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 PDFInfo
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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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- composite material
- aluminum
- polypropylene composite
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- 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
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
Description
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 |
Claims (20)
- 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。
- 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。
- 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。
- 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%。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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。
- 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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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 |
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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 |
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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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