WO2018133603A1 - 一种橡胶增韧聚丙烯复合物及其应用 - Google Patents

一种橡胶增韧聚丙烯复合物及其应用 Download PDF

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WO2018133603A1
WO2018133603A1 PCT/CN2017/116821 CN2017116821W WO2018133603A1 WO 2018133603 A1 WO2018133603 A1 WO 2018133603A1 CN 2017116821 W CN2017116821 W CN 2017116821W WO 2018133603 A1 WO2018133603 A1 WO 2018133603A1
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lubricant
rubber
polypropylene composite
elastomer
composite according
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PCT/CN2017/116821
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French (fr)
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吴国峰
孙刚
杨波
丁正亚
罗忠富
钱志军
俞飞
陈业中
李伟
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金发科技股份有限公司
上海金发科技发展有限公司
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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
    • 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
    • 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

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  • the invention belongs to the field of polymer materials and molding processing thereof, and particularly relates to a rubber toughened polypropylene composite and the application thereof in automobile interiors.
  • polypropylene materials have gradually replaced traditional engineering plastics such as ABS, PC/ABS, PBT and PA with their cost-effective advantages, and have been widely used in automotive interior materials.
  • Polypropylene for automotive interior materials is generally required to have excellent room temperature impact and low temperature impact properties. To achieve this, it is usually necessary to add a large amount of elastomer.
  • elastomers generally have poor compatibility with polypropylene, so in elastomers. Under the condition of high content, the dispersion effect of the elastomer in the polypropylene matrix is very poor, showing a large particle distribution.
  • the object of the present invention is to provide a rubber toughened polypropylene composite which greatly improves the material while having excellent normal temperature and low temperature impact properties.
  • the rigidity of the material is to provide a rubber toughened polypropylene composite which greatly improves the material while having excellent normal temperature and low temperature impact properties.
  • a rubber toughened polypropylene composite in parts by weight, comprising the following components:
  • the lubricant is a compound of an inner lubricant and an outer lubricant, and the mass ratio of the inner lubricant to the outer lubricant is 1:4-4:1.
  • the invention finds that the inner lubricant/external lubricant is compounded, and the proportion of the two compounds is controlled in the range of 1:1 to 4:1, so that the surface of the elastomer and the polypropylene during the blending process can be The tension is reduced, thereby achieving a good dispersion of the elastomer in the polypropylene matrix, so that the elastomer is distributed in the polypropylene matrix in a smaller size, thereby ensuring the material has excellent normal temperature and low temperature impact properties, and is extremely large.
  • the rigidity of the material is increased.
  • the mass ratio of the inner lubricant to the outer lubricant is 1:2-3:1, more preferably 1:1-2:1.
  • the polypropylene is a mixture of one or more of homopolypropylene or copolymerized polypropylene, and has a melt flow rate of from 1 g/10 min to 100 g/10 min at 230 ° C under a load of 2.16 kg.
  • the talc powder has a particle diameter of 3,000 mesh or more, and the talc powder having a fine particle diameter can be selected in the present invention to avoid the influence on the toughness of the polypropylene.
  • the average particle diameter (D50) of the elastomer in the rubber toughened polypropylene composite was less than 4.0 ⁇ m by scanning electron microscopy (SEM).
  • the internal lubricant is a polyethylene wax (such as PE wax), a low molecular ester (such as glyceryl monostearate), a stearic acid complex ester (such as N, N'-ethylene bis stearamide) Or one of amides (such as erucamide, oleic acid amide) or a mixture of two or more.
  • a polyethylene wax such as PE wax
  • a low molecular ester such as glyceryl monostearate
  • a stearic acid complex ester such as N, N'-ethylene bis stearamide
  • amides such as erucamide, oleic acid amide
  • the external lubricant is a stearate (such as calcium stearate, zinc stearate, magnesium stearate) or a hydroxystearate (such as magnesium hydroxystearate, zinc hydroxystearate, hydroxystearate).
  • a stearate such as calcium stearate, zinc stearate, magnesium stearate
  • a hydroxystearate such as magnesium hydroxystearate, zinc hydroxystearate, hydroxystearate.
  • One or a mixture of two of calcium acid is a stearate (such as calcium stearate, zinc stearate, magnesium stearate) or a hydroxystearate (such as magnesium hydroxystearate, zinc hydroxystearate, hydroxystearate).
  • the rubber toughened polypropylene composite of the present invention further comprises, in parts by weight, from 0.1 part to 1 part by weight of the heat stabilizer.
  • the heat stabilizer is an amine, a phosphite (such as PEP-36, 627AV, etc.), a hindered phenol (3114, 1076, 1010, etc.) or a complex of an acryl functional group and a thioester (such as 412S). a mixture of one or several of them.
  • the preparation method of the above rubber toughened polypropylene composite of the present invention can be carried out by putting each raw material into a twin-screw extruder
  • the twin-screw extruder has a length to diameter ratio of 40:1, and the temperature of each zone of the screw is maintained at a melting temperature of 180-210 °C.
  • the invention also provides the use of the above rubber toughened polypropylene composite in automotive interiors.
  • the present invention has the following beneficial effects:
  • the invention adopts the inner lubricant/external lubricant compounding in the polypropylene/talc powder/elastomer formula system, and the proportion of the two compounding is controlled within a certain range, so that the elastomer and the polypropylene can be blended in the process.
  • the reduction of the medium surface tension effectively reduces the average particle size of the elastomer in the polypropylene matrix, promotes the good dispersion of the elastomer in the polypropylene matrix, and ensures the material has excellent normal temperature and low temperature impact properties,
  • the rigidity of the material is improved, the problem of the material rigidity being significantly reduced is avoided, and the development of the automotive interior material is satisfied.
  • Polypropylene homopolypropylene, melt flow rate of 30g/10min;
  • Talc powder 3000 mesh
  • Elastomer ethylene-octene copolymer
  • External lubricant calcium stearate, zinc stearate, magnesium hydroxystearate;
  • Heat stabilizer phosphite heat stabilizer PEP-36, hindered phenol heat stabilizer 1010.
  • the components were weighed according to the parts by weight shown in Table 1.
  • the polypropylene, elastomer, talc, heat stabilizer and lubricant were melted and dispersed in a twin-screw extruder with a length to diameter ratio of 40:1.
  • the temperature was maintained at a melting temperature of 180-210 ° C, extrusion granulation, and finally a rubber-toughened polypropylene composite was obtained, and the corresponding test strips were prepared according to the standard, and the mechanical properties were determined.
  • the specific values are shown in Table 1.
  • Test items unit standard test Tensile Strength MPa ISO 527-1, 527-2 Elongation at break % ISO 527-1, 527-2 Flexural modulus MPa ISO 178 23°C notched impact strength kJ/m 2 ISO 180 -30°C notched impact strength kJ/m 2 ISO 180 Average particle size of elastomer ((D50) Mm Scanning electron microscopy (SEM) test

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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

本发明公开了一种橡胶增韧聚丙烯复合物及其应用，包括组分：聚丙烯45份-69份；滑石粉15份-25份；弹性体15份-25份；润滑剂1份-5份；其中，所述润滑剂为内润滑剂和外润滑剂的复配物，内润滑剂与外润滑剂的质量比为1：4-4：1。本发明在聚丙烯/滑石粉/弹性体配方体系中采用内润滑剂/外润滑剂复配，并将二者复配的比例控制在一定范围内，可使弹性体与聚丙烯在共混过程中表面张力降低，有效降低了弹性体在聚丙烯基体中的平均粒径，促进了弹性体在聚丙烯基体中的良好分散，从而在保证材料具有优异的常温和低温冲击性能的同时，极大的提高了材料的刚性，避免了材料刚性明显下降的问题，满足了汽车内饰材料发展的需要。

Description

一种橡胶增韧聚丙烯复合物及其应用 技术领域
本发明属于高分子材料及其成型加工领域，具体涉及一种橡胶增韧聚丙烯复合物及其在汽车内饰中的应用。
背景技术
随着石油化工工业的迅猛发展，聚丙烯材料以其高性价比的优势渐渐替代传统的ABS、PC/ABS、PBT以及PA等工程塑料，在汽车内饰材料中得到了广泛的应用。
汽车内饰材料用聚丙烯通常要求具有优异的常温冲击和低温冲击性能，为达到此要求，通常需要添加大量的弹性体，然而弹性体一般和聚丙烯的相容性较差，因此在弹性体含量比较高的条件下，弹性体在聚丙烯基体中分散效果非常差，呈现大颗粒分布，为达到标准规定的冲击性能，通常需要添加大量的弹性体，这又造成材料刚性的下降非常明显。
因此，如何解决弹性体在聚丙烯基体中的分散问题，从而满足汽车内饰材料发展的需要成为聚丙烯改性材料的重要研究方向。
发明内容
为了解决上述弹性体在聚丙烯基体中分散效果差的问题，本发明的目的在于提供一种橡胶增韧聚丙烯复合物，在保证材料具有优异的常温和低温冲击性能的同时，极大的提高了材料的刚性。
本发明是通过以下技术方案实现的：
一种橡胶增韧聚丙烯复合物，按重量份数计，包括以下组分：
Figure PCTCN2017116821-appb-000001
其中，所述润滑剂为内润滑剂和外润滑剂的复配物，内润滑剂与外润滑剂的质量比为1：4-4：1。
本发明通过研究发现，采用内润滑剂/外润滑剂复配，并将二者复配的比例控制在1：1-4：1范围内，可使弹性体与聚丙烯在共混过程中表面张力降低，从而实现了弹性体在聚丙烯基体中的良好分散，使弹性体以更小的尺寸在聚丙烯基体中分布，从而在保证材料具有优异的常温和低温冲击性能的同时，极大的提高了材料的刚性，优选的，所述内润滑剂与外润 滑剂的质量比为1：2-3：1，更优选为1：1-2：1。
所述聚丙烯为均聚聚丙烯或共聚聚丙烯中的一种或几种的混合，熔体流动速率在230℃、载荷2.16kg条件下为1g/10min-100g/10min。
所述滑石粉的粒径为3000目或以上，本发明选择粒径细的滑石粉，可以避免对聚丙烯韧性的影响。
所述弹性体为乙烯-丙烯共聚物、乙烯-辛烯共聚物、乙烯-丁烯共聚物或乙烯-丙烯-辛烯三元共聚物中的一种或两种以上的混合。
采用扫描电镜SEM测试，该橡胶增韧聚丙烯复合物中弹性体的平均粒径(D50)小于4.0μm。
所述内润滑剂为聚乙烯蜡类(如PE蜡)、低分子酯类(如甘油单硬脂酸酯)、硬脂酸复合酯类(如N,N’-乙撑双硬脂酰胺)或酰胺类(如芥酸酰胺、油酸酰胺)中的一种或者两种以上的混合。
所述外润滑剂为硬脂酸盐(如硬脂酸钙、硬脂酸锌、硬脂酸镁)或羟基硬脂酸盐(如羟基硬脂酸镁、羟基硬脂酸锌、羟基硬脂酸钙)中的一种或两种的混合。
本发明所述的橡胶增韧聚丙烯复合物，按重量份数计，还包括热稳定剂0.1份-1份。
所述热稳定剂为胺类、亚磷酸酯类(如PEP-36、627AV等)、受阻酚类(3114、1076、1010等)或丙烯酰基官能团与硫代酯的复合物类(如412S)中的一种或几种的混合。
本发明上述的橡胶增韧聚丙烯复合物的制备方法，可通过将各原料投入双螺杆挤出机中
熔融混合分散，挤出造粒，即得。双螺杆挤出机长径比为40:1，螺杆各区温度维持在熔融温度为180-210℃。
本发明还提供了上述橡胶增韧聚丙烯复合物在汽车内饰中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明在聚丙烯/滑石粉/弹性体配方体系中采用内润滑剂/外润滑剂复配，并将二者复配的比例控制在一定范围内，可使弹性体与聚丙烯在共混过程中表面张力降低，有效降低了弹性体在聚丙烯基体中的平均粒径，促进了弹性体在聚丙烯基体中的良好分散，从而在保证材料具有优异的常温和低温冲击性能的同时，极大的提高了材料的刚性，避免了材料刚性明显下降的问题，满足了汽车内饰材料发展的需要。
具体实施方式
下面给出实施例以对本发明进行具体的描述，但不限于此。
现对实施例及对比例所用的原材料做如下说明，但不限于这些材料：
聚丙烯：均聚聚丙烯，熔体流动速率为30g/10min；
滑石粉：3000目；
弹性体：乙烯-辛烯共聚物；
乙烯-丁烯共聚物；
内润滑剂：芥酸酰胺、EBS(N,N’-乙撑双硬脂酰胺)、PE蜡；
外润滑剂：硬脂酸钙、硬脂酸锌、羟基硬脂酸镁；
热稳定剂：亚磷酸酯类热稳定剂PEP-36、受阻酚类热稳定剂1010。
实施例1-12和对比例1-7：
按表1所示重量份数称取组分，将聚丙烯、弹性体、滑石粉、热稳定剂和润滑剂在长径比为40:1的双螺杆挤出机中熔融混合分散，螺杆各区温度维持在熔融温度为180-210℃，挤出造粒，最终得到橡胶增韧聚丙烯复合物，按标准制成相应的测试样条，并测定其力学性能，具体数值列于表1。
表1 橡胶增韧聚丙烯复合物组成及性能
Figure PCTCN2017116821-appb-000002
续表1
Figure PCTCN2017116821-appb-000003
续表1：
Figure PCTCN2017116821-appb-000004
各性能测试按如下表3的标准进行：
表3：
测试项目 单位 测试标准
拉伸强度 MPa ISO 527-1，527-2
断裂伸长率 ％ ISO 527-1，527-2
弯曲模量 MPa ISO 178
23℃缺口冲击强度 kJ/m 2 ISO 180
-30℃缺口冲击强度 kJ/m 2 ISO 180
弹性体平均粒径((D50) μm 采用扫描电镜(SEM)测试
由各实施例与对比例的测试结果可以看出，本发明采用内润滑剂/外润滑剂复配，并将二者复配的比例控制在1∶4-4∶1范围内，可有效降低弹性体的平均粒径，促进了弹性体在聚丙烯基体中的良好分散，从而在保证材料具有优异的常温和低温冲击性能的同时，极大的提高 了材料的刚性。

Claims (11)

  1. 一种橡胶增韧聚丙烯复合物，其特征在于，按重量份数计，包括以下组分：
    Figure PCTCN2017116821-appb-100001
    其中，所述润滑剂为内润滑剂和外润滑剂的复配物，内润滑剂与外润滑剂的质量比为1：4-4：1。
  2. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，所述内润滑剂与外润滑剂的质量比为1：2-3：1，优选为1：1-2：1。
  3. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，所述聚丙烯为均聚聚丙烯或共聚聚丙烯中的一种或几种的混合，熔体流动速率在230℃、载荷2.16kg条件下为1g/10min-100g/10min。
  4. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，所述滑石粉的粒径为3000目或以上。
  5. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，所述弹性体为乙烯-丙烯共聚物、乙烯-辛烯共聚物、乙烯-丁烯共聚物或乙烯-丙烯-辛烯三元共聚物中的一种或两种以上的混合。
  6. 根据权利要求5所述的橡胶增韧聚丙烯复合物，其特征在于，采用扫描电镜SEM测试，该橡胶增韧聚丙烯复合物中弹性体的平均粒径(D50)小于4.0μm。
  7. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，所述内润滑剂为聚乙烯蜡类、低分子酯类、硬脂酸复合酯类或酰胺类中的一种或者两种以上的混合。
  8. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，所述外润滑剂为硬脂酸盐或羟基硬脂酸盐中的一种或两种的混合。
  9. 根据权利要求1所述的橡胶增韧聚丙烯复合物，其特征在于，按重量份数计，还包括热稳定剂0.1份-1份。
  10. 根据权利要求9所述的橡胶增韧聚丙烯复合物，其特征在于，所述热稳定剂为胺类、亚磷酸酯类、受阻酚类或丙烯酰基官能团与硫代酯的复合物类中的一种或几种的混合。
  11. 根据权利要求1-10任一项所述的橡胶增韧聚丙烯复合物在汽车内饰中的应用。
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