WO2020211383A1 - 一种免喷涂聚丙烯复合材料 - Google Patents

一种免喷涂聚丙烯复合材料 Download PDF

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WO2020211383A1
WO2020211383A1 PCT/CN2019/121135 CN2019121135W WO2020211383A1 WO 2020211383 A1 WO2020211383 A1 WO 2020211383A1 CN 2019121135 W CN2019121135 W CN 2019121135W WO 2020211383 A1 WO2020211383 A1 WO 2020211383A1
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spray
zone
composite material
aluminum
polypropylene composite
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PCT/CN2019/121135
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English (en)
French (fr)
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汪理文
周明
李庆贵
牛国增
翁永华
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苏州润佳工程塑料股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0812Aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of polypropylene materials, in particular to a spray-free polypropylene composite material.
  • Spray-free material is a material that adds metal powder to plastic raw materials and directly injection molds the product to show the appearance of spraying.
  • spray paint parts have gradually replaced spray paint parts into the market.
  • the application of spray-free materials simplifies the molding process of automotive interior and exterior parts to a certain extent, enhances product competitiveness, and benefits the development of China's automotive plastics.
  • Spray-free materials have good application advantages: 1. Although spray-free materials are 10% more expensive than general products, if auto companies use this product instead of paint, the cost of auto companies will drop by 20-30%; in addition, spray-free materials Compared with the painting process, the process has a lower waste rate and can be recycled and reused at 100%, making its cost advantage more obvious; 2. At present, the surface of the plastic parts of the interior and exterior decoration of environmentally friendly automobiles usually requires post-painting treatment, and the harmful gases generated during the painting and painting process Will bring unpredictable harm to people and the environment. The spray-free plastic products can show a better appearance without post-modification.
  • spray-free parts have greater advantages compared with spray-painted parts, there are still many problems that need to be overcome in my country's spray-free technology: such as the problem of material metallic gloss and unsatisfactory color; Appearance problems such as marks. If the above problems can be solved well, the corresponding material library should be established to meet the standards of the automotive industry. It can greatly expand the application range of spray-free materials, and ultimately achieve the great goal of low-carbon and environmentally friendly automotive materials.
  • the invention overcomes the shortcomings of the prior art and provides a polypropylene material with good metallic luster, no air marks, flow marks and weld lines.
  • One aspect of the present invention provides a spray-free polypropylene composite material, which is prepared by the following method:
  • the stirring speed is 200-500 rpm.
  • the auxiliary agent includes a primary antioxidant and a secondary antioxidant.
  • the mass ratio of the surface-treated aluminum material, polypropylene resin, modified powder, polyolefin elastomer, ternary copolymer polypropylene, compatibilizer, and auxiliary agent is: flake Aluminum 0.8-1.2%, spherical aluminum 0.9-1.2%, polypropylene resin 61.6-71.4%, modified powder 20-25%, polyolefin elastomer 2.6-5%, ternary copolymer polypropylene 2.6-5% , Compatibilizer 0.6-1.2%, main antioxidant 0.1-0.5%, auxiliary antioxidant 0.3-0.8%.
  • the length of the sheet-shaped aluminum material and the diameter of the spherical aluminum material are both between 5-25 ⁇ m.
  • the polypropylene resin has a flow rate of 50-65 g/min at a temperature of 230°C and a load of 2.16 kg.
  • the modified powder material is a mixed powder of talc and titanium dioxide coated with epoxy resin.
  • the mass ratio of the talc and titanium dioxide is 9:1.
  • the ternary copolymer polypropylene material is obtained by copolymerizing ethylene, propylene, and 1-butene, and the mass ratio of ethylene, propylene, and 1-butene is 1:3:1.
  • the compatibilizer is styrene grafted maleic anhydride.
  • the raw material formula includes the following components in terms of mass percentage: sheet aluminum 0.8-1.2%, spherical aluminum 0.9-1.2%, and polypropylene resin 61.6 -71.4%, modified powder 20-25%, polyolefin elastomer 2.6-5%, ternary copolymer polypropylene 2.6-5%, compatibilizer 0.6-1.2%, main antioxidant 0.1-0.5%, auxiliary resistance Oxidizer 0.3-0.8%;
  • the flake aluminum material and the spherical aluminum material are aluminum materials after surface treatment with polyethylene wax, and the mass ratio of the polyethylene wax and the flake aluminum material is 6.5:1 10:1, the mass ratio of the polyethylene wax to the spherical aluminum material is 6.5:1-10:1.
  • the length of the sheet-shaped aluminum material and the diameter of the spherical aluminum material are both between 5-25 ⁇ m.
  • the polypropylene resin has a flow rate of 50-65 g/min under a load of 2.16 kg at a temperature of 230°C.
  • the modified powder is a mixed powder of talc and titanium dioxide coated with epoxy resin.
  • the mass ratio of the talc and titanium dioxide is 9:1.
  • the ternary copolymer polypropylene is obtained by copolymerizing ethylene, propylene, and 1-butene, and the mass ratio of ethylene, propylene, and 1-butene is 1:3:1.
  • the compatibilizer is styrene grafted maleic anhydride.
  • the surface treatment method of the aluminum material after surface treatment with polyethylene wax is: take polyethylene wax, heat it to 100-115°C to melt it, and then add the aluminum material to the poly In the ethylene wax; stirring and sonicating for 30-50 minutes to make the aluminum material uniformly dispersed in the polyethylene wax melt; then cooling and solidification to obtain the modified aluminum material.
  • the third aspect of the present invention is to provide a method for preparing the spray-free polypropylene composite material, which includes the following steps in sequence:
  • the stirring speed is 200-500 rpm.
  • the beneficial technical effect of the present invention is to provide a polypropylene material with good metallic luster, no air marks, flow marks and weld lines.
  • the present invention improves the metallic luster of the material through the combined use of various shapes of aluminum powder such as flakes and spheres, and gives the material a better and more brilliant color; at the same time, the surface treatment of the aluminum material is carried out by using polyethylene wax to make the aluminum.
  • the dispersion and contact of the material in the polypropylene material are better, which improves the metallic luster and mechanical properties of the material.
  • the surface of the parts prepared by the invention has no gas marks, flow marks and weld lines, and the problem of material delamination is improved.
  • the present invention provides a spray-free polypropylene composite material, and the raw material composition of the material is shown in Table 1.
  • polypropylene resin has a flow rate of 50-65 g/min under a load of 2.16 kg at a temperature of 230°C.
  • Aluminum materials include sheet aluminum materials and spherical aluminum materials; through the combined use of aluminum powders of different shapes, complementing each other, improving reflection and diffuse reflection effects, and enhancing the metallic luster of the material; the length of the sheet aluminum material and the diameter of the spherical aluminum material All are between 5-25 ⁇ m; the aluminum materials are all coated and modified with wax to improve compatibility with the polypropylene matrix; the wax is a polyethylene wax with a molecular weight of 3000-5000.
  • the modified powder material is a mixed powder of talc and titanium dioxide coated with epoxy resin, in which the mass ratio of talc and titanium dioxide is 9:1; the function of titanium dioxide is to increase the metallic luster of the material.
  • Polyolefin elastomer is a thermoplastic elastomer prepared with metallocene as a catalyst. It has a narrow molecular weight distribution and uniform short-chain branch distribution; the elastomer has low density, good toughness, good flexibility, and resistance to It has the advantages of high impact performance, good forming ability and reusability.
  • the ternary copolymer polypropylene material is obtained by the copolymerization of ethylene, propylene, and 1-butene.
  • the mass ratio of ethylene, propylene, and 1-butene is 1:3:1; the addition of this substance can improve POE and polypropylene base Material compatibility.
  • the compatibilizer is styrene grafted maleic anhydride.
  • the main antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is a thioether antioxidant.
  • the spray-free polypropylene composite material is prepared by the following steps:
  • this embodiment is different in:
  • step (1) of the preparation method heat the polyethylene wax to 100°C to melt, then add the aluminum material to the polyethylene wax; the mass ratio of the polyethylene wax to the aluminum material is 8:1; stir and ultrasonic For 50 min (stirring speed is 200 rpm), the aluminum material is uniformly dispersed in the polyethylene wax melt; then it is cooled and solidified to obtain the modified aluminum material.
  • step (1) of the preparation method heat the polyethylene wax to 115°C to melt, then add the aluminum material to the polyethylene wax; the mass ratio of the polyethylene wax to the aluminum material is 6.5:1; stir and ultrasonic 30min (stirring speed is 500rpm), make the aluminum material uniformly dispersed in the polyethylene wax melt; then cool and solidify to obtain the modified aluminum material.
  • this comparative example is different in that: in the raw material composition of the spray-free polypropylene composite material, only the sheet-shaped aluminum material is added, and the spherical aluminum material is not added, and the rest are the same as in Example 1. For details, see Table 1.
  • this comparative example is different in that: the aluminum material added in the raw material composition of the spray-free polypropylene composite material has not been surface-coated with polyethylene wax, and the rest are the same as in Example 1. See Table 1.
  • Example 1 Example 2
  • Example 3 Comparative example 1 Comparative example 2
  • Polypropylene resin 61.6 71.4 66.4 60.1 61.6 Sheet aluminum 1 0.8 1.2 3.5 1 * Spherical aluminum 1 1.2 0.9 0 1 * Modified powder 25 20 twenty three 25 25
  • the polypropylene composite materials provided in Examples 1-3 and Comparative Examples 1-2 were subjected to injection molding sample preparation on an injection molding machine, and performance tests were performed.
  • Flexural modulus test reference standard: ISO178; test conditions: span 64mm, speed 2mm/min.
  • Notched impact strength test reference standard: ISO179-1; test condition: span 40mm.
  • the finished product of Comparative Example 1 has a poorer metal effect than the finished product of Example 1, indicating that the combined use of aluminum powders of different shapes can improve the reflection and diffuse reflection effects and improve the material Metallic luster;
  • the finished product of Comparative Example 2 is not only inferior to the finished product of Example 1, but also has poorer mechanical properties. This is due to the relative difference between the aluminum and polypropylene substrates after surface treatment by wax. It has better capacity and more uniform dispersion, which is beneficial to the improvement of metallic luster and mechanical properties.

Abstract

本发明涉及一种免喷涂聚丙烯复合材料,采用如下方法制得:聚乙烯蜡改性铝材;原料混合均匀;熔融、挤出;循环水冷却;造粒,得到成品;铝材包括片状铝材和球状铝材。本发明通过片状、球状等多种形状的铝粉组合使用,提高了材料的金属光泽,赋予了材料更好、更绚丽的色彩;同时通过使用聚乙烯蜡对铝材进行表面处理,使得铝材在聚丙烯材料中分散和接触更好,提高了材料的金属光泽和力学性能。另外本发明所制备的部件表面无气痕、流痕以及熔接线,材料分层的问题得到改善。

Description

一种免喷涂聚丙烯复合材料 技术领域
本发明涉及聚丙烯材料领域,尤其涉及一种免喷涂聚丙烯复合材料。
背景技术
随着汽车产业的不断发展,新材料、新技术的应用为零部件的开发提供了新的思路。汽车内外饰塑料产品通常采用油漆喷涂,不仅工序繁杂,对环境也造成了很大的污染。免喷涂材料是在塑料原材料中添加金属粉,直接注塑即可使制品呈现喷涂外观效果的材料。如今,一些内外饰免喷涂件逐渐取代了喷漆件进入市场。免喷涂材料的应用在一定程度上简化了汽车内外饰件的成型工艺,提升了产品竞争力,有益于中国汽车塑料的发展。
免喷涂材料具有很好的应用优势:1.虽然免喷涂材料比一般产品贵10%,但汽车企业如果用该产品代替油漆,将会使汽车企业的成本下滑20~30%;另外,免喷涂工艺较之喷漆工艺废品率低,可实现100%回收再利用,使其成本优势愈发明显;2.目前环保汽车内外饰塑料件表面通常需喷漆后处理,油漆及喷漆过程中产生的有害气体会对人及环境带来不可预估的危害。而免喷涂塑料制品则无需后期修饰即可呈现较好的外观。
虽然免喷涂件与喷漆件相比具有较大的优越性,但我国免喷涂技术还有许多需要克服的问题:比如材料金属光泽性及色彩不理想的问 题;材料成型流动性,熔接线、流痕等外观问题。如果能很好的解决上述问题,建立相应的材料库,以达到汽车行业的标准。就可以大大拓展免喷涂材料的应用范围,最终实现汽车用材料的低碳环保伟大目标。
发明内容
本发明克服了现有技术的不足,提供了一种金属光泽佳,无气痕、流痕以及熔接线的聚丙烯材料。
为达到上述目的,本发明采用的技术方案为:
本发明一方面提供一种免喷涂聚丙烯复合材料,采用如下方法制得:
(1)取聚乙烯蜡,将其加热至100-115℃使其融化,之后将铝材加入聚乙烯蜡中;聚乙烯蜡和铝材的质量比为6.5:1-10:1;搅拌并超声30-50min,使铝材在聚乙烯蜡熔融液中分散均匀;之后冷却、固化,得到改性铝材;所述铝材包括片状铝材和球状铝材;
(2)准确称取表面处理后的铝材以及聚丙烯树脂、改性粉体、聚烯烃弹性体、三元共聚聚丙烯、相容剂、助剂,在高速混合器中干混8-15min;混合均匀后出料;
(3)将混合后的原料通入双螺杆挤出机中熔融,挤出;熔融时的温度为:一区180-190℃,二区200-210℃,三区200-210℃,四区210-215℃,五区210-215℃,六区210-215℃,七区215-225℃,八区215-225℃,九区215-225℃,十区215-225℃;在双螺杆挤出机中停留时间为2-5min;压力为12-18MPa;
(4)挤出的坯料,采用5-15℃的循环水冷却;
(5)造粒,得到聚丙烯复合材料。
作为一种优选方案,所述搅拌的速度为200-500rpm。
作为一种优选方案,所述助剂包括主抗氧化剂和助抗氧化剂。
作为一种更优选方案,所述表面处理后的铝材以及聚丙烯树脂、改性粉体、聚烯烃弹性体、三元共聚聚丙烯、相容剂、助剂的质量配比为:片状铝材0.8-1.2%、球状铝材0.9-1.2%、聚丙烯树脂61.6-71.4%、改性粉体20-25%、聚烯烃弹性体2.6-5%、三元共聚聚丙烯2.6-5%、相容剂0.6-1.2%、主抗氧化剂0.1-0.5%、助抗氧化剂0.3-0.8%。
作为一种更优选方案,所述片状铝材的长度、球状铝材的直径均在5-25μm之间。
作为一种更优选方案,所述聚丙烯树脂在230℃的温度下,2.16kg负载下的流动速率为50-65g/min。
作为一种更优选方案,所述改性粉体材料为采用环氧树脂包覆的滑石粉和钛白粉的混合粉体。
作为一种更优选方案,所述滑石粉和钛白粉的质量比为9:1。
作为一种优选方案,所述三元共聚聚丙烯材料由乙烯、丙烯、1-丁烯共聚而得,乙烯、丙烯、1-丁烯三者的质量比为1:3:1。
作为一种优选方案,所述相容剂为苯乙烯接枝马来酸酐。
本发明的另一方面提供一种免喷涂聚丙烯复合材料,按质量百分比计,其原料配方包括如下组分:片状铝材0.8-1.2%、球状铝材 0.9-1.2%、聚丙烯树脂61.6-71.4%、改性粉体20-25%、聚烯烃弹性体2.6-5%、三元共聚聚丙烯2.6-5%、相容剂0.6-1.2%、主抗氧化剂0.1-0.5%、助抗氧化剂0.3-0.8%;
其中,所述的片状铝材和所述的球状铝材为采用聚乙烯蜡表面处理后的铝材,所述的聚乙烯蜡和所述的片状铝材的质量比为6.5:1-10:1,所述的聚乙烯蜡和所述的球状铝材的质量比为6.5:1-10:1。
本发明中,所述片状铝材的长度、球状铝材的直径均在5-25μm之间。
本发明中,所述聚丙烯树脂在230℃的温度下,2.16kg负载下的流动速率为50-65g/min。
优选地,所述改性粉体为采用环氧树脂包覆的滑石粉和钛白粉的混合粉体。
进一步优选地,所述滑石粉和钛白粉的质量比为9:1。
本发明中,所述三元共聚聚丙烯由乙烯、丙烯、1-丁烯共聚而得,乙烯、丙烯、1-丁烯三者的质量比为1:3:1。
本发明中,所述相容剂为苯乙烯接枝马来酸酐。
根据一种具体且优选方案,所述的采用聚乙烯蜡表面处理后的铝材的表面处理方法为:取聚乙烯蜡,将其加热至100-115℃使其融化,之后将铝材加入聚乙烯蜡中;搅拌并超声30-50min,使铝材在聚乙烯蜡熔融液中分散均匀;之后冷却、固化,得到改性铝材。
本发明的第三方面是提供一种所述的免喷涂聚丙烯复合材料的制备方法,包括依次进行的如下步骤:
(1)准确称取表面处理后的铝材以及聚丙烯树脂、改性粉体、聚烯烃弹性体、三元共聚聚丙烯、相容剂、助剂,在高速混合器中干混8-15min;混合均匀后出料;
(2)将混合后的原料通入双螺杆挤出机中熔融,挤出;熔融时的温度为:一区180-190℃,二区200-210℃,三区200-210℃,四区210-215℃,五区210-215℃,六区210-215℃,七区215-225℃,八区215-225℃,九区215-225℃,十区215-225℃;在双螺杆挤出机中停留时间为2-5min;压力为12-18MPa;
(3)挤出的坯料,采用5-15℃的循环水冷却;
(4)造粒,得到聚丙烯复合材料。
优选地,所述搅拌的速度为200-500rpm。
本发明的有益技术效果在于:提供了一种金属光泽佳,无气痕、流痕以及熔接线的聚丙烯材料。本发明通过片状、球状等多种形状的铝粉组合使用,提高了材料的金属光泽,赋予了材料更好、更绚丽的色彩;同时通过使用聚乙烯蜡对铝材进行表面处理,使得铝材在聚丙烯材料中分散和接触更好,提高了材料的金属光泽和力学性能。另外本发明所制备的部件表面无气痕、流痕以及熔接线,材料分层的问题得到改善。
具体实施方式
下面结合具体实施例对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
实施例1
本发明提供了一种免喷涂聚丙烯复合材料,制备该材料的原料组成参见表1。
其中:聚丙烯树脂在230℃的温度下,2.16kg负载下的流动速率为50-65g/min。
铝材包括片状铝材,球状铝材;通过不同形状铝粉的组合使用,取长补短,提高了反射和漫反射效果,提升了材料的金属光泽;片状铝材的长度、球状铝材的直径均在5-25μm之间;铝材均采用蜡进行包覆改性,提高了与聚丙烯基体相容;蜡为分子量为3000-5000的聚乙烯蜡。
改性粉体材料为采用环氧树脂包覆的滑石粉和钛白粉的混合粉体,其中滑石粉和钛白粉的质量比为9:1;钛白粉的作用在于:增加材料的金属光泽。
聚烯烃弹性体(POE)为以茂金属为催化剂制备的热塑性弹性体,其具有窄相对分子质量分布和均匀的短支链分布;该弹性体具有密度小、韧性好、挠曲性好、抗冲击性能高、成型能力好、可重复使用等优点。
三元共聚聚丙烯材料由乙烯、丙烯、1-丁烯共聚而得,乙烯、丙烯、1-丁烯三者的质量比为1:3:1;该物质的加入可以提高POE与聚丙烯基材的相容性。
相容剂为苯乙烯接枝马来酸酐。
主抗氧化剂为受阻酚类抗氧剂;助抗氧化剂为硫醚类抗氧剂。
本免喷涂聚丙烯复合材料采用以下步骤制备:
(1)取聚乙烯蜡,将其加热至105℃使其融化,之后将铝材加入聚乙烯蜡中;聚乙烯蜡和铝材的质量比为10:1;搅拌并超声35min(搅拌速度为300rpm),使铝材在聚乙烯蜡熔融液中分散均匀;之后冷却、固化,得到改性铝材;
(2)按表1,准确称取表面处理后的铝材以及聚丙烯树脂、改性滑石粉材料、蜡、聚烯烃弹性体(POE)、三元共聚聚丙烯、相容剂、助剂,在高速混合器中干混8-15min;混合均匀后出料;
(3)将混合后的原料通入双螺杆挤出机中熔融,挤出;熔融时的温度为:一区180-190℃,二区200-210℃,三区200-210℃,四区210-215℃,五区210-215℃,六区210-215℃,七区215-225℃,八区215-225℃,九区215-225℃,十区215-225℃;在双螺杆挤出机中停留时间为2-5min;压力为12-18MPa;
(4)挤出的坯料,采用5-15℃的循环水冷却;
(5)造粒,得到本发明的聚丙烯复合材料。
实施例2
本实施例与实施例1相比,不同之处在于:
(1)制备免喷涂聚丙烯复合材料的原料组成不同,具体参见表1。
(2)制备方法步骤(1)中:将聚乙烯蜡加热至100℃使其融化,之后将铝材加入聚乙烯蜡中;聚乙烯蜡和铝材的质量比为8:1;搅拌并超声50min(搅拌速度为200rpm),使铝材在聚乙烯蜡熔融液中 分散均匀;之后冷却、固化,得到改性铝材。
实施例3
(1)制备免喷涂聚丙烯复合材料的原料组成不同,具体参见表1。
(2)制备方法步骤(1)中:将聚乙烯蜡加热至115℃使其融化,之后将铝材加入聚乙烯蜡中;聚乙烯蜡和铝材的质量比为6.5:1;搅拌并超声30min(搅拌速度为500rpm),使铝材在聚乙烯蜡熔融液中分散均匀;之后冷却、固化,得到改性铝材。
对比例1
本对比例与实施例1相比,不同之处在于:制备免喷涂聚丙烯复合材料的原料组成中仅加入片状铝材,不加入球状铝材,其余与实施例1均相同,具体参见表1。
对比例2
本对比例与实施例1相比,不同之处在于:制备免喷涂聚丙烯复合材料的原料组成中加入的铝材未经聚乙烯蜡进行表面包覆处理,其余与实施例1均相同,具体参见表1。
表1实施例1-3和对比例1-2的原料组成表(单位:wt%)
名称 实施例1 实施例2 实施例3 对比例1 对比例2
聚丙烯树脂 61.6 71.4 66.4 60.1 61.6
片状铝材 1 0.8 1.2 3.5 1 *
球状铝材 1 1.2 0.9 0 1 *
改性粉体 25 20 23 25 25
聚烯烃弹性体 5 2.6 3 5 5
三元共聚聚丙烯 5 2.6 3 5 5
相容剂 1 0.6 1.2 1 1
主抗氧化剂 0.1 0.3 0.5 0.1 0.1
助抗氧化剂 0.3 0.5 0.8 0.3 0.3
*片状铝材,球状铝材均未采用聚乙烯蜡进行处理。
性能测试:
将实施例1-3以及对比例1-2所提供的聚丙烯复合材料在注射成型机上进行注射成型制样,并进行性能测试。
拉伸强度测试:参考标准:ISO527-2;测试条件:跨距50mm。
弯曲强度测试:参考标准:ISO178;测试条件:跨距64mm,速度14mm/min。
弯曲模量测试:参考标准:ISO178;测试条件:跨距64mm,速度2mm/min。
冲击强度测试:参考标准:ISO179-1;测试条件:跨距40mm。
缺口冲击强度测试:参考标准:ISO179-1;测试条件:跨距40mm。
密度测试测试:参考标准:ISO 1183;测试条件:常温。
熔指测试:参考标准:ISO1133;测试条件:230℃,2.16kg。
表2实施例1-3以及对比例1-2的材料注射成品性能测试
Figure PCTCN2019121135-appb-000001
Figure PCTCN2019121135-appb-000002
根据检测结果可以发现:对比例1的成品相比于实施例1的成品,其金属效果较差,表明不同形状铝粉的组合使用,取长补短,能提高反射和漫反射效果,从而能提升材料的金属光泽;同时对比例2的成品相比于实施例1的成品,不仅金属光泽较差,而且力学性能也较差,这是由于通过蜡进行表面处理后的铝材和聚丙烯基材的相容性更好,分散也更加均匀,有利于金属光泽和力学性能的提高。
以上依据本发明的理想实施例为启示,通过上述的说明内容,相关人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必 须要根据权利要求范围来确定技术性范围。

Claims (20)

  1. 一种免喷涂聚丙烯复合材料,其特征在于:采用如下方法制得:
    (1)取聚乙烯蜡,将其加热至100-115℃使其融化,之后将铝材加入聚乙烯蜡中;聚乙烯蜡和铝材的质量比为6.5:1-10:1;搅拌并超声30-50min,使铝材在聚乙烯蜡熔融液中分散均匀;之后冷却、固化,得到改性铝材;所述铝材包括片状铝材和球状铝材;
    (2)准确称取表面处理后的铝材以及聚丙烯树脂、改性粉体、聚烯烃弹性体、三元共聚聚丙烯、相容剂、助剂,在高速混合器中干混8-15min;混合均匀后出料;
    (3)将混合后的原料通入双螺杆挤出机中熔融,挤出;熔融时的温度为:一区180-190℃,二区200-210℃,三区200-210℃,四区210-215℃,五区210-215℃,六区210-215℃,七区215-225℃,八区215-225℃,九区215-225℃,十区215-225℃;在双螺杆挤出机中停留时间为2-5min;压力为12-18MPa;
    (4)挤出的坯料,采用5-15℃的循环水冷却;
    (5)造粒,得到聚丙烯复合材料。
  2. 根据权利要求1所述的免喷涂聚丙烯复合材料,其特征在于:所述搅拌的速度为200-500rpm。
  3. 根据权利要求1所述的免喷涂聚丙烯复合材料,其特征在于:所述助剂包括主抗氧化剂和助抗氧化剂。
  4. 根据权利要求3所述的免喷涂聚丙烯复合材料,其特征在于: 所述表面处理后的铝材以及聚丙烯树脂、改性粉体、聚烯烃弹性体、三元共聚聚丙烯、相容剂、助剂的质量配比为:片状铝材0.8-1.2%、球状铝材0.9-1.2%、聚丙烯树脂61.6-71.4%、改性粉体20-25%、聚烯烃弹性体2.6-5%、三元共聚聚丙烯2.6-5%、相容剂0.6-1.2%、主抗氧化剂0.1-0.5%、助抗氧化剂0.3-0.8%。
  5. 根据权利要求4所述的免喷涂聚丙烯复合材料,其特征在于:所述片状铝材的长度、球状铝材的直径均在5-25μm之间。
  6. 根据权利要求4所述的免喷涂聚丙烯复合材料,其特征在于:所述聚丙烯树脂在230℃的温度下,2.16kg负载下的流动速率为50-65g/min。
  7. 根据权利要求4所述的免喷涂聚丙烯复合材料,其特征在于:所述改性粉体为采用环氧树脂包覆的滑石粉和钛白粉的混合粉体。
  8. 根据权利要求7所述的免喷涂聚丙烯复合材料,其特征在于:所述滑石粉和钛白粉的质量比为9:1。
  9. 根据权利要求1所述的免喷涂聚丙烯复合材料,其特征在于:所述三元共聚聚丙烯由乙烯、丙烯、1-丁烯共聚而得,乙烯、丙烯、1-丁烯三者的质量比为1:3:1。
  10. 根据权利要求1所述的免喷涂聚丙烯复合材料,其特征在于:所述相容剂为苯乙烯接枝马来酸酐。
  11. 一种免喷涂聚丙烯复合材料,其特征在于:按质量百分比计,其原料配方包括如下组分:片状铝材0.8-1.2%、球状铝材0.9-1.2%、聚丙烯树脂61.6-71.4%、改性粉体20-25%、聚烯烃弹性体2.6-5%、 三元共聚聚丙烯2.6-5%、相容剂0.6-1.2%、主抗氧化剂0.1-0.5%、助抗氧化剂0.3-0.8%;
    其中,所述的片状铝材和所述的球状铝材为采用聚乙烯蜡表面处理后的铝材,所述的聚乙烯蜡和所述的片状铝材的质量比为6.5:1-10:1,所述的聚乙烯蜡和所述的球状铝材的质量比为6.5:1-10:1。
  12. 根据权利要求11所述的免喷涂聚丙烯复合材料,其特征在于:所述片状铝材的长度、球状铝材的直径均在5-25μm之间。
  13. 根据权利要求11所述的免喷涂聚丙烯复合材料,其特征在于:所述聚丙烯树脂在230℃的温度下,2.16kg负载下的流动速率为50-65g/min。
  14. 根据权利要求11所述的免喷涂聚丙烯复合材料,其特征在于:所述改性粉体为采用环氧树脂包覆的滑石粉和钛白粉的混合粉体。
  15. 根据权利要求14所述的免喷涂聚丙烯复合材料,其特征在于:所述滑石粉和钛白粉的质量比为9:1。
  16. 根据权利要求11所述的免喷涂聚丙烯复合材料,其特征在于:所述三元共聚聚丙烯由乙烯、丙烯、1-丁烯共聚而得,乙烯、丙烯、1-丁烯三者的质量比为1:3:1。
  17. 根据权利要求11所述的免喷涂聚丙烯复合材料,其特征在于:所述相容剂为苯乙烯接枝马来酸酐。
  18. 根据权利要求11所述的免喷涂聚丙烯复合材料,其特征在于:所述的采用聚乙烯蜡表面处理后的铝材的表面处理方法为:取聚乙烯蜡,将其加热至100-115℃使其融化,之后将铝材加入聚乙烯蜡 中;搅拌并超声30-50min,使铝材在聚乙烯蜡熔融液中分散均匀;之后冷却、固化,得到改性铝材。
  19. 一种如权利要求11至18中任一项所述的免喷涂聚丙烯复合材料的制备方法,其特征在于:包括依次进行的如下步骤:
    (1)准确称取表面处理后的铝材以及聚丙烯树脂、改性粉体、聚烯烃弹性体、三元共聚聚丙烯、相容剂、助剂,在高速混合器中干混8-15min;混合均匀后出料;
    (2)将混合后的原料通入双螺杆挤出机中熔融,挤出;熔融时的温度为:一区180-190℃,二区200-210℃,三区200-210℃,四区210-215℃,五区210-215℃,六区210-215℃,七区215-225℃,八区215-225℃,九区215-225℃,十区215-225℃;在双螺杆挤出机中停留时间为2-5min;压力为12-18MPa;
    (3)挤出的坯料,采用5-15℃的循环水冷却;
    (4)造粒,得到聚丙烯复合材料。
  20. 根据权利要求19所述的免喷涂聚丙烯复合材料的制备方法,其特征在于:所述搅拌的速度为200-500rpm。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300527A (zh) * 2020-10-30 2021-02-02 福建和盛塑业有限公司 一种pp复合材料及其电力护套管的制备方法
CN114716778A (zh) * 2022-03-25 2022-07-08 江苏新日电动车股份有限公司 一种预防重金属污染的免喷涂复合材料及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109988361A (zh) * 2019-04-16 2019-07-09 苏州润佳工程塑料股份有限公司 一种免喷涂聚丙烯复合材料
CN110330723A (zh) * 2019-07-22 2019-10-15 苏州润佳工程塑料股份有限公司 一种车用免喷涂复合材料及其制备方法
CN110698764A (zh) * 2019-11-14 2020-01-17 苏州润佳工程塑料股份有限公司 一种车用免喷涂聚丙烯材料的制备方法
CN111518335A (zh) * 2020-05-26 2020-08-11 苏州润佳工程塑料股份有限公司 一种汽车外饰件用聚丙烯复合材料的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181092A (zh) * 2018-06-12 2019-01-11 佛山市顺德区杰鑫通塑料科技有限公司 一种免喷涂的、具有银色金属效果的车用外饰板聚丙烯复合材料及其制备方法
CN109988361A (zh) * 2019-04-16 2019-07-09 苏州润佳工程塑料股份有限公司 一种免喷涂聚丙烯复合材料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516663A (zh) * 2011-12-08 2012-06-27 上海普利特复合材料股份有限公司 一种高强度、超高韧性聚丙烯纳米复合材料及其制备方法
CN103910941B (zh) * 2014-04-04 2016-08-17 金发科技股份有限公司 一种免喷涂美学效果的聚丙烯组合物及其制备方法与应用
CN106751352A (zh) * 2016-12-26 2017-05-31 重庆普利特新材料有限公司 一种超高流动性聚丙烯美学树脂复合材料及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181092A (zh) * 2018-06-12 2019-01-11 佛山市顺德区杰鑫通塑料科技有限公司 一种免喷涂的、具有银色金属效果的车用外饰板聚丙烯复合材料及其制备方法
CN109988361A (zh) * 2019-04-16 2019-07-09 苏州润佳工程塑料股份有限公司 一种免喷涂聚丙烯复合材料

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300527A (zh) * 2020-10-30 2021-02-02 福建和盛塑业有限公司 一种pp复合材料及其电力护套管的制备方法
CN112300527B (zh) * 2020-10-30 2022-12-09 福建和盛塑业有限公司 一种pp复合材料及其电力护套管的制备方法
CN114716778A (zh) * 2022-03-25 2022-07-08 江苏新日电动车股份有限公司 一种预防重金属污染的免喷涂复合材料及其制备方法

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