氟乙烯、四氟乙烯中的两种或者三种单体的重均分子量为400万-900万的共聚物中的至少一种。
优选的，所述的乙烯类聚合物被热塑性树脂包覆，所述的热塑性树脂选自硅氧烷树脂、丙烯酸酯树脂、丙烯腈-苯乙烯共聚物中的至少一种；热塑性树脂与乙烯类聚合物的重量比为1:9-1:1。
按重量份计，还包括0-12份的增韧剂；所述的增韧剂选自聚丁二烯接枝丙烯腈-苯乙烯共聚物、氯化聚乙烯中的至少一种；所述的聚丁二烯接枝丙烯腈-苯乙烯共聚物中，丙烯腈的含量为2-20％，丁二烯的含量为50-80％，苯乙烯的含量为18-30％；所述的氯化聚乙烯的重均分子量为10-50万，氯含量为20-45％，优选的，氯化聚乙烯的氯含量为20-35％。
按重量份计，还包括0-20份的无机填充物；所述的无机填充物选自片状无机填充物、粉末状无机填充物、纤维状无机填充物中的至少一种；所述的片状无机填充物选自滑石粉、云母粉中的至少一种；所述的纤维状无机填充物选自硅灰石、钛酸钾晶须、硫酸镁晶须、玻纤中的至少一种；所述的粉末状无机填充物选自硫酸钡、海泡石、蛭石中是至少一种；
无机填充物的用量可以是0份、2份、5份、10份、13份、18份等。
优选的，所述的片状无机填充物、粉末状无机填充物的粒径分布范围为0.05-50微米优选的，所述的片状无机填充物、粉末状无机填充物的粒径分布范围为0.5-30微米。
粒径小，则耐疲劳性能好。但是，如果粒径太小，则加工时候不容易分散，加工困难影响产品合格率。
进一步的，按重量份计，还包括0.1-5份的润滑剂；所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑剂选自季戊四醇硬脂酸酯中的至少一种；
优选的，所述的润滑剂选自脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种。在改善ABS组合物的耐疲劳性能、低温弯折保持率方面，优选的脂肪酸类润滑剂、硬脂酸酯类润滑剂的效果非常好。
所述的ABS树脂中的丙烯腈的含量为11-36％，丁二烯的含量为8-36％，苯乙烯的含量为28-80％。
还包括0.2-5份助剂；所述的助剂选自热稳定剂、耐候剂、抗氧剂、着色剂中的至少一种。
一种ABS组合物的制备方法，包括以下步骤：按配比称量ABS树脂、阻燃剂、重均分子量为400万-900万的聚合物、增韧剂、无机填充物、助剂加入高速混料机中，混合均匀，在将混合均匀的物料加入双螺杆挤出机中，螺杆温度为180-240℃，螺杆转速为200-800转，挤出造粒得到ABS组合物。
本发明具有如下有益效果：
本发明通过在ABS中加入阻燃剂、重均分子量为400万-900万的聚合物，得到了阻燃ABS组合物的同时提高了材料的耐疲劳性能、低温弯折保持率；进一步的，使用复配的阻燃剂，阻燃性能优秀，并且，当选用磷酸盐类阻燃剂、胺盐类阻燃剂、含锑化合物阻燃协效剂、金属氢氧化物等填料型阻燃剂时，对粒径范围进行了筛选，减少了阻燃剂对材料耐疲劳性能和低温弯折保持率的影响；润滑剂的加入，可以进一步大幅提升材料的耐疲劳性能和低温弯折保持率。
用以下实施例来说明本发明，但是本发明不受以下实施例所限制。
本发明使用原材料来源如下：
ABS树脂：丙烯腈的含量为24％，丁二烯的含量为12％，苯乙烯的含量为64％；
溴代三嗪：溴系阻燃剂；
三氧化二锑A：粒径小于10微米；
三氧化二锑B：粒径小于20微米大于10微米；
聚磷酸铵盐：粒径小于10微米；
氢氧化镁：粒径小于10微米；
乙烯类聚合物A：超高分子量聚四氟乙烯，重均分子量为700万；
乙烯类聚合物B：超高分子量聚四氟乙烯，重均分子量为700万，SA树脂包覆，重量比SA树脂：超高分子量聚四氟乙烯＝1:8。
乙烯类聚合物C：超高分子量聚四氟乙烯，重均分子量为300万；
滑石粉A：粒径分布范围为1-20微米；
滑石粉B：粒径分布范围为30-50微米；
滑石粉C：粒径分布范围为51-60微米；
增韧剂A：氯化聚乙烯，重均分子量为25万，氯含量为30％；
增韧剂B：氯化聚乙烯，重均分子量为25万，氯含量为40％；
增韧剂C：聚丁二烯接枝丙烯腈-苯乙烯共聚物，丙烯腈的含量为12％，丁二烯的含量为60％，苯乙烯的含量为28％；
润滑剂A：脂肪酸酯润滑剂，PETS；
润滑剂B：硬脂酸盐润滑剂，硬脂酸锌；
实施例和对比例ABS组合物的制备方法：按配比称量ABS树脂、阻燃剂、重均分子量为400万-900万的聚合物、增韧剂、无机填充剂、润滑剂、助剂加入高速混料机中，混合均匀，在将混合均匀的物料加入双螺杆挤出机中，螺杆温度为180-240℃，螺杆转速为200-800转，挤出造粒得到ABS组合物。
各性能测试方法
(1)阻燃等级测试：
a)5VA，测试标准UL94，150mm*150mm*2.0mm的方板，125mm*13mm*2mm的样条；
b)GWIT，测试标准IEC 60695-2-13，100mm*100mm*2.0mm的方板；
(2)耐疲劳测试：注塑成符合ISO 527拉伸强度测试要求的哑铃形样条，在25℃下用于弯折疲劳性测试，结果记录样条断裂时的弯折次数。
(3)低温弯折保持率：注塑成符合ISO 527拉伸强度测试要求的哑铃形样条，在-20℃下用于弯折疲劳性测试，结果记录样条断裂时的弯折次数，对比25℃下的弯折次数的保持率。
表1：实施例1-6组分配比(重量份)及各性能测试结果
从对比例1和实施例1-5可以看出，加入重均分子量为400万-900万的聚合物可以提升产品的阻燃性能、耐疲劳性能、低温弯折保持率；当重均分子量为400万-900万的聚合物用量达到1份，耐疲劳性能、低温弯折保持率上升明显、GWIT温度上升，当乙烯类聚合物用量超过5份后，耐疲劳性能、低温弯折保持率反而稍微下降。
从实施例3和实施例6可以看出，SA树脂包覆的乙烯类聚合物，耐疲劳性能、低温弯折保持率都非常好。
表2：实施例7-9组分配比(重量份)及各性能测试结果
从实施例3和实施例7可以看出，填料型阻燃剂的粒径小于10微米时，耐疲劳性能低温弯折保持率较好。
从实施例3和实施例8-9可以看出，脂肪酸酯润滑剂对产品的耐疲劳性能和低温弯折保持率的提升较高，不加入润滑剂，耐疲劳性能和低温弯折保持率下降较大。
表3：实施例10-14组分配比(重量份)及各性能测试结果
从实施例3和实施例10/11可以看出，滑石粉的粒径小，则对耐疲劳性能和低温弯折保持率的影响较小。
从实施例3和实施例12-13可以看出，加入增韧剂可以增加耐疲劳性能和低温弯折保持率；氯化聚乙烯作为增韧剂的实施例耐疲劳性能和低温弯折保持率较好；在增强耐疲劳性能、低温弯折保持率方面氯含量为20-35％的氯化聚乙烯效果最好。
从实施例3和实施例14可以看出，增韧剂能够提升产品的耐疲劳性能以及低温弯折保持率。
表4：实施例15-18组分配比(重量份)及各性能测试结果
从实施例3和实施例15-18可以看出，优选复配的阻燃剂的实施例阻燃性能比常用的溴锑阻燃剂好，并且，虽然优选的复配阻燃剂中填料型阻燃剂加入量较大，但是耐疲劳性能接近甚至有的比实施例3好，而低温弯折保持率也保持较高的水平。
表5：对比例组分配比(重量份)及各性能测试结果
从实施例1和对比例1可以看出，不加入重均分子量为400万-900万的聚合物，阻燃性能下降、耐疲劳性能和低温弯折保持率很差。
从实施例3和对比例1-2可以看出，乙烯类聚合物的分子量只有300万，对阻燃性能、耐疲劳性能、低温弯折保持率的提升较小。
从实施例3/11和对比例1可以看出，重均分子量为400万-900万的聚合物对产品的耐疲劳性能影响较大，而润滑剂对产品的低温弯折保持率影响较大，两者协同，能够得到非常好的耐疲劳性能和低温弯折保持率。
Claims (12)
- 一种ABS组合物，其特征在于，按重量份计，包括以下组分：ABS树脂 70份；阻燃剂 10-40份；重均分子量为400万-900万的聚合物 0.05-8份；所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物或者溴系阻燃剂-含锑化合物阻燃协效剂的复配物和氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种的再复配物。
- 根据权利要求1所述的ABS组合物，其特征在于，按重量份计，包括以下组分：ABS树脂 70份；阻燃剂 15-35份；重均分子量为400万-900万的聚合物 1-5份；所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物或者溴系阻燃剂-含锑化合物阻燃协效剂的复配物和氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种的再复配物。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，所述的阻燃剂选自溴系阻燃剂-含锑化合物阻燃协效剂的复配物和氮系阻燃剂、磷系阻燃剂、磷-氮系阻燃剂、金属氢氧化物中的一种或多种的再复配物；所述的溴系阻燃剂选自四溴双酚A、溴代三嗪、溴化环氧、十溴二苯乙烷、十溴联苯醚、溴化聚酰亚胺、溴化聚苯乙烯、聚溴化苯乙烯、溴化聚碳酸酯、溴化聚丙烯酸酯中的至少一种；所述的磷系阻燃剂选自双酚A双(磷酸二苯酯)、间苯二酚(二苯基磷酸酯)、磷酸三苯酯中的至少一种；所述的磷-氮系阻燃剂选自正磷酸铵盐、焦磷酸铵盐、聚磷酸铵盐、正磷酸三聚氰胺盐、焦磷酸三聚氰胺盐、聚磷酸三聚氰胺盐中的至少一种；所述的含锑化合物阻燃协效剂选自三氧化二锑、五氧化二锑、锑酸的碱金属盐、锑酸的碱土金属盐中的至少一种；所述的金属氢氧化物阻燃剂选自氢氧化镁、氢氧化铝中的至少一种；所述的氮系阻燃剂选自胺盐类阻燃剂、铵盐类阻燃剂中的至少一种；所述的胺盐类阻燃剂选自三聚氰胺盐阻燃剂中的至少一种；所述的三聚氰胺盐阻燃剂选自三聚氰胺氰尿酸盐、三聚氰胺氢溴酸盐中的至少一种；所述的铵盐类阻燃剂选自硫酸铵、硫酸铵铝、硫酸铵镁、硫酸铵锌、硫酸铵钙、硫酸铵铁、硫酸氢铵、焦硫酸铵、氯化铵、溴化铵、甲酸铵、乙酸铵、丙酸铵、异丙酸铵、苯甲酸铵、苯乙酸铵、邻苯二甲酸铵、间苯二甲酸铵、对苯二甲酸铵、苯丙酸铵、2-甲基苯乙酸铵、3-甲基苯乙酸铵、4-甲基苯乙酸铵、2-乙基苯甲酸铵、3-乙基苯甲酸铵、4-乙基苯甲酸铵中的至少一种。
- 根据权利要求3所述的ABS组合物，其特征在于，所述的磷-氮系阻燃剂的粒径小于等于10微米；所述的胺盐类阻燃剂的粒径小于等于10微米；所述的含锑化合物阻燃协效剂的粒径小于等于10微米；所述的金属氢氧化物阻燃剂的粒径小于等于10微米。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，所述的重均分子量为400万-900万的聚合物选自重均分子量为400万-900万的乙烯类聚合物；所述的重均分子量为400万-900万的乙烯类聚合物选自重均分子量为400万-900万的聚乙烯、重均分子量为400万-900万的聚氯乙烯、重均分子量为400万-900万的聚偏氯乙烯、重均分子量为400万-900万的聚偏氟乙烯、重均分子量为400万-900万的聚四氟乙烯、重均分子量为400万-900万的聚硅氧烷、或者乙烯、偏氯乙烯、偏氟乙烯、四氟乙烯中的两种或者三种单体的重均分子量为400万-900万的共聚物中的至少一种。
- 根据权利要求5所述的ABS组合物，其特征在于，所述的乙烯类聚合物被热塑性树脂包 覆，所述的热塑性树脂选自硅氧烷树脂、丙烯酸酯树脂、丙烯腈-苯乙烯共聚物中的至少一种；热塑性树脂与乙烯类聚合物的重量比为1:9-1:1。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，按重量份计，还包括0-12份的增韧剂；所述的增韧剂选自聚丁二烯接枝丙烯腈-苯乙烯共聚物、氯化聚乙烯中的至少一种；所述的聚丁二烯接枝丙烯腈-苯乙烯共聚物中，丙烯腈的含量为2-20％，丁二烯的含量为50-80％，苯乙烯的含量为18-30％；所述的氯化聚乙烯的重均分子量为10-50万，氯含量为20-45％；优选的，氯化聚乙烯的氯含量为20-35％。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，按重量份计，还包括0-20份的无机填充物；所述的无机填充物选自片状无机填充物、粉末状无机填充物、纤维状无机填充物中的至少一种；所述的片状无机填充物选自滑石粉、云母粉中的至少一种；所述的纤维状无机填充物选自硅灰石、钛酸钾晶须、硫酸镁晶须、玻纤中的至少一种；所述的粉末状无机填充物选自硫酸钡、海泡石、蛭石中是至少一种；所述的片状无机填充物、粉末状无机填充物的粒径分布范围为0.05-50微米；优选的，所述的片状无机填充物、粉末状无机填充物的粒径分布范围为0.5-30微米。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，按重量份计，还包括0.1-5份的润滑剂；所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑剂选自季戊四醇硬脂酸酯中的至少一种；优选的，所述的润滑剂选自脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，所述的ABS树脂中的丙烯腈的含量为11-36％，丁二烯的含量为8-36％，苯乙烯的含量为28-80％。
- 根据权利要求1-2任一项所述的ABS组合物，其特征在于，按重量份计，还包括0.2-5份助剂；所述的助剂选自热稳定剂、耐候剂、抗氧剂、着色剂中的至少一种。
- 一种ABS组合物的制备方法，其特征在于，包括以下步骤：按配比称量ABS树脂、阻燃剂、重均分子量为400万-900万的聚合物、增韧剂、无机填充物、助剂加入高速混料机中，混合均匀，在将混合均匀的物料加入双螺杆挤出机中，螺杆温度为180-240℃，螺杆转速为200-800转，挤出造粒得到ABS组合物。
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| CN110643138B (zh) * | 2019-09-26 | 2022-06-03 | 广东圆融新材料有限公司 | 改性阻燃abs材料及其制备方法 |
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| CN112143162B (zh) * | 2020-09-22 | 2023-04-18 | 上海金发科技发展有限公司 | 一种abs复合材料及其制备方法 |
| CN114736453B (zh) * | 2022-03-14 | 2023-09-26 | 金发科技股份有限公司 | 一种低卤阻燃pp材料及其制备方法和应用 |
| CN114573942B (zh) * | 2022-03-23 | 2023-11-03 | 金发科技股份有限公司 | 一种abs组合物及其制备方法和应用 |
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