WO2022110663A1 - 一种低烟密度含卤阻燃增强pbt/pet复合物及其制备方法和应用 - Google Patents

一种低烟密度含卤阻燃增强pbt/pet复合物及其制备方法和应用 Download PDF

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WO2022110663A1
WO2022110663A1 PCT/CN2021/092768 CN2021092768W WO2022110663A1 WO 2022110663 A1 WO2022110663 A1 WO 2022110663A1 CN 2021092768 W CN2021092768 W CN 2021092768W WO 2022110663 A1 WO2022110663 A1 WO 2022110663A1
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pet
pbt
halogen
smoke density
flame retardant
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French (fr)
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陈伟
黄险波
叶南飚
冯健
陈锐
付学俊
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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention relates to the technical field of engineering plastics, and more particularly, to a low smoke density halogen-containing flame retardant reinforced PBT/PET compound and a preparation method and application thereof.
  • Plastic materials are generally accompanied by a large amount of smoke during the combustion process, which will cause environmental pollution and cause great harm to the human body.
  • low smoke flame retardant has become a new direction for the development of flame retardant plastics.
  • Rail transit, building materials, cables and other industries have increasingly clear and standardized requirements for low-smoke flame retardant.
  • Such industries have clearly required that the plastic parts in the application must meet the smoke density level 2 or above required by the EN45545-2 standard. (Level 2 requires ISO5659-2 test smoke density Ds max ⁇ 300).
  • Polybutylene terephthalate is obtained by the polymerization of terephthalic acid and butanediol through a polycondensation reaction.
  • glass fiber reinforced PBT materials have been widely used in lighting fixtures, cooling fans, connectors , coil bobbins, electrical enclosures and other electrical and electronic components.
  • the pressure of cost also forces changes.
  • glass fiber reinforced PBT/PET alloy materials with better performance came into being.
  • Polyethylene terephthalate (PET) has good heat resistance and low cost, and PET can effectively prevent glass fibers from being exposed in the glass fiber reinforced PBT system, and has the effect of high gloss on the surface of the product.
  • Chinese patent application CN 102532826 A discloses a low-cost flame retardant glass fiber reinforced PBT engineering plastic.
  • the flame retardant glass fiber reinforced PBT engineering plastic utilizes the smoke suppression effect of silicate to obtain a low cost flame retardant glass fiber reinforced PBT.
  • Engineering plastics have good flame retardancy, but their smoke density cannot meet the level 3 of the EN45545-2 standard.
  • the present invention provides a low smoke density halogen-containing flame retardant reinforced PBT/PET compound, the low smoke density halogen-containing flame retardant reinforced PBT/PET compound.
  • the PET compound has good gloss, flame retardancy, and the smoke density reaches the level 3 of the EN45545-2 standard.
  • Another object of the present invention is to provide a preparation method of the above-mentioned low smoke density halogen-containing flame retardant reinforced PBT/PET composite.
  • Another object of the present invention is to provide the application of the above-mentioned low smoke density halogen-containing flame retardant reinforced PBT/PET compound.
  • the technical scheme adopted in the present invention is:
  • a halogen-containing flame-retardant reinforced PBT/PET compound with low smoke density comprising the following components by weight:
  • PET polyethylene terephthalate
  • the PBT to PET weight ratio is (1 ⁇ 4): 1,
  • the particle size D 50 of the magnesium stearate is less than or equal to 5 ⁇ m.
  • Described magnesium stearate is preferably the product of Jiangxi Hongyuan Chemical's trade mark YZM-32C.
  • the molecular formula of boehmite is ⁇ -AlOOH, and the average grain size of boehmite described in this application is ⁇ 10 nm.
  • Boehmite with lower grain size has special physical and chemical properties different from boehmite with large grain size due to its low density, larger surface area, special structure and morphology.
  • the halogen-containing flame retardant reinforced PBT/PET system can more significantly reduce the amount of smoke generated when the material is burned.
  • the average grain size of the boehmite is preferably 10-20 nm.
  • the boehmite is preferably a product of Nanjing Apry Nanomaterials Co., Ltd. whose model is Boehmite 235.
  • the particle size of the kaolin is preferably D 50 ⁇ 0.5 ⁇ m.
  • the pH value of the kaolin is preferably 4-5.
  • the kaolin is preferably the product of Hangzhou Chongke New Materials Co., Ltd. with the brand name of Eckalite 1 PLUS.
  • the weight ratio of the boehmite, kaolin, and magnesium stearate is 1:(1-2):1.
  • the inventor's research found that when boehmite, kaolin, and magnesium stearate are compounded in a weight ratio of 1: (1-2): 1, the prepared halogen-containing flame retardant reinforced PBT/PET composite can obtain better performance. smoke suppression effect.
  • the intrinsic viscosity of the PBT is 0.7-1.3 dL/g at 25°C
  • the intrinsic viscosity of the PET is 0.5-0.8 dL/g at 25°C.
  • the intrinsic viscosity test method is based on GB/T 14190-2017.
  • the PBT/PET compound can obtain better comprehensive properties.
  • the brominated flame retardant can be a brominated flame retardant commonly used in PBT or PET systems, such as polymer brominated epoxy, brominated polystyrene, brominated polycarbonate flame retardant, decabromodiphenyl ether. Wait.
  • the brominated flame retardant is preferably one or more of polymer brominated epoxy, brominated polystyrene and brominated polycarbonate flame retardants. These brominated flame retardants are more environmentally friendly.
  • the synergistic flame retardant is preferably antimony white.
  • the weight ratio of the brominated flame retardant to the synergistic flame retardant is (2-4):1.
  • the glass fibers are treated with a coupling agent.
  • the coupling agent is N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane and isopropylbis( The blend of methacryloyl) isostearoyl titanate, the blending weight ratio of the three is 1:2:1.
  • the epoxy resin is bisphenol A glycidyl ether, and the epoxy equivalent is 2500-3100 g/eq.
  • the epoxy equivalent test method is based on GB/T 4612-2008.
  • epoxy resin can significantly improve the performance stability of PBT/PET composites.
  • the present invention also protects the preparation method of the above-mentioned low smoke density halogen-containing flame retardant reinforced PBT/PET compound, comprising the steps:
  • the first premix and the second premix are added to the extruder, mixed, dispersed, melted, extruded and granulated to obtain a low smoke density halogen-containing flame retardant reinforced PBT/PET compound.
  • the extruder is a twin-screw extruder.
  • the temperature of the first zone of the twin-screw extruder from the feeding port to the die head is 200-230°C
  • the temperature of the second zone is 240-260°C
  • the temperature of the third zone is 235-255°C
  • the temperature of the fourth zone is 235 ⁇ 255°C
  • five zone temperature is 235 ⁇ 255°C
  • six zone temperature is 240 ⁇ 260°C
  • seventh zone temperature is 240 ⁇ 260°C
  • eighth zone temperature is 220 ⁇ 240°C
  • ninth zone temperature is 220 ⁇ 240°C
  • the temperature in the tenth zone is 240-260° C.
  • the screw speed of the twin-screw extruder is 200-450 rpm.
  • the present invention also protects the application of the above-mentioned low-smoke-density halogen-containing flame-retardant reinforced PBT/PET compound in the preparation of plastic parts for rail transit, building materials or cables.
  • the invention develops a halogen-containing flame-retardant reinforced PBT/PET compound with low smoke density and good surface gloss.
  • the smoke density of the PBT/PET compound reaches the level 3 smoke density required by the EN45545-2 standard, and the smoke density Ds max is less than or equal to 150 in the ISO5659-2 test.
  • the PET/PET products made from this PBT/PET compound have a glossy appearance. high degree.
  • the halogen-containing flame-retardant reinforced PBT/PET compound with low smoke density of the present invention is suitable for applications where extremely high requirements for smoke density are required and the product has good appearance.
  • the raw materials in the embodiment can all be obtained commercially;
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • the preparation method is as follows: according to Table 1, the brominated flame retardant and the synergistic flame retardant are mixed to make the first premix; the epoxy resin is mixed with boehmite, kaolin, and magnesium stearate to make the second premix. Mixing; PBT, PET, glass fiber, the first premix and the second premix are added to the twin-screw extruder, mixed, dispersed, melted and extruded to obtain low smoke density halogen-containing flame retardant reinforced PBT/ PET compound.
  • the temperature of the first zone of the twin-screw extruder from the feeding port to the die head is 200-230°C
  • the temperature of the second zone is 240-260°C
  • the temperature of the third zone is 235-255°C
  • the temperature of the fourth zone is 235-255°C
  • the temperature in the fifth zone is 235 ⁇ 255°C
  • the temperature in the sixth zone is 240 ⁇ 260°C
  • the temperature in the seventh zone is 240 ⁇ 260°C
  • the temperature in the eighth zone is 220 ⁇ 240°C
  • the temperature in the ninth zone is 220 ⁇ 240°C
  • the temperature in the tenth zone is 240-260° C.
  • the screw speed of the twin-screw extruder is 200-450 rpm.
  • the preparation method is as follows: according to Table 1, the brominated flame retardant and the synergistic flame retardant are mixed to make the first premix; the epoxy resin is mixed with boehmite, kaolin, and magnesium stearate to make the second premix. Mixing; PBT, PET, glass fiber, the first premix and the second premix are added to the twin-screw extruder, mixed, dispersed, melted and extruded to obtain low smoke density halogen-containing flame retardant reinforced PBT/ PET compound.
  • the temperature of the first zone of the twin-screw extruder from the feeding port to the die head is 200-230°C
  • the temperature of the second zone is 240-260°C
  • the temperature of the third zone is 235-255°C
  • the temperature of the fourth zone is 235-255°C
  • the temperature in the fifth zone is 235 ⁇ 255°C
  • the temperature in the sixth zone is 240 ⁇ 260°C
  • the temperature in the seventh zone is 240 ⁇ 260°C
  • the temperature in the eighth zone is 220 ⁇ 240°C
  • the temperature in the ninth zone is 220 ⁇ 240°C
  • the temperature in the tenth zone is 240-260° C.
  • the screw speed of the twin-screw extruder is 200-450 rpm.
  • the PBT/PET compound is injection-molded into a swatch with a smooth surface and tested with a gloss meter.
  • the incident angle is 60°, and the swatch size is ⁇ 60*60mm;
  • the PBT/PET composites prepared in each example of the present application have good gloss, the flame retardancy is V0, and the smoke density reaches the level 3 standard of smoke density required by the EN45545-2 standard.
  • the low smoke density halogen-containing flame retardant reinforced PBT /PET compound has lower smoke density.
  • the average grain size of boehmite is preferably 10-20 nm
  • the particle size of kaolin is preferably D 50 ⁇ 0.5 ⁇ m
  • the pH of kaolin is preferably 4-5.

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Abstract

本发明公开了一种低烟密度含卤阻燃增强PBT/PET复合物及其制备方法和应用。所述低烟密度含卤阻燃增强PBT/PET复合物包括如下组分：PBT，PET，玻璃纤维，溴系阻燃剂，协效阻燃剂，环氧树脂，勃姆石，高岭土，硬脂酸镁；所述PBT与PET重量比为(1～4)∶1，所述硬脂酸镁的粒径D50≤5μm。通过PET以适当的比例与PBT复配，以及勃姆石、高岭土和特定粒径的硬脂酸镁的协同作用，该PBT/PET复合物的烟密度达到EN45545-2标准所要求的烟密度3级，ISO5659-2测试烟密度Ds max≤150，同时使用此PBT/PET复合物制得的PET/PET制品外观光泽度高。本发明的低烟密度含卤阻燃增强PBT/PET复合物适合应用于对烟密度有极高要求且产品具有良好外观的场合。

Description

一种低烟密度含卤阻燃增强PBT/PET复合物及其制备方法和应用 技术领域
本发明涉及工程塑料技术领域，更具体的，涉及一种低烟密度含卤阻燃增强PBT/PET复合物及其制备方法和应用。
背景技术
塑料材料在燃烧过程中一般会伴随大量烟雾产生，会造成环境的污染并对人体造成巨大伤害。近年来，随着塑料阻燃技术的发展，低烟阻燃已成为阻燃塑料发展的新方向。轨道交通、建材、线缆等行业在低烟阻燃方面的需求越发明朗且规范化，该类行业已明确要求，应用中的塑料部件必须达到EN45545-2标准所要求的烟密度2级或以上水平(2级要求ISO5659-2测试烟密度Ds max≤300)。
聚对苯二甲酸丁二醇酯(PBT)，是由对苯二甲酸和丁二醇通过缩聚反应聚合而成，目前经玻璃纤维增强的PBT材料已广泛应用于照明灯具、冷却风扇、连接器、线圈骨架、电器外壳及其它电子电气部件中。随着技术的发展，人们对PBT改性材料性能要求越来越高，同时成本的压力也迫使做出改变，这种情况下，具有更优异性能的玻纤增强PBT/PET合金材料应运而生。聚对苯二甲酸乙二醇酯(PET)具有良好的耐热性和较低的成本，且PET在玻纤增强的PBT体系中能够有效防止玻璃纤维外露，起到产品表面高光的效果。
当玻纤增强的PBT/PET合金应用于轨道交通、建材、线缆等行业时，对其进行阻燃、抑烟改性是不可或缺的，尤其是应用于某些对抑烟性能有极高要求的场景时，要求烟密度达到EN45545-2标准3级水平(ISO5659-2测试烟密度Ds max≤150)。中国专利CN111534060A公开了一种增强阻燃PBT/PET合金，该增强阻燃PBT/PET合金包括PBT、PET、玻璃纤维、溴系阻燃剂及其他组分，制得的增强阻燃PBT/PET合金具有较好的耐热性好和阻燃性，但并未关注其发烟量或烟密度指标。中国专利申请CN 102532826 A公开了一种低成本阻燃玻纤增强PBT工程塑料，该阻燃玻纤增强PBT工程塑料利用硅酸盐的抑烟作用，制得的低成本阻燃玻纤增强PBT工程塑料具有较好的阻燃性，但其烟密度无法满足EN45545-2标准3级水平。
因此，对于含卤阻燃增强PBT/PET复合物的抑烟性能提升，是亟待进行的。
发明内容
本发明为克服上述现有技术所述的表面浮纤、烟密度较高的缺陷，提供一种低烟密度含卤阻燃增强PBT/PET复合物，该低烟密度含卤阻燃增强PBT/PET复合物具有良好的光泽度、阻燃性，且烟密度达到EN45545-2标准3级水平。
本发明的另一目的在于提供上述低烟密度含卤阻燃增强PBT/PET复合物的制备方法。
本发明的另一目的在于提供上述低烟密度含卤阻燃增强PBT/PET复合物的应用。
为解决上述技术问题，本发明采用的技术方案是：
一种低烟密度含卤阻燃增强PBT/PET复合物，包括如下重量份的组分：
聚对苯二甲酸丁二醇酯(PBT)15～50份，
聚对苯二甲酸乙二醇酯(PET)8～30份，
玻璃纤维10～40份，
溴系阻燃剂10～16份，
协效阻燃剂3～7份，
环氧树脂0.5～1份，
勃姆石2～4份，
高岭土2～8份，
硬脂酸镁2～4份；
所述PBT与PET重量比为(1～4)∶1，
所述硬脂酸镁的粒径D 50≤5μm。
发明人通过研究发现，当PET以适当的比例与PBT复配时，不仅可以显著减少浮纤、提升材料的表面光泽度，还能对有效降低复合物的烟密度水平有帮助。进一步的，在勃姆石、高岭土和特定粒径的硬脂酸镁的协同作用下，本发明的含卤阻燃增强PBT/PET复合物的烟密度可以达到极低的水平，ISO5659-2-2016测试烟密度Ds max≤150，满足EN45545-2标准3级要求。在本发明技术方案中所述硬脂酸镁的粒径D 50要求≤5μm，若硬脂酸镁的粒径过大，则无法达到本发明所述抑烟效果。
所述硬脂酸镁优选江西宏远化工牌号为YZM-32C的产品。
勃姆石的分子式为γ-AlOOH，本申请中所述勃姆石的平均晶粒度≥10nm。
较低晶粒度的勃姆石由于具有低密度、更大的表面积、特殊的结构和形貌等特性，从而使其具有不同于大晶粒度勃姆石的特殊的物理和化学性质，在含卤阻燃增强PBT/PET体系中能够更显著地降低材料燃烧时的发烟量。优选地，所述勃姆石的平均晶粒度优选为10～20nm。
所述勃姆石优选南京埃普瑞纳米材料有限公司，型号为勃姆石235的产品。
发明人发现，酸性适中且粒径更低的高岭土在PBT/PET体系中能够起到更优的抑烟效果。
优选地，所述高岭土的粒径优选为D 50≤0.5μm。
优选地，所述高岭土的pH值优选为4～5。
所述高岭土优选杭州崇科新材料有限公司牌号为Eckalite 1 PLUS的产品。
优选地，所述勃姆石、高岭土、硬脂酸镁的重量比为1∶(1～2)∶1。
发明人研究发现，当勃姆石、高岭土、硬脂酸镁以重量比1∶(1～2)∶1进行复配时，制得的含卤阻燃增强PBT/PET复合物能够获得更优的抑烟效果。
优选地，所述PBT在25℃下特性粘度为0.7～1.3dL/g，所述PET在25℃下特性粘度为0.5～0.8dL/g。特性粘度测试方法依据GB/T 14190-2017。
在此特性粘度范围下，PBT/PET复合物能够获得更优的综合性能。
所述溴系阻燃剂可以是PBT或PET体系中常用的溴系阻燃剂，如高分子溴化环氧、溴化聚苯乙烯、溴化聚碳酸酯阻燃剂、十溴联苯醚等。
优选地，所述溴系阻燃剂优选为高分子溴化环氧、溴化聚苯乙烯和溴化聚碳酸酯阻燃剂中的一种或几种。这些溴系阻燃剂更符合环保要求。
优选地，所述协效阻燃剂优选为锑白。
优选地，所述溴系阻燃剂与协效阻燃剂的重量比为(2～4)∶1。
优选地，所述玻璃纤维经过偶联剂处理。
更优选地，所述偶联剂为N-(β-氨基乙基)-γ-氨基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷和异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯的共混物，三者共混重量比为1∶2∶1。
优选地，所述环氧树脂为双酚A型缩水甘油醚，环氧当量为2500～3100g/eq。环氧当量测试方法依据GB/T 4612-2008。
环氧树脂的加入可以显著改善PBT/PET复合物的性能稳定性。
本发明还保护上述低烟密度含卤阻燃增强PBT/PET复合物的制备方法，包 括如下步骤：
将溴系阻燃剂与协效阻燃剂混合制成第一预混物；
将环氧树脂与勃姆石、高岭土、硬脂酸镁混合制成第二预混物；
将PBT、PET、玻璃纤维、第一预混物、第二预混物加入挤出机，经混合分散、熔融挤出造粒，得到低烟密度含卤阻燃增强PBT/PET复合物。
优选地，所述挤出机为双螺杆挤出机。
更优选地，所述双螺杆挤出机从喂料口到机头的一区温度为200～230℃，二区温度为240～260℃，三区温度为235～255℃，四区温度为235～255℃，五区温度为235～255℃，六区温度为240～260℃，七区温度为240～260℃，八区温度为220～240℃，九区温度为220～240℃，十区温度为240～260℃，所述双螺杆挤出机的螺杆转速为200～450转/分钟。
本发明还保护上述低烟密度含卤阻燃增强PBT/PET复合物在制备轨道交通、建材或线缆的塑料部件中的应用。
与现有技术相比，本发明的有益效果是：
本发明开发出了一种具有低烟密度且表面光泽度良好的含卤阻燃增强PBT/PET复合物。该PBT/PET复合物的烟密度达到EN45545-2标准所要求的烟密度3级，ISO5659-2测试烟密度Ds max≤150，同时使用此PBT/PET复合物制得的PET/PET制品外观光泽度高。本发明的低烟密度含卤阻燃增强PBT/PET复合物适合应用于对烟密度有极高要求且产品具有良好外观的场合。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例中的原料均可通过市售得到；
Figure PCTCN2021092768-appb-000001
Figure PCTCN2021092768-appb-000002
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1～18
实施例1～18的PBT/PET复合物中各组分的含量如表1所示。
其制备方法为：根据表1将溴系阻燃剂与协效阻燃剂混合制成第一预混物；将环氧树脂与勃姆石、高岭土、硬脂酸镁混合制成第二预混物；将PBT、PET、玻璃纤维、第一预混物、第二预混物加入双螺杆挤出机，经混合分散、熔融挤出造粒，得到低烟密度含卤阻燃增强PBT/PET复合物。
其中，双螺杆挤出机从喂料口到机头的一区温度为200～230℃，二区温度为240～260℃，三区温度为235～255℃，四区温度为235～255℃，五区温度为235～255℃，六区温度为240～260℃，七区温度为240～260℃，八区温度为220～240℃，九区温度为220～240℃，十区温度为240～260℃，所述双螺杆挤出机 的螺杆转速为200～450转/分钟。
表1实施例1～18的PBT/PET复合物的组分含量(重量份)
Figure PCTCN2021092768-appb-000003
表1续实施例1～18的PBT/PET复合物的组分含量(重量份)
Figure PCTCN2021092768-appb-000004
对比例1～8
对比例1～8的PBT/PET复合物中各组分的含量如表1所示。
其制备方法为：根据表1将溴系阻燃剂与协效阻燃剂混合制成第一预混物；将环氧树脂与勃姆石、高岭土、硬脂酸镁混合制成第二预混物；将PBT、PET、 玻璃纤维、第一预混物、第二预混物加入双螺杆挤出机，经混合分散、熔融挤出造粒，得到低烟密度含卤阻燃增强PBT/PET复合物。
其中，双螺杆挤出机从喂料口到机头的一区温度为200～230℃，二区温度为240～260℃，三区温度为235～255℃，四区温度为235～255℃，五区温度为235～255℃，六区温度为240～260℃，七区温度为240～260℃，八区温度为220～240℃，九区温度为220～240℃，十区温度为240～260℃，所述双螺杆挤出机的螺杆转速为200～450转/分钟。
表1对比例1～8的PBT/PET复合物的组分含量(重量份)
Figure PCTCN2021092768-appb-000005
性能测试
对上述实施例及对比例制备的PBT/PET复合物进行性能测试，测试方法如下：
光泽度：将PBT/PET复合物注塑为表面光滑的色板后使用光泽度仪测试，入射角为60°，色板尺寸≥60*60mm；
阻燃性@1.0mm：UL94:2003；
烟密度Ds max@1.0mm：ISO5659-2:2012。
测试结果
各实施例的PBT/PET复合物的性能测试结果见表3，各对比例的PBT/PTT复合物的性能测试结果见表4。
表3实施例1～18的性能测试结果
  1 2 3 4 5 6 7 8 9
光泽度 72 70 68 68 71 70 71 70 71
阻燃性 V0 V0 V0 V0 V0 V0 V0 V0 V0
烟密度 127 131 137 136 132 128 146 144 147
  10 11 12 13 14 15 16 17 18
光泽度 72 72 71 70 72 67 66 68 72
阻燃性 V0 V0 V0 V0 V0 V0 V0 V0 V0
烟密度 128 127 148 146 145 128 145 141 129
由表3可以看出，本申请各实施例制得的PBT/PET复合物均具有良好的光泽度，阻燃性为V0，烟密度达到EN45545-2标准所要求的烟密度3级标准。根据实施例1、实施例6～9，当勃姆石、高岭土、硬脂酸镁以重量比1∶(1～2)∶1进行复配时，所述低烟密度含卤阻燃增强PBT/PET复合物具有更低的烟密度。根据实施例1、实施例12～14，勃姆石平均晶粒度优选为10～20nm，高岭土的粒径优选为D 50≤0.5μm，高岭土的pH值优选为4～5。
表4对比例1～8的性能测试结果
  1 2 3 4 5 6 7 8
光泽度 71 70 71 69 71 48 45 69
阻燃性 V0 V0 V0 V0 V0 V0 V0 HB
烟密度 359 362 357 396 195 178 135 236
根据表4的测试结果，由对比例1～4，当勃姆石、高岭土、硬脂酸镁中缺少其中某一组分或几种组分时，PBT/PET复合物虽具有良好的阻燃性和光泽度，但烟密度较高，Ds max≥350，无法满足低烟密度的要求。由对比例5，当硬脂酸镁的粒径过高时，烟密度为189，也达不到EN45545-2标准所要求的烟密度3级标准。由对比例6～7，当PBT与PET的重量比超出本申请技术方案的范围时，PBT/PET复合物的光泽度较差。由对比例8，PBT和PET的添加量过大，PBT/PET复合物的阻燃性为HB，达不到实际阻燃需求。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，包括如下重量份的组分：
    PBT15～50份，PET8～30份，玻璃纤维10～40份，溴系阻燃剂10～16份，协效阻燃剂3～7份，环氧树脂0.5～1份，勃姆石2～4份，高岭土2～8份，硬脂酸镁2～4份；
    所述PBT与PET重量比为(1～4)∶1，
    所述硬脂酸镁的粒径D 50≤5μm。
  2. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述勃姆石的平均晶粒度为10～20nm。
  3. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述高岭土的粒径为D 50≤0.5μm。
  4. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述高岭土的pH值为4～5。
  5. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述勃姆石、高岭土、硬脂酸镁的重量比为1∶(1～2)∶1。
  6. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述PBT在25℃下特性粘度为0.7～1.3dL/g，所述PET在25℃下特性粘度为0.5～0.8dL/g。
  7. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述溴系阻燃剂为高分子溴化环氧、溴化聚苯乙烯和溴化聚碳酸酯阻燃剂中的一种或几种。
  8. 根据权利要求1所述低烟密度含卤阻燃增强PBT/PET复合物，其特征在于，所述环氧树脂为双酚A型缩水甘油醚，环氧当量为2500～3100g/eq。
  9. 权利要求1～8任一项所述低烟密度含卤阻燃增强PBT/PET复合物的制备方法，其特征在于，包括如下步骤：
    将溴系阻燃剂与协效阻燃剂混合制成第一预混物；
    将环氧树脂与勃姆石、高岭土、硬脂酸镁混合制成第二预混物；
    将PBT、PET、玻璃纤维、第一预混物、第二预混物加入挤出机，经混合分散、熔融挤出造粒，得到低烟密度含卤阻燃增强PBT/PET复合物。
  10. 权利要求1～8任一项所述低烟密度含卤阻燃增强PBT/PET复合物在制备轨道交通、建材或线缆的塑料部件中的应用。
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