WO2020108203A1 - 一种高阻燃等级hips复合材料 - Google Patents

一种高阻燃等级hips复合材料 Download PDF

Info

Publication number
WO2020108203A1
WO2020108203A1 PCT/CN2019/113841 CN2019113841W WO2020108203A1 WO 2020108203 A1 WO2020108203 A1 WO 2020108203A1 CN 2019113841 W CN2019113841 W CN 2019113841W WO 2020108203 A1 WO2020108203 A1 WO 2020108203A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame retardant
parts
composite material
inorganic filler
hips composite
Prior art date
Application number
PCT/CN2019/113841
Other languages
English (en)
French (fr)
Inventor
王亮
叶南飚
邹声文
秦旺平
付锦锋
杜荣华
刘凯
杨霄云
Original Assignee
金发科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Publication of WO2020108203A1 publication Critical patent/WO2020108203A1/zh

Links

Classifications

    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • 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
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a high flame retardant grade HIPS composite material.
  • Polystyrene (PS) includes ordinary polystyrene, expanded polystyrene (EPS), high impact polystyrene (HIPS) and syndiotactic polystyrene (SPS).
  • EPS expanded polystyrene
  • HIPS high impact polystyrene
  • SPS syndiotactic polystyrene
  • High impact polystyrene is produced by blending a small amount of elastomer in PS, which overcomes the shortcomings of brittleness of polystyrene, so it is widely used in internal and external components of household appliances and office automation equipment. Such as monitors, video recorders, copiers, fax machines, printers, air conditioners, refrigerators, etc. Styrene-based polymers are easy to burn.
  • Existing flame retardant modification technology has been able to solve the flame-retardant problems of styrene-based polymers, and can provide environmental protection, high weather resistance, good environmental compatibility, No dioxin/difuran problem, flame retardant styrene polymer compound with good thermal stability and good processability.
  • halogenated flame retardant such as adding bromine-containing flame retardant and antimony oxide flame retardant synergist to achieve flame retardant effect
  • halogen-free flame retardant For example, adding phosphorus-containing, nitrogen-containing flame retardants and carbon-forming agent.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a high flame retardant grade HIPS composite material.
  • the technical solution adopted by the present invention is: a high flame retardant grade HIPS composite material, comprising the following parts by weight of components: PS resin 40 to 60 parts, thermoplastic styrene butadiene rubber 10 to 27 parts, toughening agent 3 to 10 parts, 10 to 18 parts of flame retardant, 2.5 to 6 parts of flame retardant synergist, 5 to 20 parts of inorganic filler, 0.1 to 0.5 parts of anti-drip agent, and 0 to 2 parts of additives;
  • the weight average molecular weight of the resin is greater than or equal to 15*10 4 g/mol, and the melt flow rate MFR is 3 to 6 g/10 min.
  • the molecular weight of the PS matrix resin is medium
  • the high flame retardant grade HIPS composite material of the present invention selects a high molecular weight PS resin, and the poor flowability of the high molecular weight matrix is not easy to drip and burn through, so the present invention
  • the PS resin of the above molecular weight is selected.
  • the content of commercially available ordinary HIPS resin rubber generally accounts for only 8-9%. Increasing the rubber content is beneficial to increasing the viscosity of the material, making the melt of the material difficult to flow during combustion, and helping to achieve 5VA flame retardancy.
  • HIPS composite material made by the above formula: 1. High flame retardant grade, up to 2.0mm and 5VA grade; 2. Good overall performance, balanced strength and notched impact performance; 3. Low cost, can replace high flame retardant in some occasions Grade ABS; 4. Good appearance and wide processing window.
  • the high flame retardant grade HIPS material can be used in the field of household appliances and electronic products with high performance and flame retardant grade requirements.
  • the average aspect ratio of the inorganic filler is ⁇ 5:1. Because the inorganic filler cannot be burnt, the inorganic fillers of this aspect ratio can be staggered together to play a role as a framework support, making the material difficult to burn through.
  • the average aspect ratio of the inorganic filler is ⁇ 10:1, and the diameter of the inorganic filler is D50 ⁇ 8 ⁇ m.
  • the flame retardant effect is better when the inorganic filler is used.
  • the inorganic filler is at least one of talc powder, inorganic salt whiskers, marble powder, mica powder, calcium metasilicate, kaolin and montmorillonite One; the inorganic salt whiskers are at least one of SiC whiskers, potassium titanate whiskers, aluminum borate whiskers, calcium sulfate whiskers, calcium carbonate whiskers, aluminum oxide whiskers, and zinc oxide whiskers.
  • the toughening agent is chlorinated polyethylene, and the weight percentage of chlorine in the chlorinated polyethylene is 30-40%.
  • the chlorinated polyethylene is used as a toughening agent, in the system of the present invention, the flame retardant effect and the toughening effect are superior to other toughening agents.
  • the toughening agent is chlorinated polyethylene.
  • the thermoplastic styrene-butadiene rubber is polystyrene-polybutadiene-polystyrene triblock copolymer and hydrogenated styrene-butadiene- At least one of styrene block copolymers; the weight percentage of styrene in the thermoplastic styrene-butadiene rubber is 20-40%.
  • the flame retardant is tris(tribromophenoxy)triazine, brominated epoxy, decabromodiphenylethane, brominated polyacryl At least one of imine, brominated polystyrene, polybrominated styrene, brominated polycarbonate, and brominated polyacrylate.
  • the flame retardant is preferably a bromine-based flame retardant; more preferably the above-mentioned bromine-based flame retardant.
  • the flame retardant synergist is antimony trioxide, colloidal antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, At least one of antimony phosphite, antimony polyphosphate, and complex antimony.
  • the anti-dripping agent is polytetrafluoroethylene;
  • the auxiliary agent includes at least one of an antioxidant, a lubricant, a weathering agent, and a colorant Species.
  • the antioxidant includes a hindered phenolic antioxidant and a phosphite antioxidant
  • the lubricant includes an amide lubricant and stearic acid At least one of a salt lubricant, an ester lubricant, and a silicone lubricant
  • the weathering agent includes a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a hindered amine light stabilizer At least one of them.
  • the colorant includes at least one of a pigment type, a dye type, and other colorants having special aesthetic effects.
  • the invention also provides a preparation method of the high flame retardant grade HIPS 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 a high flame retardant grade HIPS material.
  • the beneficial effect of the present invention is that the present invention provides a high flame retardant grade HIPS composite material.
  • the high flame retardant grade HIPS composite material of the present invention 1. High flame retardant grade, can reach 2.0mm and 5VA grade at the highest; 2. Good overall performance, balanced strength and notch impact performance; 3. Low cost, can replace high in some occasions Flame retardant ABS; 4. Good appearance, wide processing window.
  • the PS resin was selected from GPPS-500NT of PetroChina Dushanzi Petrochemical Company and GPPS 123P of Shanghai Secco Petrochemical Co., Ltd.
  • the weight-average molecular weight of GPPS-500NT was about 18*10 4 g/ mol, the weight-average molecular weight of GPPS 123P is about 13*10 4 g/mol; the weight-average molecular weight of ordinary HIPS resin is less than 15*10 4 g/mol;
  • the thermoplastic styrene-butadiene rubber is selected from SBS LG501S of South Korea LG Chemical; the choice of ordinary HIPS resin is HIPS MA5210 produced by Chevron Phillips; toughening agent selected is CPE 235C of Hangzhou Keli Chemical Co., Ltd., POE 1450 of polyolefin elastomer of DOW Chemical Company of the United States, EPDM Vistalon 3666 of ExxonMobil of the United States; flame retardant Tris(trib
  • HTPUltra5L, HTPUltra5L talc powder has a length-to-diameter ratio of more than 90wt% particles ⁇ 5:1; anti-dripping agent selects Guangzhou Entropy SN80-SA7; other additives use antioxidants: lubricant mass ratio 3:5 mixture.
  • the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 produced by Shanghai Ciba Refining and Chemicals Co., Ltd. in a weight ratio of 1:2.
  • the lubricant is Zhongshan Huamingtai Chemical Co., Ltd. The company's zinc stearate BS-2818.
  • the preparation method of the HIPS 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 to 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 HIPS composite material.
  • the HIPS composite material formulations of Examples 6-9 differ from Example 4 only in the ratio of the toughening agent and the inorganic filler.
  • the HIPS composite material formulations of Examples 6-9 are shown in Table 2.
  • Example 6 Example 7
  • Example 8 Example 9 PS resin: GPPS-500NT 48 48 48 48 Thermoplastic SBR 20 20 20 20 20 Toughener CPE235C 3 3.75 7.5 10 Flame retardant FR-245 12 12 12 12 Flame retardant synergist 4 4 4 4 Inorganic filler 12 11.25 7.5 5 Anti-dripping agent 0.2 0.2 0.2 0.2 Additives 0.8 0.8 0.8 0.8
  • ABS composite material formulations of Examples 10-12 are different from Example 4 only in the types of tougheners.
  • the ABS composite material formulations of Examples 10-12 are shown in Table 3.
  • HIPS composite materials prepared by 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 4 above; Such performance test data is shown in Tables 5-7.
  • Example 1 and Comparative 1 ratio of weight average molecular weight is less than 15 * 10 4 g / mol of PS resin and a GPPS 123P HIPS resin and general level of flame retardancy was significantly lower than in Example 1, a When the PS resin weight average molecular weight is greater than 15*10 4 g/mol, it can effectively improve the flame retardant grade of the HIPS composite material. It can be seen from the comparison between Example 1 and Comparative Example 3 that the inorganic filler can significantly improve the flame retardant grade of the HIPS composite material.
  • thermoplastic styrene-butadiene rubber can improve the flame retardant grade and impact resistance of the HIPS composite material. It can be seen from the comparison between Example 1 and Comparative Example 5 that increasing the content of thermoplastic styrene-butadiene rubber contributes to increasing the flame retardant grade in the HIPS composite material system of the present invention. It can be seen from the comparison between Example 4 and Comparative Example 6 that the PS resin with a higher molecular weight has a higher flame retardant grade in the HIPS composite material system of the present invention.
  • Example 6 Example 7
  • Example 8 Example 9 IZOD notched impact strength (kJ/m 2 ) 8.5 10 13 15 Burning/2.0mm V-0 5VB 5VB V-0 Burning/2.5mm V-0 5VA 5VA V-0 Burning/3.0mm 5VA 5VA 5VA 5VB
  • Example 10 Example 11
  • Example 12 IZOD notched impact strength (kJ/m 2 ) 13 10 9 Burning/2.0mm 5VB 5VB 5VB Burning/2.5mm 5VB 5VB 5VB Burning/3.0mm 5VA 5VA 5VA

Landscapes

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

Abstract

一种高阻燃等级HIPS复合材料，包含以下重量份的组分：PS树脂40～60份、热塑性丁苯橡胶10～27份、增韧剂3～10份、阻燃剂10～18份、阻燃协效剂2.5～6份、无机填充物5～20份、抗滴落剂0.1～0.5份和助剂0～2份；所述PS树脂的重均分子量大于等于15×10 4g/mol，熔体流动速率MFR为3～6g/10min。所述高阻燃等级HIPS复合材料：1、阻燃等级高，最高可以达到2.0mm 5VA等级；2、综合性能好，强度和缺口冲击性能均衡；3、成本低，部分场合可以替代高阻燃等级ABS；4、外观好，加工窗口宽。

Description

一种高阻燃等级HIPS复合材料 技术领域
本发明涉及工程塑料技术领域，具体涉及一种高阻燃等级HIPS复合材料。
背景技术
聚苯乙烯(PS)包括普通聚苯乙烯、发泡聚苯乙烯(EPS)、高抗冲聚苯乙烯(HIPS)及间规聚苯乙烯(SPS)，BASF于1930年开始在德国商业化生产聚苯乙烯。作为五大通用塑料之一，它具有成形性优良、质硬、透明、刚性、电绝缘性、低吸湿性、容易染色和价格低廉等优点。
高抗冲聚苯乙烯(HIPS)是在PS中掺入少量弹性体后产生出来的，其克服了聚苯乙烯性脆的缺点，因而广泛用于家用电器及办公自动化设备的内部及外部构件，如显示器、录像机、复印机、传真机、打印机、空调器、电冰箱等。苯乙烯类聚合物容易燃烧，现有的阻燃改性技术已经能较好地解决苯乙烯类聚合物的阻燃问题，可以根据需要提供环保的、高耐候的、与环境相容性好、无二噁暎/二呋喃问题，热稳定性好、加工性能良好的阻燃苯乙烯类聚合物复合物。这些阻燃改性技术主要有两大类：一类是有卤阻燃，例如加入含溴的阻燃剂和氧化锑阻燃协效剂来达到阻燃效果；另一类是无卤阻燃，例如加入含磷、含氮阻燃剂和成炭剂。由于第一类(有卤阻燃)阻燃技术成本相对较低，阻燃效率高，是目前应用最广泛的技术。
随着社会的发展，以及人们对安全的日益重视，部分家用电器、电子产品对材料的阻燃提出了更高要求，例如冰箱、微波炉等电子控制器外壳，要求5VA阻燃，厚度也随着设计趋势变得越来越薄(2.5-2.0mm)，现有普通V-0阻燃HIPS材料已不能满足该要求。
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高阻燃等级 HIPS复合材料。
为实现上述目的，本发明采取的技术方案为：一种高阻燃等级HIPS复合材料，包含以下重量份的组分：PS树脂40～60份、热塑性丁苯橡胶10～27份、增韧剂3～10份、阻燃剂10～18份、阻燃协效剂2.5～6份、无机填充物5～20份、抗滴落剂0.1～0.5份和助剂0～2份；所述PS树脂的重均分子量大于等于15*10 4g/mol，熔体流动速率MFR为3～6g/10min。
市售的普通的HIPS树脂，PS基体树脂的分子量属于中等，本发明所述高阻燃等级HIPS复合材料选用高分子量的PS树脂，高分子量基体流动性差不容易滴落和烧穿，因此本发明选用上述分子量的PS树脂。另外，市售的普通的HIPS树脂橡胶的含量一般只占8～9％，提高橡胶含量有利于提升材料的粘度，使燃烧时材料熔体不易流动，有利于实现5VA阻燃。采用上述配方制得的HIPS复合材料：1、阻燃等级高，最高可以达到2.0mm 5VA等级；2、综合性能好，强度和缺口冲击性能均衡；3、成本低，部分场合可以替代高阻燃等级ABS；4、外观好，加工窗口宽。该高阻燃等级HIPS材料可用于性能和阻燃等级要求较高的家用电器、电子产品领域。
作为本发明所述高阻燃等级HIPS复合材料的优选实施方式，所述无机填充物的平均长径比≥5:1。因为无机填充物不能燃烧，该长径比的无机填充物并能交错搭在一起，起到骨架支撑的作用，使材料不易烧穿。
作为本发明所述高阻燃等级HIPS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，所述无机填充物的直径D50≤8μm。采用该无机填充物时阻燃效果更佳。
作为本发明所述高阻燃等级HIPS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；所述无机盐晶须为SiC晶须、钛酸钾晶须、硼酸铝晶须、硫酸钙晶须、碳酸钙晶须、氧化铝晶须和氧化锌晶须中的至少一种。
作为本发明所述高阻燃等级HIPS复合材料的优选实施方式，所述增韧剂为氯化聚乙烯，所述氯化聚乙烯中氯的重量百分含量为30～40％。采用该氯化聚乙 烯为增韧剂时，在本发明的体系中，阻燃效果和增韧效果均优于其他增韧剂。
作为本发明所述高阻燃等级HIPS复合材料的优选实施方式，所述增韧剂与无机填充物的重量之比为：增韧剂：无机填充物＝1:3～1:1。增韧剂为氯化聚乙烯，氯化聚乙烯与无机填充物采用上述配比时，能与无机填充物发挥协同增效的阻燃效果，并且在该范围内阻燃和机械性能比较均衡，超过该范围的材料性能实用价值不大。
优选地，所述增韧剂与无机填充物的重量之比为：增韧剂：无机填充物＝1:2。尤其是在该配比下，阻燃效果最佳。
作为本发明所述高阻燃等级HIPS复合材料的优选实施方式，所述热塑性丁苯橡胶为聚苯乙烯—聚丁二烯—聚苯乙烯三嵌段共聚物和氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物中至少一种；所述热塑性丁苯橡胶中的苯乙烯重量百分含量为20～40％。
作为本发明所述高阻燃等级HIPS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、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。阻燃剂优选采用溴系阻燃剂；更优选为上述溴系阻燃剂。
作为本发明所述高阻燃等级HIPS复合材料的优选实施方式，所述阻燃协效剂为三氧化二锑、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。
作为本发明所述高阻燃等级HIPS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。
作为本发明所述高阻燃等级HIPS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高阻燃等级HIPS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、干燥得到高阻燃等级HIPS材料。
本发明的有益效果在于：本发明提供了一种高阻燃等级HIPS复合材料。本发明所述高阻燃等级HIPS复合材料：1、阻燃等级高，最高可以达到2.0mm 5VA等级；2、综合性能好，强度和缺口冲击性能均衡；3、成本低，部分场合可以替代高阻燃等级ABS；4、外观好，加工窗口宽。
具体实施方式
实施例和对比例的原料中，PS树脂选用中石油独山子石化分公司的GPPS-500NT和上海赛科石油化工有限责任公司的GPPS 123P，GPPS-500NT的重均分子量约为18*10 4g/mol，GPPS 123P的重均分子量约为13*10 4g/mol；普通HIPS树脂的重均分子量小于15*10 4g/mol；热塑性丁苯橡胶选用韩国LG化学的SBS LG501S；普通HIPS树脂选用雪佛龙菲利普斯生产的HIPS MA5210；增韧剂选用杭州科利化工股份有限公司的CPE 235C，美国DOW化学公司的聚烯烃弹性体POE 1450，美国埃克森美孚的EPDM Vistalon 3666；阻燃剂选用以色列死海溴公司的三(三溴苯氧基)三嗪FR-245；阻燃协效剂选用三氧化二锑，由华昌锑业公司生产；无机填充物选用意大利依米发比(IMIFABI)滑石粉HTPUltra5L，HTPUltra5L的滑石粉中90wt％以上颗粒的长径比≥5:1；抗滴落剂选用广州熵能公司的SN80-SA7；其它助剂选用抗氧剂：润滑剂质量比为3:5的混合物，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，润滑剂选用中山华明泰化工股份有限公司的硬脂酸锌BS-2818。
实施例和对比例的HIPS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HIPS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1～5和对比例1～6
实施例1～5和对比例1～6的HIPS复合材料配方见表1。
表1实施例1～5和对比例1～6的HIPS复合材料配方
Figure PCTCN2019113841-appb-000001
Figure PCTCN2019113841-appb-000002
“-”表示不添加。
实施例6～9
实施例6～9的HIPS复合材料配方与实施例4的不同之处仅在于增韧剂和无机填充物的比值的不同，实施例6～9的HIPS复合材料配方见表2。
表2实施例6～9的HIPS复合材料配方
原料(重量份) 实施例6 实施例7 实施例8 实施例9
PS树脂：GPPS-500NT 48 48 48 48
热塑性丁苯橡胶 20 20 20 20
增韧剂CPE235C 3 3.75 7.5 10
阻燃剂FR-245 12 12 12 12
阻燃协效剂 4 4 4 4
无机填充物 12 11.25 7.5 5
抗滴落剂 0.2 0.2 0.2 0.2
助剂 0.8 0.8 0.8 0.8
实施例10～12
实施例10～12的ABS复合材料配方与实施例4的不同之处仅在于增韧剂的种类的不同，实施例10～12的ABS复合材料配方见表3。
表3实施例10～12的HIPS复合材料配方
Figure PCTCN2019113841-appb-000003
Figure PCTCN2019113841-appb-000004
“-”表示不添加。
实施例13
产品性能测试方法见表4。
表4性能测试方法
性能指标 测试条件 测试方法
IZOD缺口冲击强度 23℃ ISO180
阻燃等级测试 2.0-3.0mm UL94
将上述各实施例和对比例所制得的HIPS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4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5～7所示。
表5实施例1～5和对比例1～6的试样的性能测试数据
Figure PCTCN2019113841-appb-000005
从表5的数据可以看出，实施例1～5的阻燃效果均较好，有些实施例能达 到2mm5VA等级，且缺口冲击性能较好。从实施例1和对比例1、2的比较可以看出，重均分子量低于15*10 4g/mol的PS树脂GPPS 123P和普通HIPS树脂和的阻燃等级明显低于实施例1，说明PS树脂重均分子量大于15*10 4g/mol时，能有效提高HIPS复合材料的阻燃等级。从实施例1和对比例3的比较可以看出，无机填充物能明显提高HIPS复合材料的阻燃等级。从实施例1和对比例4的比较可以看出，热塑性丁苯橡胶能提高HIPS复合材料的阻燃等级和抗冲击性能。从实施例1和对比例5的比较可以看出，增加热塑性丁苯橡胶的含量在本发明HIPS复合材料体系内有助于增加阻燃等级。从实施例4和对比例6的比较可以看出，分子量较高的PS树脂在本发明HIPS复合材料体系内的阻燃等级更高。
表6实施例6～9试样的性能测试数据
测试项目 实施例6 实施例7 实施例8 实施例9
IZOD缺口冲击强度(kJ/m 2) 8.5 10 13 15
燃烧/2.0mm V-0 5VB 5VB V-0
燃烧/2.5mm V-0 5VA 5VA V-0
燃烧/3.0mm 5VA 5VA 5VA 5VB
从表5、6中实施例4、6～9的比较可以看出，在增韧剂与无机填充物总添加量一致的情况下，当增韧剂与无机填充物的配比为增韧剂：无机填充物＝1:3～1:1时，阻燃效果优于其他配比，说明在该配比时，增韧剂和无机填充物能相互补充，发挥协同增效的效果，尤其是当增韧剂：无机填充物＝1:2时，阻燃效果最好。
表7实施例10～12试样的性能测试数据
测试项目 实施例10 实施例11 实施例12
IZOD缺口冲击强度(kJ/m 2) 13 10 9
燃烧/2.0mm 5VB 5VB 5VB
燃烧/2.5mm 5VB 5VB 5VB
燃烧/3.0mm 5VA 5VA 5VA
从表5、7中实施例4、10～12的比较可以看出，当增韧剂为氯化聚乙烯时，阻燃效果和机械性能比较均衡。
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. 一种高阻燃等级HIPS复合材料，其特征在于，包含以下重量份的组分：PS树脂40～60份、热塑性丁苯橡胶10～27份、增韧剂3～10份、阻燃剂10～18份、阻燃协效剂2.5～6份、无机填充物5～20份、抗滴落剂0.1～0.5份和助剂0～2份；所述PS树脂的重均分子量大于等于15*10 4g/mol，熔体流动速率MFR为3～6g/10min。
  2. 如权利要求1所述高阻燃等级HIPS复合材料，其特征在于，所述无机填充物的平均长径比≥5:1；优选地，所述无机填充物的平均长径比≥10:1，所述无机填充物的直径D50≤8μm。
  3. 如权利要求2所述高阻燃等级HIPS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；所述无机盐晶须为SiC晶须、钛酸钾晶须、硼酸铝晶须、硫酸钙晶须、碳酸钙晶须、氧化铝晶须和氧化锌晶须中的至少一种。
  4. 如权利要求1所述高阻燃等级HIPS复合材料，其特征在于，所述增韧剂为氯化聚乙烯，所述氯化聚乙烯中氯的重量百分含量为30～40％。
  5. 如权利要求4所述高阻燃等级HIPS复合材料，其特征在于，所述增韧剂与无机填充物的重量之比为：增韧剂：无机填充物＝1:3～1:1；优选地，所述增韧剂与无机填充物的重量之比为：增韧剂：无机填充物＝1:2。
  6. 如权利要求1所述高阻燃等级HIPS复合材料，其特征在于，所述热塑性丁苯橡胶为聚苯乙烯—聚丁二烯—聚苯乙烯三嵌段共聚物和氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物中至少一种；所述热塑性丁苯橡胶中的苯乙烯重量百分含量为20～40％。
  7. 如权利要求1所述高阻燃等级HIPS复合材料，其特征在于，所述阻燃剂为三(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。
  8. 如权利要求1所述高阻燃等级HIPS复合材料，其特征在于，所述阻燃 协效剂为三氧化二锑、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。
  9. 如权利要求1所述高阻燃等级HIPS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。
  10. 如权利要求1所述高阻燃等级HIPS复合材料，其特征在于，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。
PCT/CN2019/113841 2018-11-27 2019-10-29 一种高阻燃等级hips复合材料 WO2020108203A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811429805.2 2018-11-27
CN201811429805.2A CN109503970B (zh) 2018-11-27 2018-11-27 一种高阻燃等级hips复合材料

Publications (1)

Publication Number Publication Date
WO2020108203A1 true WO2020108203A1 (zh) 2020-06-04

Family

ID=65750846

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/113841 WO2020108203A1 (zh) 2018-11-27 2019-10-29 一种高阻燃等级hips复合材料

Country Status (2)

Country Link
CN (1) CN109503970B (zh)
WO (1) WO2020108203A1 (zh)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109503970B (zh) * 2018-11-27 2021-09-07 金发科技股份有限公司 一种高阻燃等级hips复合材料
CN110218398A (zh) * 2019-06-14 2019-09-10 晋江市春水衣架有限公司 一种塑料衣架及其制备方法
CN110951207A (zh) * 2019-12-12 2020-04-03 武汉金发科技有限公司 一种阻燃abs复合材料
CN112608561B (zh) * 2020-11-26 2022-07-12 金发科技股份有限公司 一种高韧高光泽gpps/cpe复合材料及其制备方法和应用
CN112745591B (zh) * 2020-12-21 2022-10-04 武汉金发科技有限公司 一种阻燃高刚性ps/ppe复合材料及其制备方法和应用
CN112724574B (zh) * 2020-12-21 2022-12-06 武汉金发科技有限公司 一种阻燃高刚性acs复合材料及其制备方法和应用
CN114591588B (zh) * 2022-03-18 2023-08-25 广东圆融新材料有限公司 一种阻燃吸波pc/asa复合材料及其制备方法
CN115181344B (zh) * 2022-07-28 2023-08-22 金发科技股份有限公司 一种高耐热阻燃hips材料及其制备方法和应用
CN115556443A (zh) * 2022-09-29 2023-01-03 常州市贝美家居科技有限公司 一种轻质隔音墙板及其生产工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875746A (zh) * 2010-05-14 2010-11-03 金发科技股份有限公司 苯乙烯系无卤阻燃型注塑级木塑复合材料及其制备方法
CN102604246A (zh) * 2012-03-19 2012-07-25 上海锦湖日丽塑料有限公司 高效阻燃的苯乙烯类树脂组合物
CN103709703A (zh) * 2013-12-11 2014-04-09 上海交通大学 回收碳纤维再生利用增强热塑性树脂复合材料及其制备方法
CN105462144A (zh) * 2015-12-11 2016-04-06 天津金发新材料有限公司 一种抗静电阻燃hips材料及其制备方法
CN108623968A (zh) * 2018-04-16 2018-10-09 安徽江淮汽车集团股份有限公司 一种低收缩、阻燃高抗冲聚苯乙烯材料及制备方法
CN109503970A (zh) * 2018-11-27 2019-03-22 金发科技股份有限公司 一种高阻燃等级hips复合材料

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0125873B1 (ko) * 1992-12-21 1997-12-26 채오병 난연성이 우수한 에이치아이피에스(hips) 수지 조성물
CN106380770A (zh) * 2016-08-26 2017-02-08 青岛海尔新材料研发有限公司 一种阻燃苯乙烯类树脂组合物及其制备方法
CN106221104A (zh) * 2016-08-26 2016-12-14 青岛海尔新材料研发有限公司 阻燃苯乙烯类树脂组合物及其制备方法
CN106633580A (zh) * 2016-10-17 2017-05-10 珠海格力电器股份有限公司 具有高耐热性、高阻燃等级的抗冲击性聚苯乙烯复合材料、其制备方法及用途
CN106751336A (zh) * 2016-12-14 2017-05-31 广东圆融新材料有限公司 一种高cti值的溴系阻燃hips材料及其制备方法
CN107603111A (zh) * 2017-08-17 2018-01-19 合肥会通新材料有限公司 一种低气味、低voc阻燃改性hips材料及其制备方法
CN107501834A (zh) * 2017-08-22 2017-12-22 合肥会通新材料有限公司 一种电器外壳用低气味、高光泽和高流动性的阻燃hips材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101875746A (zh) * 2010-05-14 2010-11-03 金发科技股份有限公司 苯乙烯系无卤阻燃型注塑级木塑复合材料及其制备方法
CN102604246A (zh) * 2012-03-19 2012-07-25 上海锦湖日丽塑料有限公司 高效阻燃的苯乙烯类树脂组合物
CN103709703A (zh) * 2013-12-11 2014-04-09 上海交通大学 回收碳纤维再生利用增强热塑性树脂复合材料及其制备方法
CN105462144A (zh) * 2015-12-11 2016-04-06 天津金发新材料有限公司 一种抗静电阻燃hips材料及其制备方法
CN108623968A (zh) * 2018-04-16 2018-10-09 安徽江淮汽车集团股份有限公司 一种低收缩、阻燃高抗冲聚苯乙烯材料及制备方法
CN109503970A (zh) * 2018-11-27 2019-03-22 金发科技股份有限公司 一种高阻燃等级hips复合材料

Also Published As

Publication number Publication date
CN109503970A (zh) 2019-03-22
CN109503970B (zh) 2021-09-07

Similar Documents

Publication Publication Date Title
WO2020108203A1 (zh) 一种高阻燃等级hips复合材料
CN109627671B (zh) 一种abs复合材料
CN103396607A (zh) 一种阻燃增强的抗静电pp复合材料及其制备方法
KR101482027B1 (ko) 저경도 열가소성 고무 조성물 및 이를 포함하는 다이아프램
CN107955368B (zh) 一种改进耐热性的导热尼龙及其制备方法
KR20120075053A (ko) 난연성 열가소성 수지 조성물
KR101425285B1 (ko) 난연 폴리프로필렌 수지 조성물
CN111019242A (zh) 一种抗冲击、耐热、阻燃mpp电力管料及其制备方法
CN103073809B (zh) 一种高冲击高耐候环保溴系阻燃asa材料及其制备方法与应用
EP3504261B1 (en) Flame-retarded polyamide composition
US9670361B2 (en) Halogen based flame retardant glass fiber reinforced polyamide resin composition and method for preparing the same
WO2013057841A1 (ja) 難燃剤マスターバッチ及びそれを使用したスチレン系難燃性樹脂組成物の製造方法
JP6128926B2 (ja) 難燃剤マスターバッチ、その製造方法、及びそれを使用したスチレン系難燃性樹脂組成物の製造方法
CN102816405B (zh) 一种低烟无卤阻燃热塑性弹性体及其制备方法
CN105131576A (zh) 一种无卤阻燃环保移动电源用柔软型线缆护套料及其制备方法
CN103923395A (zh) 汽车内饰件用无卤阻燃耐热pp塑料及其制备方法
JP6155058B2 (ja) ポリフェニレンエーテル系樹脂組成物、成形品および太陽光発電モジュール用接続構造体
CN108219351B (zh) 低内应力、高抗冲阻燃abs组合物及其制备方法和应用
CN110713684A (zh) 一种abs复合材料及其应用
JP2013518957A (ja) 五酸化アンチモンを含む芳香族ビニルポリマーをベースにした耐火組成物
CN102585377B (zh) 一种阻燃聚丙烯材料及其制备方法
CN114133691A (zh) 一种无卤阻燃抗菌abs材料及其制备方法
JPH07122014B2 (ja) 難燃性ゴム変性スチレン系樹脂組成物
WO2022110661A1 (zh) 一种高韧高光泽gpps/cpe复合材料及其制备方法和应用
JP2018087261A (ja) 再生ポリスチレン樹脂組成物およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19890029

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19890029

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 22.12.2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19890029

Country of ref document: EP

Kind code of ref document: A1