WO2024061104A1 - 一种聚丙烯复合材料及制备方法和应用 - Google Patents

一种聚丙烯复合材料及制备方法和应用 Download PDF

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WO2024061104A1
WO2024061104A1 PCT/CN2023/118864 CN2023118864W WO2024061104A1 WO 2024061104 A1 WO2024061104 A1 WO 2024061104A1 CN 2023118864 W CN2023118864 W CN 2023118864W WO 2024061104 A1 WO2024061104 A1 WO 2024061104A1
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polypropylene
composite material
parts
phase
polypropylene composite
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PCT/CN2023/118864
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English (en)
French (fr)
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陈锐
王林
陈平绪
叶南飚
陈延安
吴国峰
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成都金发科技新材料有限公司
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Publication of WO2024061104A1 publication Critical patent/WO2024061104A1/zh

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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

Definitions

  • the present invention relates to the technical field of polymer materials, and more specifically, to a polypropylene composite material and its preparation method and application.
  • the prior art discloses a polypropylene composition for automotive interior parts, which mainly adds reactive polyamide and coats it on the surface of talc powder to form a protective film to inhibit antioxidants caused by metal ions in the talc powder. degradation, thereby inhibiting the production of organic volatile compounds, and the reactive polyamide is alkaline, which can neutralize acidic organic volatile compounds and play a scavenging role, thereby reducing the odor of the polypropylene composition.
  • the above-mentioned polypropylene composition to solve the odor problem requires the addition of other additives, which cannot be used at the same time. Solve the appearance problem of polypropylene composite materials.
  • the purpose of the present invention is to overcome the defects and deficiencies in appearance and odor problems of existing polypropylene composite material injection molded parts, and to provide a polypropylene composite material that has a specific glass transition temperature difference through the synergy of the main resin of the high-flow polypropylene material.
  • the high-value linear low-density polyethylene resin not only eliminates the appearance defects of bulging injection molded parts, but also directly injection molds automotive interior parts with excellent odor quality and meets the standards of major OEMs.
  • a polypropylene composite material comprising the following components in parts by weight:
  • melt mass flow rate of the polypropylene is 30-100g/10min, test standard ISO1133-1-2011, 230°C, 2.16Kg load;
  • the two-phase glass transition temperature difference between the PP phase in polypropylene resin and the EPR phase in linear low-density polyethylene is Tg (PP phase) - Tg (EPR phase) ⁇ 50°C.
  • the test method of glass transition temperature adopts DSC method.
  • DSC characterizes the glass transition temperature of materials by measuring the change of specific heat capacity of the material with temperature.
  • the specific heat capacity will change greatly before and after the glass transition temperature Tg.
  • the glass transition temperature can be determined according to the curve. .
  • the glass transition temperature is usually a step in the endothermic direction, and the glass transition is a region. This method usually uses the intersection of a line that is equidistant from the two extrapolated baselines and the curve as the glass transition temperature.
  • the test temperature range is - 60°C-100°C, the heating and cooling rate is 20°C/min, first heat up from 23°C to 100°C, then cool down from 100°C to -60°C, and then heat up from -60°C to 100°C.
  • Filler components can be added to the polypropylene composite material of the present invention, and the filler can be one or more of talcum powder, calcium carbonate, wollastonite and whiskers.
  • the melt mass flow rate of polypropylene as the main resin is 30-100g/10min. It is a high-flow polypropylene material. It has good flow properties and can be molded at a lower injection temperature. It quickly fills large mold cavities, reducing the degree of heating and shearing of the material. The material can be injection molded at a lower injection molding temperature. The lower processing temperature can effectively avoid overheating and decomposition of the material and reduce the volatilization of small odor molecules. , which is conducive to ensuring the quality of smell.
  • the two-phase glass transition temperature of the polypropylene matrix resin and linear low-density polyethylene added in the present invention The degree difference is ⁇ 50°C, and the difference is small.
  • the linear low-density polyethylene easily forms a continuous distribution phase in the polypropylene matrix resin, and the phase between the EPR phase of the linear low-density polyethylene resin and the PP phase of the polypropylene resin is It has better capacitance and will not form too many microscopic gaps between the two phases during the processing, thereby solving the problem of difficulty in completely discharging small molecular substances contained in the plastic melt.
  • the small molecular substances in the plastic melt can be smoothly discharged. It avoids the bulging phenomenon of injection molded parts and improves the appearance quality of injection molded products.
  • the parts have good appearance and low odor quality level, and are especially suitable for the high-efficiency production of large interior low-odor parts.
  • the polypropylene composite material of the present invention has good injection molding appearance properties. It can also have good appearance properties during injection molding preparation, especially when large-size molds are formed. It can be widely used in various types of mold structures, reducing the need for mold structure design. High demands.
  • linear low-density polyethylene in the polypropylene composite material of the present invention is also crucial. If the synergistic amount of linear low-density polyethylene is too small, the toughness of the composite material is poor ( ⁇ 10KJ/m 2 ), and the linear low-density polyethylene cannot form a continuous phase in the polypropylene material, and the two phases are easily separated microscopically, which easily produces bubbles and odor small molecules. If the synergistic amount of linear low-density polyethylene is too large, the rigidity of the polypropylene composite material is poor, the overall product is soft, and cannot meet the requirements of most working conditions.
  • the two-phase glass transition temperature difference between the Tg (EPR phase) of the linear low-density polyethylene and the Tg (PP phase) of the polypropylene resin is 45 to 48°C.
  • the glass transition temperature difference between the two phases needs to be controlled within a reasonable range. If the temperature difference is too small, it means that the Tg (EPR phase) of LLDPE is too high, and the composite material is too hard under low temperature ( ⁇ -20°C) conditions. , toughness is not enough.
  • the melt mass flow rate of the polypropylene is 50-90g/10min, test standard ISO 1133-1-2011, 230°C, 2.16Kg load.
  • the melt mass flow rate of the linear low-density polyethylene is 15 ⁇ 25g/10min, test standard ISO 1133-1-2011, 190°C, 2.16Kg load,
  • the present invention also adds linear low-density polyethylene.
  • a too low melting index of linear low-density polyethylene is not conducive to the formation of a stable continuous dispersed phase in the polypropylene base resin, and will also Reduce the fluidity of the entire composite material; linear low-density polyethylene melt index is too high, which is not conducive to modification Improve the appearance and performance of interior parts after injection molding.
  • the odor of the polypropylene is 3.5 to 4.0 according to the Volkswagen PV3900 standard test.
  • the linear low-density polyethylene smell is 3.5 to 4.0 according to the Volkswagen PV3900 standard test.
  • Controlling the odor level of raw materials is the basis for obtaining low-odor composite materials.
  • low odor of raw materials alone cannot meet the strict odor quality requirements of the OEM.
  • the above-mentioned polypropylene and linear low-density polyethylene combined with the specific formula of the present invention can achieve this. Higher quality requirements.
  • the filler is one or more of talc, calcium carbonate, wollastonite and whiskers.
  • processing aids in order to meet other application requirements of polypropylene composite materials, 0.05 to 5 parts by weight of processing aids can also be added to the polypropylene composite materials, where the processing aids can be pigments and antioxidants. , one or more of weathering agents and lubricants.
  • the pigment of the present invention can be an organic or inorganic pigment.
  • Inorganic pigments can be titanium white, chrome yellow, cadmium yellow, molybdenum chromium red, iron red (yellow), cadmium red, ultramarine blue, cobalt blue, iron blue, chrome green, cobalt green, metal powder, mica pearlescent, carbon black, etc.
  • Organic pigments can be azo, chromidine, phthalocyanine, dye, etc.
  • the antioxidant of the present invention may be: hindered phenolic antioxidants, phosphite antioxidants, etc.
  • the weathering agent of the present invention may be: hindered amine weathering agent.
  • the lubricant of the present invention may be: calcium stearate, zinc stearate, etc.
  • the invention also specifically protects a method for preparing the above-mentioned polypropylene composite material, which includes the following steps:
  • the extruder of the present invention can be a twin-screw extruder or a reciprocating single-screw extruder, and the screw length-to-diameter ratio is not less than 32.
  • the polypropylene composite material of the present invention has good injection molding appearance quality, can well eliminate bulge appearance defects on the surface of the product, and the injection molded automobile interior decoration has good odor quality, and can be widely used in automobile interiors of different structures and sizes.
  • the injection molding production of decorative parts, such as car door panels, dashboards, pillars, etc., can meet the quality requirements of high appearance and low odor.
  • the polypropylene composite material of the present invention uses high-flow polypropylene material as the main resin, can quickly fill cavities with different wall thicknesses, and can achieve low-temperature injection molding, which reduces the degree of thermal and shear decomposition of the material and ensures odor quality.
  • linear low-density polyethylene with a two-phase glass transition temperature difference of ⁇ 50°C from polypropylene is added, which can significantly reduce the phase separation of the two phases and avoid microscopic voids and inclusion of air and small particles in the plastic melt. It is difficult to completely eliminate the problem of molecular organic gases. Injection molded interior parts have good appearance quality and outstanding low odor quality advantages.
  • the appearance bulging grade of the polypropylene composite material of the present invention can reach level 2 and below, and the odor level can reach level 3.5 and below. It has outstanding anti-bulging appearance effect and good odor quality, and its bending performance can reach above 1600MPa, and its toughness
  • the notched impact performance of the cantilever beam can reach more than 15kJ/m2, which meets the comprehensive mechanical property requirements of rigid and tough balance.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • the raw material information of the examples and comparative examples of the present invention is as follows:
  • PP-1 PP-BX3900
  • melt mass flow rate is 60g/10min
  • test standard ISO 1133-1-2011 test conditions 230°C, 2.16Kg
  • odor level 3.5 (PV3900 standard)
  • PP-2 PP BX3920, melt mass flow rate is 100g/10min, test standard ISO 1133-1-2011, test conditions 230°C, 2.16Kg, odor level 3.5 (PV3900 standard), manufacturer: SK;
  • PP-3 PP BX3800, melt mass flow rate is 30g/10min, test standard ISO 1133-1-2011, test conditions 230°C, 2.16Kg, odor level 4.0 (PV3900 standard), manufacturer: SK;
  • PP-4 PP EP640V, melt mass flow rate is 90g/10min, test standard ISO 1133-1-2011, test conditions 230°C, 2.16Kg, odor level 3.5 (PV3900 standard), manufacturer: CNOOC Shell;
  • PP-5 PP SP179 (blue), melt mass flow rate is 10g/10min, test standard ISO 1133-1-2011, test conditions: 230°C, 2.16Kg, odor level 3.5 (PV3900 standard), manufacturer: Lanzhou Petrochemical;
  • Linear low density polyethylene 1 LLDPE M2320, melt mass flow rate is 20g/10min, test standard ISO 1133-1-2011, test conditions 190°C, 2.16Kg, odor level 3.5 (PV3900 standard), manufacturer: Maoming Petrochemical;
  • Linear low density polyethylene 2 LLDPE M2320 (DNDA-7144), melt mass flow rate is 20g/10min, test standard ISO 1133-1-2011, test conditions 190°C, 2.16Kg, odor level 3.5 (PV3900 standard), Manufacturer: Maoming Petrochemical;
  • Linear low density polyethylene 3 LLDPE-L M2320 (ZHONGYUAN), melt mass flow rate is 17g/10min, test standard ISO 1133-1-2011, test conditions 190°C, 2.16Kg, odor level 3.5 (PV3900 standard), Manufacturer: Maoming Petrochemical;
  • Linear low density polyethylene 4 SABIC 6201RQ powder, melt mass flow rate is 50g/10min, test standard ISO 1133-1-2011, test conditions 190°C, 2.16Kg, odor level 4.0 (PV3900 standard), manufacturer: SABIC;
  • Linear low density polyethylene 5 LLDPE EXCEED 3518PA, melt mass flow rate is 1g/10min, test standard ISO 1133-1-2011, test conditions 190°C, 2.16Kg, odor level 4.0 (PV3900 standard), manufacturer: EK Sam Mobil;
  • Talcum powder is commercially available, and the parallel embodiments and comparative examples of the present invention are all of the same type;
  • Antioxidant hindered phenolic main antioxidant + phosphite auxiliary antioxidant, the mass ratio of the main antioxidant and auxiliary antioxidant is 1:1, commercially available, parallel embodiments and comparative examples of the present invention All are the same commercially available products.
  • a polypropylene composite material comprises the components shown in Table 1 below, in parts by weight.
  • the preparation method of the polypropylene composite material of the above embodiments 1 to 15 includes the following steps:
  • the components were uniformly mixed in a mixing device according to the weight proportions of the components in Table 1, and then added into a twin-screw extruder with a length-to-diameter ratio of 40:1, melt-kneaded at 200°C, and then granulated, cooled, and baked at 120°C for 6 hours to obtain a polypropylene composition.
  • plastic sheets with sizes of 100mm*100mm*3mm and ISO standard bending and notch impact were obtained through injection molding. module.
  • a polypropylene composite material in parts by weight, includes the components shown in Table 2 below.
  • the preparation method of the polypropylene composite materials of Comparative Examples 1 to 3 above includes the following steps:
  • each component evenly in the mixing equipment according to the weight of each component in Table 2, then add it to a twin-screw extruder with an aspect ratio of 40:1, and perform melting and mixing at a temperature of 200°C. Then, it was granulated, cooled, and baked at 120°C for 6 hours to obtain a polypropylene composition.
  • plastic sheets with sizes of 100mm*100mm*3mm and ISO standard bending and notch impact were obtained through injection molding. module.
  • Plastic plain plates (length, width and thickness dimensions of 100mm*100mm*3mm) were evaluated for odor (VDA270 standard, 1L test bottle, experimental conditions 80°C/2h) and bulging effect (visual evaluation), with the best being level 1 and the worst being level 6. Five professional evaluators gave scores and took the average value (rounded off).
  • the bending performance is tested to characterize the rigidity of polypropylene composite materials.
  • the testing standard is ISO 178-2010, MPa.
  • the notched cantilever beam impact performance is tested to characterize the toughness of polypropylene composites.
  • the test standard is ISO180-2019, type A notch, kJ/m 2 .
  • the present invention uses high-flow, low-odor polypropylene material as the main resin, and adds LLDPE resin with a small difference in the two-phase glass transition temperature Tg (PP phase)-Tg (EPR phase) and By controlling the addition amount within an appropriate range, a polypropylene composite material with elimination of bulge defects ( ⁇ 2.0 grade) and odor quality ( ⁇ 3.5 grade) can be prepared.
  • the polypropylene composite material of the present invention can be obtained by injection molding for automotive interiors. The piece has outstanding anti-bulging appearance and good odor quality.
  • the polypropylene composite material of the present invention also has good mechanical properties.
  • the bending performance in the rigidity test can reach more than 1600MPa, and the Izod notch impact performance in the toughness test can reach more than 15kJ/m2, which meets the comprehensive mechanical property requirements of rigidity and toughness balance.
  • the material of the invention is particularly suitable for the injection molding requirements of large automobile interior parts with low odor and good appearance, and effectively solves the problems faced by the automobile injection molding industry in that the parts have excessive odor and are prone to bulging.
  • the polypropylene PP-5 in Comparative Example 3 is not within the protection scope of the present invention.
  • the appearance and smell of the polypropylene composite material are significantly deteriorated, and the rigidity of the polypropylene composite material is also seriously deteriorated, and it cannot meet the comprehensive mechanical property requirements of balance of rigidity and toughness.

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  • Polymers & Plastics (AREA)
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Abstract

本发明提供了一种聚丙烯复合材料及制备方法和应用，属于高分子材料技术领域。本发明的聚丙烯复合材料以重量份数计，包括如下组分：聚丙烯40～95份，填料0～40份，线性低密度聚乙烯5～20份；其中，所述聚丙烯的熔体质量流动速率为30～100g/10min，测试标准ISO 1133-1-2011，230℃，2.16Kg载荷，聚丙烯树脂中PP相与线性低密度聚乙烯中EPR相的两相玻璃化转变温度差≤50℃。本发明以高流动的聚丙烯材料作为主体树脂，添加线性低密度聚乙烯明显降低两相相分离的作用，解决了塑料熔体出现微观空隙且夹杂的空气和小分子有机气体难以彻底排除的问题，注塑成型的内饰制件具体良好的外观质量和突出的低气味品质。

Description

一种聚丙烯复合材料及制备方法和应用 技术领域
本发明涉及高分子材料技术领域，更具体地，涉及一种聚丙烯复合材料及制备方法和应用。
背景技术
近年来，伴随着汽车行业的发展，越来越多的塑料被应用于汽车内饰件，其中聚丙烯材料因其综合性能优良、来源广泛和质优价廉等优点，更是占据了车用塑料用量较大的比例。随着人民群众生活水平的日益提高，消费者对汽车内饰件的要求也是越来越高，如对内饰件的外观以及散发性能等格外关注。目前大型车用内饰件成型模具尺寸往往较大，注塑成型周期又要求较短，如果制件结构复杂，模具结构设计不能高精度匹配，或者排气槽或者排气孔的数量和位置设置不合理，注塑出来的制件很容易出现鼓包的外观缺陷，这严重影响成品制件的合格率，一般常见的解决办法是不断优化模具结构、对模具设计和加工提出了非常高的精度要求，这需要大量实践经验的积累，另外在成型工艺方面往往需要延长成型周期，以往在材料方面优化改善的办法不多，并且效果也不显著。另外，汽车内饰制件的气味品质一直都是行业内的一大难题，关于聚丙烯复合材料降低气味方法的报道其实有很多，包括加入吸附剂、加入萃取剂、烘烤脱挥等，但是即使制备得到的聚丙烯复合材料的气味效果很好，在注塑成型环节，材料再次经过熔融剪切会继续产生小分子有机物质，导致注塑成的汽车内饰件气味很多不能满足主机厂和终端消费者期望的要求，批量烘烤处理气味不合格的制件效率很低，也不具备连续生产操作性，因此开发适合注塑成型要求的低气味聚丙烯复合材料也是一件迫在眉睫的事情。
现有技术公开了一种汽车内饰件用聚丙烯组合物，主要通过添加反应性聚酰胺，将其粘结包覆在滑石粉的表面形成保护膜，抑制滑石粉中金属离子导致的抗氧化剂的降解，从而抑制有机挥发性化合物的产生，而且反应性聚酰胺呈碱性，可以中和酸性的有机挥发性化合物，起到清除的作用，从而降低聚丙烯组合物的气味性。上述解决气味问题的聚丙烯组合物需要额外添加其他助剂，其也不能同 时解决聚丙烯组复合材料的外观问题。
发明内容
本发明的目的是克服现有聚丙烯复合材料注塑制件存在外观和气味问题的的缺陷和不足，提供一种聚丙烯复合材料，通过高流动聚丙烯材料主体树脂协同具有特定玻璃化转变温度差值的线性低密度聚乙烯树脂，不仅消除了注塑制件鼓包的外观缺陷，且直接注塑成型的汽车内饰件气味品质优异，满足各大主机厂标准要求。
本发明上述目的通过以下技术方案实现：
一种聚丙烯复合材料，以重量份数计，包括如下组分：
聚丙烯40～95份，填料0～40份，线性低密度聚乙烯5-20份；
其中，所述聚丙烯的熔体质量流动速率为30～100g/10min，测试标准ISO1133-1-2011，230℃，2.16Kg载荷；
聚丙烯树脂中PP相与线性低密度聚乙烯中EPR相的两相玻璃化转变温度差Tg(PP相)-Tg(EPR相)≤50℃。
其中，需要说明的是：
玻璃化转变温度的测试方法采用DSC法，DSC表征材料的玻璃化转变温度是测量材料的比热容随温度的变化，玻璃化转变温度Tg前后比热容会发生较大变化，根据曲线可以确定玻璃化转变温度。玻璃化转变温度通常是一个吸热方向的台阶，玻璃化转变是一个区域，此法通常以与两条外推基线的距离相等的线与曲线的交点作为玻璃化转变温度，测试温度范围在-60℃-100℃，升降温速率为20℃/min，先从23℃升温至100℃，再从100℃降温至-60℃，再从-60℃升温至100℃。
在本发明的聚丙烯复合材料中可以添加填料成分，填料可以为滑石粉、碳酸钙、硅灰石和晶须中的一种或几种。
本发明的聚丙烯复合材料中，作为主体树脂的聚丙烯的熔体质量流动速率为30～100g/10min，为高流动聚丙烯材料，本身有很好的流动性能，可以在较低的注塑温度下快速充满各大型模具型腔，降低材料受热和剪切的程度，材料可以在较低的注塑温度下进行注塑加工，加工温度较低可以有效避免材料过热分解，减少了气味小分子的挥发产生，有利于气味品质的保证。
本发明所添加的聚丙烯基体树脂与线性低密度聚乙烯的两相玻璃化转变温 度差≤50℃，差值较小，该线性低密度聚乙烯容易在聚丙烯基体树脂中形成连续分布相，且线性低密度聚乙烯树脂的EPR相与聚丙烯树脂的PP相之间的相容性更好，在加工过程中两相间不会形成过多的微观空隙，从而解决了塑料熔体中夹杂的小分子物质难以彻底排出的问题，塑料熔体中的小分子物质可以顺利排出就避免了注塑成型的制件鼓包现象的出现，提高了注塑产品的外观质量，同时因为制备过程中小分子物质顺利排出，也降低了注塑制件的气味，解决了气味超标的问题，注塑成型所得的制件具有良好的外观效果和低气味的品质水平，尤其适合于大型内饰低气味制件的高效率生产。
本发明的聚丙烯复合材料具有良好的注塑外观性能，在注塑制备时，尤其是大尺寸模具成型时也可以具有良好的外观性能，可以广泛适用于各类模具结构，降低了对模具结构设计的高要求。
在本发明的聚丙烯复合材料中线性低密度聚乙烯的含量也是至关重要的，线性低密度聚乙烯的协同用量过小，则复合材料的韧性较差(≤10KJ/m2)，且线性低密度聚乙烯在聚丙烯材料里面不能形成连续相，两相间容易形成微观分离，容易产生鼓泡和气味小分子残留。线性低密度聚乙烯的协同用量过大，则聚丙烯复合材料的刚性较差，制件整体偏软，不能满足大部分工况使用要求。
优选地，以重量份数计，包括如下组分：
聚丙烯65～80份，填料10～20份；线性低密度聚乙烯10～15份。
优选地，所述线性低密度聚乙烯的Tg(EPR相)与聚丙烯树脂的Tg(PP相)的两相玻璃化转变温度差为45～48℃。
这里需要说明的是两相玻璃化转变温度差需要控制在一个合理的范围内，温度差太小说明LLDPE的Tg(EPR相)偏高，复合材料在低温(≤-20℃)条件下偏硬，韧性不够。
优选地，所述聚丙烯的熔体质量流动速率为50～90g/10min，测试标准ISO 1133-1-2011，230℃，2.16Kg载荷。
优选地，所述线性低密度聚乙烯的熔体质量流动速率为15～25g/10min，测试标准ISO 1133-1-2011，190℃，2.16Kg载荷，
本发明在以上述聚丙烯为基体树脂的基础上，还添加了线性低密度聚乙烯，线性低密度聚乙烯熔指过低不利于在聚丙烯基体树脂里面形成稳定的连续分散相，同时也会降低整个复合材料的流动性；线性低密度聚乙烯熔指过高不利于改 善注塑成内饰制件后的外观性能。
进一步，为了进一步改善聚丙烯复合材料的气味品质，优选地，所述聚丙烯的气味按照大众PV3900标准测试为3.5～4.0级。
优选地，所述线性低密度聚乙烯气味按照大众PV3900标准测试为3.5～4.0级。
原料气味等级的控制是获得低气味复合材料的基础，但是光靠原材料气味低是没法满足主机厂严格的气味品质要求，优选上述聚丙烯和线性低密度聚乙烯结合本发明的具体配方可以达到更高的品质要求。
优选地，所述填料为滑石粉、碳酸钙、硅灰石和晶须中的一种或几种。
在具体的实施方式中，为了满足聚丙烯复合材料的其他应用需求，聚丙烯复合材料中还可以添加以重量份计0.05～5份的加工助剂，其中加工助剂可以为颜料、抗氧剂、耐候剂和润滑剂中的一种或几种。
其中，本发明的颜料可以为有机或无机颜料。
无机颜料可以为钛白，铬黄，镉黄，钼铬红，铁红(黄)，镉红，群青，钴蓝，铁蓝，铬绿，钴绿，金属粉，云母珠光，炭黑等。
有机颜料可以为偶氮类，色啶类，酞菁类，染料类等。
本发明的抗氧剂可以为：受阻酚类抗氧剂、亚磷酸酯类抗氧剂等。
本发明的耐候剂可以为：受阻胺类耐候剂。
本发明的润滑剂可以为：硬脂酸钙和硬脂酸锌等。
本发明还具体保护一种上述聚丙烯复合材料的制备方法，包括如下步骤：
将各组分混合均匀，再加入到挤出机中，在170℃～240℃的温度下进行熔融混炼，然后造粒、冷却、干燥得到聚丙烯复合材料。
本发明的挤出机可以为双螺杆挤出机或往复式单螺杆挤出机，螺杆长径比不小于32。
本发明的聚丙烯复合材料在制备汽车内饰中的应用也在本发明的保护范围内。
本发明的聚丙烯复合材料具有良好注塑外观质量，可以很好地消除制件表面的鼓包外观缺陷，并且所注塑的汽车内饰具有良好的气味品质，可以广泛应用于不同结构和尺寸的汽车内饰件的注塑生产，例如汽车门板、仪表板、立柱等，可以满足高外观低气味品质要求。
与现有技术相比，本发明的有益效果是：
本发明的聚丙烯复合材料以高流动的聚丙烯材料作为主体树脂，能够快速填满不同壁厚的型腔且能实现低温注塑，减少了材料受热和剪切分解的程度，保证气味品质。且还添加了与聚丙烯两相玻璃化转变温差差值≤50℃的线性低密度聚乙烯，能够起到明显降低两相相分离的作用，避免塑料熔体出现微观空隙且夹杂的空气和小分子有机气体难以彻底排除的问题，注塑成型的内饰制件具体良好的外观质量和突出的低气味品质优势。
本发明的聚丙烯复合材料的外观鼓包等级可以达到2级及以下，气味等级可以达到3.5级及以下，具有突出的抗鼓包的外观效果和良好的气味品质，且曲性能可以达到1600MPa以上，韧性测试悬臂梁缺口冲击性能可以达到15kJ/m2以上，满足刚韧平衡的综合力学性能要求。
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，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
本发明的实施例和对比例的原料信息如下：
聚丙烯：
PP-1：PP-BX3900，熔体质量流动速率为60g/10min，测试标准ISO 1133-1-2011，测试条件230℃，2.16Kg，气味3.5级(PV3900标准)，厂家：SK；
PP-2：PP BX3920，熔体质量流动速率为100g/10min，测试标准ISO 1133-1-2011，测试条件230℃，2.16Kg，气味3.5级(PV3900标准)，厂家：SK；
PP-3：PP BX3800，熔体质量流动速率为30g/10min，测试标准ISO 1133-1-2011，测试条件230℃，2.16Kg，气味4.0级(PV3900标准)，厂家：SK；
PP-4：PP EP640V，熔体质量流动速率为90g/10min，测试标准ISO 1133-1-2011，测试条件230℃，2.16Kg，气味3.5级(PV3900标准)，厂家：中海壳牌；
PP-5：PP SP179(兰化)，熔体质量流动速率为10g/10min，测试标准ISO  1133-1-2011，测试条件230℃，2.16Kg，气味3.5级(PV3900标准)，厂家：兰州石化；
线性低密度聚乙烯1：LLDPE M2320，熔体质量流动速率为20g/10min，测试标准ISO 1133-1-2011，测试条件190℃，2.16Kg，气味3.5级(PV3900标准)，厂家：茂名石化；
线性低密度聚乙烯2：LLDPE M2320(DNDA-7144)，熔体质量流动速率为20g/10min，测试标准ISO 1133-1-2011，测试条件190℃，2.16Kg，气味3.5级(PV3900标准)，厂家：茂名石化；
线性低密度聚乙烯3：LLDPE-L M2320(ZHONGYUAN)，熔体质量流动速率为17g/10min，测试标准ISO 1133-1-2011，测试条件190℃，2.16Kg，气味3.5级(PV3900标准)，厂家：茂名石化；
线性低密度聚乙烯4：SABIC 6201RQ粉，熔体质量流动速率为50g/10min，测试标准ISO 1133-1-2011，测试条件190℃，2.16Kg，气味4.0级(PV3900标准)，厂家：SABIC；
线性低密度聚乙烯5：LLDPE EXCEED 3518PA，熔体质量流动速率为1g/10min，测试标准ISO 1133-1-2011，测试条件190℃，2.16Kg，气味4.0级(PV3900标准)，厂家：埃克森美孚；
滑石粉，市购可得，本发明的平行实施例和对比例均为同种；
抗氧剂：受阻酚类主抗氧剂+亚磷酸酯类辅抗氧剂，主抗氧剂和辅抗氧剂的质量比为1:1，市售，本发明的平行实施例和对比例均为同种市售产品。
实施例1～15
一种聚丙烯复合材料，以重量份数计，包括如下表1所示组分。
表1.实施例1～15的聚丙烯复合材料的组成

上述实施例1～15的聚丙烯复合材料的制备方法包括如下步骤：
根据表1中各组分的重量份将各组分在混合设备中混合均匀，再加入到长径比为40:1的双螺杆挤出机中，在200℃的温度下进行熔融混炼，然后造粒、冷却、在120℃烘烤6小时后得到聚丙烯组合物。
在注塑温度为200℃，注塑压力45MPa，注塑速度45m/s，保压压力30MPa，保压时间5s的条件下通过注塑成型分别得到尺寸为100mm*100mm*3mm塑料光板以及ISO标准弯曲和缺口冲击样条。
对比例1～3
一种聚丙烯复合材料，以重量份数计，包括如下表2所示组分。
表2.对比例1～3的聚丙烯复合材料的组成
上述对比例1～3的聚丙烯复合材料的制备方法包括如下步骤：
根据表2中各组分的重量份将各组分在混合设备中混合均匀，再加入到长径比为40:1的双螺杆挤出机中，在200℃的温度下进行熔融混炼，然后造粒、冷却、在120℃烘烤6小时后得到聚丙烯组合物。
在注塑温度为200℃，注塑压力45MPa，注塑速度45m/s，保压压力30MPa，保压时间5s的条件下通过注塑成型分别得到尺寸为100mm*100mm*3mm塑料光板以及ISO标准弯曲和缺口冲击样条。
结果检测
对上述实施例1～15和对比例1～3的聚丙烯复合材料的外观质量，气味品质和相关力学性能进行检测，具体检测方法如下：
(1)气味和外观测试
塑料光板(长宽厚尺寸为100mm*100mm*3mm)分别评估气味(VDA270标准，1L试验瓶，实验条件80℃/2h)和鼓包效果(目视评价)，最好为1级，最差为6级，由5名专业评测者分别打分并取平均值(四舍五入)。
具体评级标准如下表3：
表3.气味和外观评价标准
(2)力学性能测试
检测弯曲性能表征聚丙烯复合材料的刚性，检测标准为ISO 178-2010，MPa。
检测悬臂梁缺口冲击性能表征聚丙烯复合材料的韧性，检测标准ISO180-2019，A型缺口，kJ/m2。
具体评估结果见下表4。
表4.实施例1-15和对比例1～3的聚丙烯复合材料的检测结果

从上述表4的数据可以看出，本发明采用高流动低气味聚丙烯材料作为主体树脂，添加两相玻璃化转变温度Tg(PP相)-Tg(EPR相)差值较小的LLDPE树脂并将其添加量控制在合适范围内，可制备出具有消除鼓包缺陷(≤2.0级)和气味品质(≤3.5级)的聚丙烯复合材料，本发明的聚丙烯复合材料通过注塑所得的汽车内饰件具有突出的抗鼓包的外观效果和良好的气味品质。
且本发明的聚丙烯复合材料还具有良好的力学性能，刚性测试弯曲性能可以达到1600MPa以上，韧性测试悬臂梁缺口冲击性能可以达到15kJ/m2以上，满足刚韧平衡的综合力学性能要求。
本发明材料尤其适合于汽车大型内饰低气味良外观制件的注塑要求，有效解决了汽车注塑行业面临的制件气味超标和容易鼓包的难题。
对比例1中线性低密度聚乙烯的用量过高，不仅聚丙烯复合材料的外观和气味无法达到相关要求，且聚丙烯复合材料的刚性也不佳，无法满足刚韧平衡的综合力学性能要求。
对比例2中线性低密度聚乙烯的用量过低，不仅聚丙烯复合材料的外观和气味无法达到相关要求，且聚丙烯复合材料韧性也不佳，无法满足刚韧平衡的综合力学性能要求。
对比例3中聚丙烯PP-5不在本发明的保护范围内，聚丙烯复合材料的外观和气味显著劣化，且聚丙烯复合材料的刚性也劣化严重，无法满足刚韧平衡的综合力学性能要求。
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. 一种聚丙烯复合材料，其特征在于，以重量份数计，包括如下组分：
    聚丙烯40～95份，填料0～40份，线性低密度聚乙烯5～20份；
    其中，所述聚丙烯的熔体质量流动速率为30～100g/10min，测试标准ISO 1133-1-2011，230℃，2.16Kg载荷；
    聚丙烯树脂中PP相与线性低密度聚乙烯中EPR相的两相玻璃化转变温度差Tg(PP相)-Tg(EPR相)≤50℃。
  2. 如权利要求1所述聚丙烯复合材料，其特征在于，以重量份数计，包括如下组分：
    聚丙烯65～80份，填料10～20份；线性低密度聚乙烯10～15份。
  3. 如权利要求1所述聚丙烯复合材料，其特征在于，聚丙烯树脂中PP相与线性低密度聚乙烯中EPR相的两相玻璃化转变温度差Tg(PP相)-Tg(EPR相)为45～48℃。
  4. 如权利要求1所述聚丙烯复合材料，其特征在于，所述聚丙烯的熔体质量流动速率为50～90g/10min，测试标准ISO 1133-1-2011，230℃，2.16Kg载荷。
  5. 如权利要求1所述聚丙烯复合材料，其特征在于，所述线性低密度聚乙烯的熔体质量流动速率为15～25g/10min，测试标准ISO1133-1-2011，190℃，2.16Kg载荷。
  6. 如权利要求1所述聚丙烯复合材料，其特征在于，所述聚丙烯的气味按照大众PV3900：2019-04标准测试为3.5～4.0级。
  7. 如权利要求1所述聚丙烯复合材料，其特征在于，所述线性低密度聚乙烯气味按照大众PV3900：2019-04，标准测试为3.5～4.0级。
  8. 如权利要求1所述聚丙烯复合材料，其特征在于，所述填料为滑石粉、碳酸钙、硅灰石和晶须中的一种或几种。
  9. 一种权利要求1～8任意一项所述聚丙烯复合材料的制备方法，其特征在于，包括如下步骤：
    将各组分混合均匀，再加入到挤出机中，在170℃～240℃的温度下进行熔融混炼，然后造粒、冷却、干燥得到聚丙烯复合材料。
  10. 一种权利要求1～8任意一项所述聚丙烯复合材料在制备汽车内饰制品中的应用。
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