WO2023103858A1 - 一种高模量高耐热透明聚丙烯组合物及其制备方法 - Google Patents

一种高模量高耐热透明聚丙烯组合物及其制备方法 Download PDF

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WO2023103858A1
WO2023103858A1 PCT/CN2022/135557 CN2022135557W WO2023103858A1 WO 2023103858 A1 WO2023103858 A1 WO 2023103858A1 CN 2022135557 W CN2022135557 W CN 2022135557W WO 2023103858 A1 WO2023103858 A1 WO 2023103858A1
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modulus
heat
polypropylene composition
transparent polypropylene
product
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PCT/CN2022/135557
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French (fr)
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赵治国
陈平绪
叶南飚
杨霄云
陆湛泉
李栋栋
王爱东
谢修好
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金发科技股份有限公司
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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
    • C08K5/00—Use of organic ingredients
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to a high-modulus, high-heat-resistant transparent polypropylene composition and a preparation method thereof.
  • random polypropylene PP (PP-Random) is more and more widely used in the fields of food and medicine because of its good hygiene.
  • transparent PP materials have many advantages over traditional transparent materials (PC, PET, PS, PVC, PPSU, etc.) in terms of density, flexibility, chemical resistance, cost, and environmental stress cracking resistance.
  • rigidity and heat resistance limit the application of transparent polypropylene materials in optical lampshades, steam pot lids, and high-temperature sterilization milk bottles; in addition, the transparency of atactic polypropylene is affected by many factors, and a small amount of additives Additives may lead to a significant decrease in the transparency of the processed product.
  • high-transparency PP materials are mainly prepared by adding nucleating agents or metallocene catalyzed synthesis into the matrix, and the transparency is improved by controlling the crystallinity and grain size of polypropylene.
  • the proportion of fillers in the formulations of these products is relatively small , so its rigidity performance is poor, and although the increase of filler content can objectively improve the rigidity of the product, its transparency cannot be guaranteed;
  • some existing technologies introduce organic rigidity modifiers to adjust the modified PP matrix It improves the rigidity, but these modifiers have poor compatibility with the PP matrix, which will also affect the appearance and transparency of the product.
  • the purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a high-modulus, high-heat-resistant transparent polypropylene composition.
  • This product introduces specific fillers and nucleating agents as components, while ensuring transparency. , can effectively improve its heat resistance, and the flexural modulus can be adjusted according to the actual application, up to 2200MPa.
  • a transparent polypropylene composition with high modulus and high heat resistance comprising the following components in parts by weight: 70-90 parts of random polypropylene resin, 5-20 parts of filler, 5-10 parts of compatibilizer, and 0.1 parts of nucleating agent ⁇ 0.5 parts;
  • the filler is PMMA cross-linked microspheres, and the D50 of the PMMA cross-linked microspheres is 1-2 ⁇ m;
  • the nucleating agent is a sorbitol nucleating agent.
  • the random polypropylene resin has a haze (Haze) ⁇ 20% under the test according to GB/T 2410-2008 (2mm thickness, 100mm*100mm injection molded square plate).
  • the high-transparency resin such as atactic polypropylene resin is used as the matrix resin, and PMMA crosslinked microspheres are introduced as fillers simultaneously, and due to the PMMA crosslinking
  • the light transmittance of microspheres is relatively close to that of polypropylene resin, and it will not affect the transparency of the product after being introduced as a component under a specific particle size, and its high hardness and thermal oxidation resistance can effectively improve the heat resistance of the product and adjust Flexural modulus; in addition, the use of sorbitol-based compatibilizers in the components not only refines the grains of polypropylene resin, effectively improves the transparency of the product, but also synergistically further improves the flexural modulus of the product, and if the nucleating agent is selected Improper types may cause the performance of the product to decline.
  • PMMA cross-linked microspheres of not any size can achieve the above-mentioned performance improvement effect.
  • mechanical properties if the particle size is too small, there will be no enhancement; and if the particle size is too large, not only It will not significantly improve the flexural modulus of the product, but will also greatly affect the impact properties of the resulting product, making it very brittle and narrowing the application range; in terms of heat resistance and transparency, the inventors have found through experiments that PMMA crosslinking If the particle size of the microsphere is too large or too small, the effect is similar to that of other types of fillers, and it does not significantly improve the transparency or heat resistance, but may cause some performance to be weakened. After screening, the properties of the PMMA cross-linked microspheres with a particle size of 1-2 ⁇ m meet the requirements.
  • the mass ratio of the random polypropylene resin to the filler in the components of the high modulus and high heat-resistant transparent polypropylene composition is (8.5:1) to (8:1.5).
  • PMMA cross-linked microspheres as a filler can improve the transparency and heat resistance of the product compared to other types of fillers, but too much PMMA cross-linked microspheres will still reduce the transparency of the product to a certain extent, while the impact properties It will also be affected.
  • the amount of filler added exceeds a certain range, due to the large particle size of the PMMA crosslinked microspheres used, the comprehensive mechanical properties of the product will be greatly reduced (including rigidity and toughness). Therefore, considering the comprehensive properties, the mass ratio of polypropylene resin to PMMA crosslinked microspheres is (8.5:1)-(8:1.5) the most appropriate.
  • the atactic polypropylene resin in the components of the high modulus and high heat-resistant transparent polypropylene composition can be compounded with a variety of different properties
  • random polypropylene resin Although the transparency of random polypropylene resin is generally high, its rigidity and toughness vary greatly among different types or brands of products. Using different types of random polypropylene resin for compounding can effectively adjust the rigidity or toughness of the product. Toughness performance, so that the scope of application of the product becomes wider.
  • the compatibilizer is a polar monomer grafted polypropylene polymer, and the polar monomer is at least one of maleic anhydride, acrylic acid, and acrylate derivatives;
  • the polar monomer is maleic anhydride
  • the graft ratio of the polar monomer maleic anhydride is 1-3 wt%.
  • the preferred compatibilizer can effectively strengthen the connection between PMMA crosslinked microspheres and random polypropylene resin, further enhance the particle reinforcement of PMMA crosslinked microspheres, and the inventors found that the polymerization of polypropylene grafted with polar monomers
  • the compound When the compound is used as a compatibilizer, it has the best compatibility with random polypropylene resin, and when the polar monomer is maleic anhydride, the product can obtain the best flexural modulus and heat resistance;
  • the grafting rate of polar monomers also has a certain impact on the performance of the product. If the grafting rate is low, it cannot play a good role as a compatibilizer, and the reinforcing effect on the material is limited, and the final prepared material is bent. The modulus is low; and if the grafting rate of the polar monomer is too high, because the material itself is soft, it cannot play a good compatibility effect, and the high grafting rate will also reduce the heat resistance of the product. Then the product is prone to yellowing, which reduces the light transmittance, and also brings a certain odor, which limits the scope of use of the product.
  • the components of the high-modulus, high-heat-resistant transparent polypropylene composition further include 0-2 parts of processing aids;
  • the processing aid is at least one of an antioxidant, a lubricant, and a coupling agent;
  • the antioxidant is at least one of hindered phenol antioxidants, phosphite antioxidants, and thioether antioxidants
  • the lubricant is metal soap lubricants, stearin At least one of acid complex ester lubricants and amide lubricants
  • the coupling agent is at least one of titanate coupling agents, aluminate coupling agents, and silane coupling agents.
  • Another object of the present invention is also to provide a preparation method of the high-modulus high-heat-resistant transparent polypropylene composition, comprising the following steps:
  • the preparation method of the high-modulus and high-heat-resistant transparent polypropylene composition of the invention has simple operation steps and can realize industrial scale production.
  • Another object of the present invention is to provide the application of the high-modulus and high-heat-resistant transparent polypropylene composition in the preparation of household electrical appliances.
  • the household appliance is any one of an optical lampshade, a steam pot cover, and a high-temperature sterilization bottle.
  • the polypropylene parts used in household appliances have defects such as difficulty in light transmission, poor heat resistance or poor mechanical properties, and the performance is difficult to meet the requirements of use, while the high modulus and high heat resistance of the present invention is transparent
  • the polypropylene composition has high transparency, good heat resistance and high flexural modulus, and can be completely used to replace existing products.
  • the invention provides a high-modulus, high-heat-resistant transparent polypropylene composition.
  • a high-transparency resin such as atactic polypropylene resin is used as a matrix resin, and PMMA crosslinked microspheres are introduced as a filler at the same time.
  • PMMA crosslinked microspheres are introduced as a filler at the same time.
  • the filler content does not exceed 20wt%
  • the maximum can reach 2200MPa (even if the content is less than 5wt%, it can reach at least 1350MPa); in addition, the compatibilizer of sorbitol in the component not only refines the crystal grains of polypropylene resin, but also effectively improves the transparency of the product. It can also synergistically further improve the flexural modulus of the product.
  • the invention also provides a preparation method of the high-modulus and high-heat-resistant transparent polypropylene composition and its application in the preparation of household electrical appliances.
  • Polypropylene resin 1 high-strength atactic polypropylene, UT8012 product produced by Sinopec Maoming Company, the initial haze under the test according to GB/T 2410-2008 is less than 20%;
  • Polypropylene resin 2 high-impact random polypropylene, PPR-MT25 product produced by Sinopec Maoming Company, the initial haze under the test according to GB/T 2410-2008 is less than 20%;
  • Filler 5 hollow glass microspheres
  • Compatibilizer 1 Maleic anhydride grafted polypropylene, AD-110 product produced by Nanhai Baichen, the maleic anhydride grafting rate is 2%;
  • Compatibilizer 2 maleic anhydride grafted polypropylene, AD-130 product produced by Nanhai Baichen, the grafting ratio of maleic anhydride is 0.3%;
  • Compatibilizer 3 maleic anhydride grafted polypropylene, AD-150 product produced by Nanhai Baichen, the grafting rate of maleic anhydride is 3.5%;
  • Compatibilizer 4 acrylic acid grafted polypropylene, PC-103 product produced by Nanhai Baichen, with acrylic acid grafting rate of 4%;
  • Compatibilizer 5 ethylene and acrylic acid copolymer EAA, ESCOR5050 product produced by Exxon Company, the content of acrylic acid is 5wt%;
  • Nucleating agent 1 sorbitol nucleating agent, NX-800 product produced by Milliken Company;
  • Nucleating agent 2 phosphate nucleating agent, TMP-6 product produced by Shanxi Institute of Chemical Industry;
  • Antioxidant a mixture of commercially available phosphite antioxidants and hindered phenolic antioxidants, the mass ratio is 1:1;
  • Coupling agent commercially available titanate coupling agent
  • Lubricant commercially available zinc stearate.
  • Cantilever beam notched impact strength test test according to ISO180-2000 standard, type A notch, impact pendulum capacity is 5.5J;
  • the high modulus and high heat-resistant transparent polypropylene composite material transparency that each embodiment of the present invention obtains is high (1mm light transmittance can reach more than 90%, 2mm light transmittance can reach 85% and above) and good heat resistance (HDT temperature can reach more than 100 °C), and according to actual application requirements, when the filler content accounts for only about 5-20wt%, the flexural modulus of the product obtained in the present invention can reach 1350-20wt%. 2200MPa; As can be seen from Examples 1 to 4, the proportioning of random polypropylene resin and filler in the product obtained by the present invention has an impact on the various properties of the product.
  • the heat resistance and flexural modulus are gradually increased, but the impact performance and transparency are reduced to a certain extent. Therefore, when the ratio of the two is (8.5:1) ⁇ (8:1.5), the product can maintain a high level at the same time.
  • Heat resistance, flexural modulus, impact performance and high transparency the overall performance of the product is the best; from the performance comparison of the products obtained in Example 3 and Examples 9-12, it can be known that the type of compatibilizer also affects the performance of the product , when the compatibilizer is maleic anhydride grafted polypropylene polymer, and the grafting rate is 1-3%, the flexural modulus and heat resistance of the product are high and the transparency is high.
  • Comparative Example 1 does not contain PMMA cross-linked microspheres, and compared with Example 3, both the mechanical properties and the heat resistance are all poor, while in Comparative Examples 5 and 6, polymer Styrene cross-linked microspheres and hollow glass microspheres are used as fillers to prepare products, and the transparency, mechanical properties or compatibility of the two fillers are not as good as PMMA cross-linked microspheres, although the flexural modulus of the product is somewhat higher than that of the comparative example 1 product.

Abstract

本发明涉及一种高模量高耐热透明聚丙烯组合物及其制备方法，属于高分子材料领域。本发明所述高模量高耐热透明聚丙烯组合物的组分中，采用无规聚丙烯树脂这种高透明度树脂作为基体树脂，同时引入PMMA交联微球作为填料，在不影响产品的透明度的前提下，可有效提升产品的弯曲模量的耐热性能；此外，组分中选用山梨醇类的相容剂不仅细化聚丙烯树脂的晶粒，有效提升产品的透明度，也可协同进一步提升产品的弯曲模量。本发明还公开了所述高模量高耐热透明聚丙烯组合物的制备方法及其在制备家电电器中的应用。

Description

一种高模量高耐热透明聚丙烯组合物及其制备方法 技术领域
本发明属于高分子材料领域，具体涉及一种高模量高耐热透明聚丙烯组合物及其制备方法。
背景技术
无规聚丙烯PP(PP-Random)作为常用的透明容器产品，由于产品具有较好卫生性，所以在食品和药品领域应用越来越广泛。现有技术中，透明PP材料在密度、柔韧性、抗化学性、成本和耐环境应力开裂性能等方面对比传统的透明材料(PC、PET、PS、PVC、PPSU等)有很多优势，但是在刚性和耐热性方面存在不足，这些劣势限制了透明聚丙烯材料在光学灯罩，蒸汽锅盖，高温消毒奶瓶方面的应用；此外，无规聚丙烯的透明度受影响因素较多，少量的添加助剂便可能导致加工产品透明度大幅度下降。
一般而言，高透明PP材料主要在通过基体中加入成核剂或者茂金属催化合成制备，通过控制聚丙烯的结晶度和晶粒大小来达到提高透明度，然而这些产品的配方中填料占比较少，因此其刚性性能均较差，而虽然填料含量的增加可客观提升产品的刚性，但相对而言其透明度又无法得到保障；此外，一些现有技术引入有机刚性改性剂调整改性PP基体使其刚性提升，但这些改性剂与PP基体相容性较差，同样会影响产品的外观及透明度。同时，现有技术中对于透明PP材料产品的耐热性能暂还没有有效方法进行改善。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种高模量高耐热透明聚丙烯组合物，该产品通过引入特定的填料及成核剂作为组分，在保障透明度的同时，可有效提升其耐热性能，而弯曲模量可根据实际应用进行调节， 最高可达2200MPa。
为实现上述目的，本发明采取的技术方案为：
一种高模量高耐热透明聚丙烯组合物，包含如下重量份的组分：无规聚丙烯树脂70～90份、填料5～20份、相容剂5～10份、成核剂0.1～0.5份；
所述填料为PMMA交联微球，所述PMMA交联微球的D50为1～2μm；
所述成核剂为山梨醇类成核剂。
优选地，所述无规聚丙烯树脂根据GB/T 2410-2008测试下(2mm厚度，100mm*100mm的注塑方板)雾度(Haze)≤20％。
本发明所述高模量高耐热透明聚丙烯组合物的组分中，采用无规聚丙烯树脂这种高透明度树脂作为基体树脂，同时引入PMMA交联微球作为填料，而由于PMMA交联微球的透光率与聚丙烯树脂比较接近，在特定粒径下作为组分引入后并不会影响产品的透明度，且其高硬度和耐热氧化性可有效提升产品的耐热性能及调节弯曲模量；此外，组分中选用山梨醇类的相容剂不仅细化聚丙烯树脂的晶粒，有效提升产品的透明度，也可协同进一步提升产品的弯曲模量，而若选用成核剂种类不当，很可能引起产品的各项性能均有所下降。
本发明的发明人经过实验后发现，并非任意尺寸的PMMA交联微球可实现上述性能提升效果，在力学性能方面，若其粒径过小，则没有增强作用；而粒径过大，不仅不会明显提升产品的弯曲模量，还会极大影响所得产品的冲击性能，使其变得非常脆，应用范围变窄；在耐热性和透明度方面，发明人经过实验发现，PMMA交联微球的粒径过大或过小时的效果与其他种类的填料效果相近，并没有明显的提高透明度或者耐热性的性能，反而可能会造成部分性能的削弱。经过筛选后，以粒径为1～2μm的PMMA交联微球性质符合要求。
优选地，所述无规聚丙烯树脂与填料在高模量高耐热透明聚丙烯组合物组分的质量之比为(8.5:1)～(8:1.5)。
虽然使用PMMA交联微球作为填料相比其他种类的填料可使产品的透明度 和耐热性能有所提升，然而过多的PMMA交联微球还是会一定程度地降低产品的透明度，同时冲击性能也会受到影响，此外，若填料添加量超过一定范围，由于所使用的PMMA交联微球粒径较大，因此会造成产品的综合力学性能大幅度下降(包括刚性性能和韧性性能)。因此经各综合性能考虑，以聚丙烯树脂与PMMA交联微球的质量之比为(8.5:1)～(8:1.5)最为合适。
优选地，所述高模量高耐热透明聚丙烯组合物的组分中无规聚丙烯树脂可选用多种不同性质的种类进行复配；
无规聚丙烯树脂虽然透明度总体上较高，但其本身无论是刚性或是韧性不同种类或牌号商品间差异较大，采用不同种类的无规聚丙烯树脂进行复配可有效调节产品的刚性或韧性性能，使产品适用范围变广。
优选地，所述相容剂为极性单体接枝聚丙烯聚合物，所述极性单体为马来酸酐、丙烯酸、丙烯酸酯类衍生物中的至少一种；
更优选地，所述极性单体为马来酸酐；
更优选地，所述极性单体马来酸酐的接枝率为1～3wt％。
优选的相容剂可有效加强PMMA交联微球与无规聚丙烯树脂的连接，进一步提升PMMA交联微球的粒子增强作用，而发明人发现，采用极性单体接枝的聚丙烯聚合物作为相容剂时与无规聚丙烯树脂的相容性最好，且当极性单体为马来酸酐时，产品可获得最佳的弯曲模量和耐热性能；
此外，极性单体的接枝率也对产品的性能有一定影响，接枝率较低，则不能够起到很好的相容剂作用，对材料的增强作用有限，最终制备的材料弯曲模量偏低；而如果极性单体的接枝率过高，由于材料本身较软，同样无法起到很好的相容作用，且高接枝率还会造成产品的耐热性能降低，进而产品容易产生发黄现象，降低透光度，同时还会带来一定的气味性，使产品的使用范围受限。
优选地，所述高模量高耐热透明聚丙烯组合物的组分中还包括0～2份加工助剂；
更优选地，所述加工助剂为抗氧剂、润滑剂、偶联剂中的至少一种；
更优选地，所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂、硫醚类抗氧剂中的至少一种；所述润滑剂为金属皂类润滑剂、硬脂酸复合酯类润滑剂、酰胺类润滑剂中的至少一种；所述偶联剂为钛酸酯偶联剂、铝酸酯偶联剂、硅烷偶联剂中的至少一种。
本发明的另一目的还在于提供所述高模量高耐热透明聚丙烯组合物的制备方法，包括以下步骤：
将无规聚丙烯树脂、成核剂、相容剂、加工助剂按配比混合均匀并加入至双螺杆挤出机，随后在双螺杆挤出机侧喂料口加入填料混合挤出造粒，即得所述高模量高耐热透明聚丙烯组合物。
本发明所述高模量高耐热透明聚丙烯组合物的制备方法操作步骤简单，可实现工业化规模生产。
本发明的再一目的在于提供所述高模量高耐热透明聚丙烯组合物在制备家电电器中的应用。
优选地，所述家用电器为光学灯罩、蒸汽锅盖、高温消毒瓶中的任一种。
现有技术中应用于家电电器中的聚丙烯部件零件等存在难以透光、耐热性能差或者力学性能较差的缺陷，性能难以达到使用需求，而本发明所述高模量高耐热透明聚丙烯组合物透明度高，耐热性能好，弯曲模量高，完全可用于替代现有产品。
与现有技术相比，本发明的有益效果为：
本发明提供了一种高模量高耐热透明聚丙烯组合物，该产品的组分中，采用无规聚丙烯树脂这种高透明度树脂作为基体树脂，同时引入PMMA交联微球作为填料，在不影响产品的透明度的前提下，可有效提升产品的耐热性能(热变形温度达到100℃以上)，同时可根据实际应用需求调节弯曲模量，在填料含量占比不超过20wt％的情况下最高可达2200MPa(即使含量占比不足5wt％也可 至少达到1350MPa以上)；此外，组分中选用山梨醇类的相容剂不仅细化聚丙烯树脂的晶粒，有效提升产品的透明度，也可协同进一步提升产品的弯曲模量。本发明还提供了所述高模量高耐热透明聚丙烯组合物的制备方法及其在制备家电电器中的应用。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
本发明实施例及对比例中聚丙烯组合物的制备方法为：
将无规聚丙烯树脂、成核剂、相容剂、加工助剂按配比混合均匀并加入至双螺杆挤出机，随后在双螺杆挤出机侧喂料口加入填料混合挤出造粒，即得所述聚丙烯组合物。
本发明实施例及对比例中使用的原料信息如下：
聚丙烯树脂1：高强度无规聚丙烯，中石化茂名公司生产UT8012产品，根据GB/T 2410-2008测试下的初始雾度小于20％；
聚丙烯树脂2：高冲击无规聚丙烯，中石化茂名公司生产PPR-MT25产品，根据GB/T 2410-2008测试下的初始雾度小于20％；
填料1：PMMA交联微球，综研化学公司生产MX-1500产品，D50＝1.5μm；
填料2：PMMA交联微球，综研化学公司生产MX-80产品，D50＝0.5μm；
填料3：PMMA交联微球，综研化学公司生产MX-300产品，D50＝3μm；
填料4：聚苯乙烯交联微球，ThermoFisher生产3125A产品，D50＝0.3μm；
填料5：中空玻璃微珠产品：3M公司生产的IM16k产品，D50＝15μm；
相容剂1：马来酸酐接枝聚丙烯，南海柏晨生产AD-110产品，马来酸酐接枝率为2％；
相容剂2：马来酸酐接枝聚丙烯，南海柏晨生产AD-130产品，马来酸酐接枝率为0.3％；
相容剂3：马来酸酐接枝聚丙烯，南海柏晨生产AD-150产品，马来酸酐接枝率为3.5％；
相容剂4：丙烯酸接枝聚丙烯，南海柏晨生产PC-103产品，丙烯酸接枝率为4％；
相容剂5：乙烯和丙烯酸共聚物EAA，Exxon公司生产的ESCOR5050产品，丙烯酸的含量为5wt％；
成核剂1：山梨醇类成核剂，美利肯公司生产的NX-800产品；
成核剂2：磷酸盐类的成核剂，山西化工研究所生产的TMP-6产品；
抗氧剂：市售亚磷酸酯类抗氧剂和受阻酚类类抗氧剂的混合物，质量比为1:1；
偶联剂：市售钛酸酯偶联剂；
润滑剂：市售硬脂酸锌。
实施例1～13
各实施例所述高硬度聚丙烯复合材料的各组分及用量如表1所示。
对比例1～7
各对比例所述聚丙烯复合材料的各组分及用量如表2所示，各组分所用的原料与各实施例所用均为同一市售品种。
表1
Figure PCTCN2022135557-appb-000001
Figure PCTCN2022135557-appb-000002
表2
Figure PCTCN2022135557-appb-000003
效果例1
为了考察本发明所述高模量高耐热透明聚丙烯复合材料的性能，对各实施例和对比例所得产品进行如下测试：
(1)弯曲模量测试：根据ISO178-2019标准进行测试，弯曲速率2mm/min；
(2)悬臂梁缺口冲击强度测试：根据ISO180-2000标准进行测试，A型缺口，冲击摆锤能力为5.5J；
(3)热变形温度(HDT)测试：根据ISO75-2-2013测试，所述测试压力条件0.45MPa；
(4)透明度测试：根据ASTM D1003-2007测试，测试厚度1mm和2mm；分别测试产品的透光率和雾度。
各产品测试结果如表3和表4所示。
表3
Figure PCTCN2022135557-appb-000004
表4
Figure PCTCN2022135557-appb-000005
从表3及表4可知，本发明所述各实施例得到的高模量高耐热透明聚丙烯复合材料透明度高(1mm透光率可达到90％以上，2mm透光率可达到85％及以上)且耐热性能好(HDT温度可达到100℃以上)，而根据实际应用要求，在填料含量占比仅约5～20wt％的情况下，本发明所得产品的弯曲模量可达到1350～2200MPa；从实施例1～4可知，本发明所得产品中无规聚丙烯树脂和填料的配比对产品的各项性能有所影响，随着PMMA交联微球的占比逐渐提升，产品的耐热性和弯曲模量逐渐增高，但是冲击性能和透明度则出现了一定幅度的降低，因此，两者的配比以(8.5:1)～(8:1.5)时产品可同时维持较高的耐热性能、弯曲模量、冲击性能和高透明度，产品的综合性能最好；从实施例3与实施例9～12所得产品的性能比较可知，相容剂的种类对产品的性能也有所影响，当所述相容剂为马来酸酐接枝聚丙烯聚合物，且接枝率为1～3％时，产品的弯曲模量和耐热性较高且透明度高。相比之下，对比例1所得产品中不含PMMA交联微球，与实施例3相比无论是力学性能亦或是耐热性能均较差，而对比例5和6中则分别采用聚苯乙烯交联微球和中空玻璃微珠作为填料制备产品，两种填料的透明度、力学性能或者相容性均不如PMMA交联微球，虽然产品的弯曲模量相比对比例1产品有所提升，但是耐热性能并没有明显提升，且产品的冲击性能和透明度明显降低；另一方面，对比例3和4所得产品中采用了粒径过小或过大的PMMA交联微球作为填料，其中对比例3所得产品与实施例3相比，无论是弯曲模量和冲击性能相比均较低，说明该填料对产品的力学性能没有显著的提升，而对比例4所得产品的冲击性能还出现了削弱，同时所得产品与不添加填料的对比例1相比并没有明显的耐热性能提升，而透光性甚至出现了削 弱。综上，说明采用本发明权利要求保护范围之外的粒径及种类的填料均无法达到理想的技术效果；而从对比例2还可知，若PMMA交联微球添加过多，不仅会造成产品的冲击性能和弯曲模量的同时降低，产品的透明度也将受到较大影响。从对比例7可知，成核剂种类的选择若不当，很可能会造成产品的各项性能均有所下降。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (8)

  1. 一种高模量高耐热透明聚丙烯组合物，其特征在于，包含如下重量份的组分：无规聚丙烯树脂70～90份、填料5～20份、相容剂5～10份、成核剂0.1～0.5份；
    所述填料为PMMA交联微球，所述PMMA交联微球的D50为1～2μm；
    所述成核剂为山梨醇类成核剂。
  2. 如权利要求1所述高模量高耐热透明聚丙烯组合物，其特征在于，所述无规聚丙烯树脂与填料在高模量高耐热透明聚丙烯组合物组分的质量之比为(8.5:1)～(8:1.5)。
  3. 如权利要求1所述高模量高耐热透明聚丙烯组合物，其特征在于，所述相容剂为极性单体接枝聚丙烯聚合物，所述极性单体为马来酸酐、丙烯酸、丙烯酸酯类衍生物中的至少一种。
  4. 如权利要求3所述高模量高耐热透明聚丙烯组合物，其特征在于，所述极性单体为马来酸酐。
  5. 如权利要求4所述高模量高耐热透明聚丙烯组合物，其特征在于，所述极性单体的接枝率为1～3wt％。
  6. 如权利要求1所述高模量高耐热透明聚丙烯组合物，其特征在于，所述高模量高耐热透明聚丙烯组合物的组分中还包括0～2份加工助剂；优选地，所述加工助剂为抗氧剂、润滑剂、偶联剂中的至少一种。
  7. 如权利要求1～6任一项所述高模量高耐热透明聚丙烯组合物的制备方法，其特征在于，包括以下步骤：
    将各组分按配比混合均匀并加入至双螺杆挤出机，随后在双螺杆挤出机侧喂料口加入填料混合挤出造粒，即得所述高模量高耐热透明聚丙烯组合物。
  8. 如权利要求1～6任一项所述高模量高耐热透明聚丙烯组合物在制备家电 电器中的应用。
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