WO2018036039A1 - 一种阻燃型碳纤维增强聚酮复合材料 - Google Patents

一种阻燃型碳纤维增强聚酮复合材料 Download PDF

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WO2018036039A1
WO2018036039A1 PCT/CN2016/111068 CN2016111068W WO2018036039A1 WO 2018036039 A1 WO2018036039 A1 WO 2018036039A1 CN 2016111068 W CN2016111068 W CN 2016111068W WO 2018036039 A1 WO2018036039 A1 WO 2018036039A1
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weight
carbon fiber
parts
resin composition
phosphorus
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沙月华
李俊伟
王东晖
周杉鸿
汪凯
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五行科技股份有限公司
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a high physical flame retardant composition.
  • Polyketone is a new green polymer material synthesized from carbon monoxide and olefin (ethylene, propylene). As an engineering plastic, it has many excellent properties such as excellent chemical resistance, hydrolysis resistance, and friction properties. Flame retardant, fuel resistant, high heat distortion temperature, high impact strength, high (gas) barrier properties, etc., can be applied to industrial (gear, seat, etc.), automotive fuel system and hood, automotive exterior components, barrier Tubes and packaging, electrical components, etc. In recent years, many industries such as computers, tablets, mobile phones, televisions, and automobiles have become lighter and thinner. Carbon fiber has the characteristics of small density, light weight and strong rigidity, and is widely used in 3C, automobile and other industries. In view of this, there is a need to develop a high-rigidity POK resin composition to solve the problem of low POK rigidity, and to be lightweight and thin-walled to expand the application range of POK materials.
  • An object of the present invention is to provide a carbon fiber reinforced polyketone (POK) resin composition which is excellent in flexural modulus, impact strength and abrasion resistance.
  • a carbon fiber reinforced polyketone resin composition comprising 10 to 60 parts by weight of carbon fibers, 5 to 30 parts by weight of a phosphorus-based flame retardant, and 0 to 5 parts by weight of other auxiliary agent with respect to 100 parts by weight of the polyketone.
  • the polyketone has a melt index of 30-90 g/10 min at an ambient temperature of 240 ° C and a load of 2.16 Kg.
  • the carbon fibers are chopped carbon fibers or continuous carbon fibers having a diameter of from 0.4 to 0.9 microns.
  • the phosphorus-based flame retardant is added in an amount of 5 to 25 parts by weight, more preferably 10 to 20 parts by weight.
  • the phosphorus-based flame retardant is at least one of a phosphate ester, a hypophosphite, and a phosphonate.
  • the phosphorus-based flame retardant has a phosphorus content of 7-40% by weight.
  • the other auxiliary agent includes at least one of a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a release agent, and a colorant.
  • a carbon fiber reinforced polyketone resin composition of the present invention can obtain fluidity, strength, rigidity and flame retardancy by adding a specific amount of carbon fiber and a phosphorus-based flame retardant to the polyketone.
  • a good polyketone resin composition, the high strength and high rigidity of the composition can be applied to products such as a hood, a fuel tank, a fuel pipe and the like which are resistant to chemicals, hydrolysis, fuel and rigidity.
  • the fluidity of the composition is easy to shape and reduces floating fibers.
  • carbon fiber-reinforced polyketone resin composition of the present invention 10 to 60 parts by weight of carbon fiber, 5 to 30 parts by weight of a phosphorus-based flame retardant, and 0 to 5 parts by weight of other auxiliary agent are added with respect to 100 parts by weight of the polyketone. .
  • the polyketone when the ambient temperature is 240 ° C and the load is 2.16 Kg, the polyketone has a melt index of 30-90 g/10 min.
  • the carbon fiber has a diameter of 0.4 to 0.9 ⁇ m, which can improve the fluidity, strength and rigidity of the composition, and may use chopped carbon fibers or continuous carbon fibers. On thin-walled products, chopped carbon fiber modified polyketone materials are used to improve the surface of the product.
  • the amount of the phosphorus-based flame retardant added is less than 5 parts by weight, the flame retarding effect is not obtained.
  • the amount is more than 30 parts by weight, the physical properties of the composition are seriously lowered, and the phosphorus-based flame retardant is preferably added. It is 5-25 parts by weight, more preferably 10-20 parts by weight.
  • the phosphorus-based flame retardant is at least one of a phosphate ester, a hypophosphite, and a phosphonate, and the phosphorus-based flame retardant has a phosphorus content of 7-40% by weight of the phosphorus-based flame retardant. Better flame retardant effect.
  • the polyketone resin composition further includes at least one of a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a release agent, and a colorant.
  • each component of the corresponding weight is weighed; then, each component is stirred using a uniaxial stirring tank; the above mixture is separately fed to a twin-screw extruder for melt extrusion granulation.
  • each component of the corresponding weight is weighed; then, each component is stirred using a uniaxial stirring tank; the above mixture is separately fed to a twin-screw extruder for melt extrusion granulation.
  • each component of the corresponding weight is weighed; then, each component is stirred using a uniaxial stirring tank; the above mixture is separately fed to a twin-screw extruder for melt extrusion granulation.
  • the glass fiber having a circular cross-sectional shape in the comparative example was a commercially available circular cross-sectional shape glass fiber of Jushi Corporation.
  • each component of the corresponding weight is weighed; then, each component is stirred using a uniaxial stirring tank; the above mixture is separately fed to a twin-screw extruder for melt extrusion granulation.
  • Comparative Example 2 is a commercial product DuPont HTN 53G50HSLR, a commercial product of DuPont, grade HTN 53G50HSLR, which is a 50% by weight glass fiber having a flat cross-sectional shape added to a high temperature resistant nylon (PPA).
  • PPA high temperature resistant nylon

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

Abstract

本发明公开了一种碳纤维增强聚酮树脂组合物，相对于100重量份的聚酮，添加有10-60重量份碳纤维，5-30重量份磷系阻燃剂和0-5重量份的其他助剂。该聚酮树脂组合物流动性、强度、刚性及阻燃性俱佳，流动性易于产品成型，并可以减少浮纤；能广泛应用在发动机盖罩、燃油罐、燃油管和薄壁化的产品上。

Description

一种阻燃型碳纤维增强聚酮复合材料 技术领域
本发明涉及高分子材料技术领域，具体是涉及一种高物性阻燃组合物。
背景技术
聚酮是(POK)由一氧化碳、烯烃(乙烯、丙烯)合成的新型绿色聚合物材料，作为一种工程塑胶，拥有许多优异的性能，如优异的耐化学性和耐水解稳定性、摩擦性能、阻燃性、耐燃油性，并且具有高热变形温度、高冲击强度、高(气体)阻隔性等，可应用于工业(齿轮、座椅配等)、汽车燃油系统和引擎盖、汽车外部组件、阻隔管和包装、电气部件等。近年来，计算机、平板、手机、电视、汽车等众多行业向更轻更薄化发展。碳纤维具有密度小、重量轻、刚性强等特性，在3C、汽车等行业应用日益广泛。有鉴于此，需要开发一种高刚性POK树脂组合物以解决POK刚性偏低的问题，并且质轻，可薄壁化，以扩展POK材料的应用范围。
发明内容
本发明的目的在于提供一种碳纤维增强聚酮(POK)树脂组合物，使其得到在弯曲模量、冲击强度和耐磨性方面俱佳的产品。
本发明所要解决的技术问题是通过以下技术方案实现的：
一种碳纤维增强聚酮树脂组合物，相对于100重量份的聚酮，添加有10-60重量份碳纤维，5-30重量份磷系阻燃剂和0-5重量份的其他助剂。
可选地，所述聚酮为在环境温度为240℃，负荷为2.16Kg时，熔融指数为30-90g/10min。
可选地，所述碳纤维为短切碳纤维或连续性碳纤维，其直径为0.4-0.9微米。
可选地，所述磷系阻燃剂的添加量为5-25重量份，更佳的为10-20重量份。
可选地，所述磷系阻燃剂为磷酸酯、次磷酸盐及膦酸脂中的至少一种。
可选地，所述磷系阻燃剂中磷的重量含量为7-40％。
可选地，所述其他助剂包括润滑剂、静电防止剂、抗氧剂、紫外线吸收剂、脱模剂及着色剂中的至少一种。
相较于现有技术，本发明的一种碳纤维增强聚酮树脂组合物，通过在聚酮中添加特定量的碳纤维及磷系阻燃剂，可以得到流动性、强度、刚性及阻燃性俱佳的聚酮树脂组合物，该组合物的高强度、高刚性可以应用在发动机盖罩、燃油罐、燃油管等对材料耐化学、耐水解、耐燃油、刚性要求高的产品上，也可应用于笔电等薄壁化的产品上，该组合物的流动性易于产品成型，并可以减少浮纤。
具体实施方式
本发明的碳纤维增强聚酮树脂组合物中，相对于100重量份的聚酮，添加有10-60重量份碳纤维，5-30重量份磷系阻燃剂和0-5重量份的其他助剂。
其中，在环境温度为240℃，负荷为2.16Kg时，所述聚酮的熔融指数为30-90g/10min。
其中，所述碳纤维的直径为0.4-0.9微米，能提高组合物的流动性、强度及刚性，可使用短切碳纤维，也可以使用连续型碳纤维。在薄壁化产品上，使用短切碳纤维改性聚酮材料，产品表面更优。
其中，所述磷系阻燃剂添加量低于5重量份时，无法起到阻燃效果，高于30重量份，则组合物的物性下降严重，磷系阻燃剂的较佳的添加量为5-25重量份，更佳的为10-20重量份。所述磷系阻燃剂为磷酸酯、次磷酸酯及膦酸脂中的至少一种，所述磷系阻燃剂中磷重量含量为磷系阻燃剂重量的7-40％，能达到更优的阻燃效果。
其中，所述聚酮树脂组合物中还包括润滑剂、静电防止剂、抗氧剂、紫外线吸收剂、脱模剂及着色剂中的至少一种。
为对本发明的目的、技术手段及技术功效有进一步的了解，现结合具体实施例说明如下。
实施例1
Figure PCTCN2016111068-appb-000001
Figure PCTCN2016111068-appb-000002
称取相应重量的各组分；然后，将各组分利用单轴搅拌桶搅拌；将上述混合物分别加入到双螺杆挤出机中熔融挤出造粒。
实施例2
Figure PCTCN2016111068-appb-000003
称取相应重量的各组分；然后，将各组分利用单轴搅拌桶搅拌；将上述混合物分别加入到双螺杆挤出机中熔融挤出造粒。
实施例3
Figure PCTCN2016111068-appb-000004
称取相应重量的各组分；然后，将各组分利用单轴搅拌桶搅拌；将上述混合物分别加入到双螺杆挤出机中熔融挤出造粒。
对比例1
Figure PCTCN2016111068-appb-000005
该对比例中圆形截面形状的玻璃纤维为Jushi公司的市售的圆形截面形状的玻璃纤维。
称取相应重量的各组分；然后，将各组分利用单轴搅拌桶搅拌；将上述混合物分别加入到双螺杆挤出机中熔融挤出造粒。
对比例2
对比例2为市售商品杜邦
Figure PCTCN2016111068-appb-000006
HTN 53G50HSLR，即为杜邦公司的一种市售商品，牌号
Figure PCTCN2016111068-appb-000007
HTN 53G50HSLR，其为耐高温尼龙(PPA)中添加50％重量的扁平截面形状的玻璃纤维。
以上各实施例及对比例熔融挤出造粒后，然后在注塑机上注塑成型GB标准测试样条，按GB标准测试所得材料的机械性能，并按照UL94标准测试阻燃性能，测试结果如表1所示：
表1：实施例及对比例的测试结果
测试项目 实施例1 实施例2 实施例3 对比例1 对比例2
比重(g/cm3) 1.32 1.4 1.40 1.30 1.64
拉伸强度(MPa) 200 190 220 85 220
断裂伸长率(％) 2.1 1.8 1.7 3.5 1.8
弯曲强度(MPa) 260 260 300 130 270
弯曲模量(MPa) 18000 20000 22500 4500 16000
冲击强度(KJ/m2) 9 10 9.5 7.5 13
阻燃等级 1.2mm V-0 0.8mm V-0 1.2mmV-0 0.4mm V-0 0.4mmV-0
热变形温度(℃) 245 265 270 230 260
以上对本发明所提供的一种阻燃型碳纤维增强聚酮树脂组合物进行了详细介绍。本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (7)

  1. 一种碳纤维增强聚酮树脂组合物，其特征在于，相对于100重量份的聚酮，添加有10-60重量份碳纤维，5-30重量份磷系阻燃剂和0-5重量份的其他助剂。
  2. 根据权利要求1所述的一种碳纤维增强聚酮树脂组合物，其特征在于，所述聚酮为在环境温度为240℃，负荷为2.16Kg时，熔融指数为30-90g/10min。
  3. 根据权利要求1所述的一种碳纤维增强聚酮树脂组合物，其特征在于，所述碳纤维为短切碳纤维或连续性碳纤维，其直径为0.4-0.9微米。
  4. 根据权利要求1所述的一种碳纤维增强聚酮树脂组合物，其特征在于，所述磷系阻燃剂的添加量为5-25重量份，更佳的为10-20重量份。
  5. 根据权利要求1所述的一种碳纤维增强聚酮树脂组合物，其特征在于，所述磷系阻燃剂为磷酸酯、次磷酸盐及膦酸脂中的至少一种。
  6. 根据权利要求5所述的一种碳纤维增强聚酮树脂组合物，其特征在于，所述磷系阻燃剂中磷的重量含量为7-40％。
  7. 根据权利要求1所述的一种碳纤维增强聚酮树脂组合物，其特征在于，所述其他助剂包括润滑剂、静电防止剂、抗氧剂、紫外线吸收剂、脱模剂及着色剂中的至少一种。
PCT/CN2016/111068 2016-08-24 2016-12-20 一种阻燃型碳纤维增强聚酮复合材料 WO2018036039A1 (zh)

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