WO2022057181A1 - 一种聚烯烃材料及其制备方法和应用 - Google Patents

一种聚烯烃材料及其制备方法和应用 Download PDF

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WO2022057181A1
WO2022057181A1 PCT/CN2021/072997 CN2021072997W WO2022057181A1 WO 2022057181 A1 WO2022057181 A1 WO 2022057181A1 CN 2021072997 W CN2021072997 W CN 2021072997W WO 2022057181 A1 WO2022057181 A1 WO 2022057181A1
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polyolefin
polyolefin material
material according
fibers
mixture
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PCT/CN2021/072997
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French (fr)
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陆湛泉
黄险波
叶南飚
程文建
程书文
关安南
谢湘
杨霄云
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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
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to a polyolefin material and a preparation method and application thereof.
  • Polyolefin materials are the most widely used in real life due to their abundant raw materials, low price, easy processing and molding, and excellent comprehensive performance.
  • the reinforcement method of conventional polyolefin mainly uses glass fiber as the reinforcement medium, and uses the high strength and high rigidity of glass fiber to improve the strength and heat resistance of the product.
  • the glass fiber reinforced polyolefin after adding glass fiber has defects such as high density, poor wave transmission performance (high dielectric constant and dielectric loss), and poor toughness, which cannot meet the requirements of weight or wave transmission performance. Use in high places.
  • a method of adding low-dielectric glass fibers or quartz fibers has been studied. Although this method can achieve better wave-transmitting properties, it also has the defects of high density and high cost.
  • the primary purpose of the present invention is to provide a polyolefin material, which has the advantages of high heat resistance, high strength, low density and high wave transmittance.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polyolefin material.
  • a polyolefin material by weight, comprising the following components:
  • the polyolefin resin is selected from one or a mixture of polypropylene, polyethylene and polybutene.
  • the compatibilizer is a graft polymer of a polar monomer and a polyolefin, wherein the polar monomer is selected from one or more mixtures of maleic anhydride, acrylic acid, and acrylate derivatives,
  • the polyolefin is selected from one or a mixture of polypropylene and polyethylene.
  • the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers, preferably glass fibers, and the average diameter of the glass fibers is 5-20 ⁇ m.
  • the hollow mullite microspheres of the invention contain air, have strong wave-transmitting ability, low density, light weight, higher hardness than glass, and stronger pressure resistance.
  • the particle size D50 of the hollow mullite microspheres is 10-50 microns, preferably 15-30 microns, the density is 0.2-0.9 g/cm 3 , preferably 0.3-0.5 g/cm 3 , and the pressure is 5000PSI- 50000PSI, preferably 10000-30000PSI; if the bearing pressure is too poor, it will be easily broken during the extrusion process.
  • the bearing pressure in the present invention refers to the compressive strength of the hollow mullite microspheres, which is tested by the water isostatic pressure detection method. get.
  • the mass ratio of the reinforcing fibers to the hollow mullite microspheres is 1:5-5:1, preferably 1:2-2:1.
  • the present invention also provides a method for preparing the above-mentioned polyolefin material, comprising the following steps:
  • the polyolefin resin and compatibilizer are mixed and added to the main feeding system of the extruder.
  • the reinforcing fibers and hollow mullite microspheres are added to the side feeding system. All components are mixed and extruded by the extruder.
  • the polyolefin material is obtained by pelleting.
  • the present invention also provides the application of the above-mentioned polyolefin material in the fields of household appliances, automobiles or communications.
  • the present invention has the following beneficial effects:
  • the two synergistically synergize not only can significantly reduce the density of the material, improve the wave-transmitting performance of the material, but also improve the strength and heat resistance of the material , so that the density of the prepared polyolefin material is less than 1.0g/cm 3 , even less than 0.9g/cm 3 , the dielectric constant is less than 2.6;
  • the advantages of high strength, low density and high wave transmission are not only can significantly reduce the density of the material, improve the wave-transmitting performance of the material, but also improve the strength and heat resistance of the material , so that the density of the prepared polyolefin material is less than 1.0g/cm 3 , even less than 0.9g/cm 3 , the dielectric constant is less than 2.6;
  • Polypropylene resin PP SP179;
  • Polyethylene resin HDPE 5000S;
  • Glass fiber 1 with an average diameter of 10 ⁇ m
  • Glass fiber 2 with an average diameter of 22 ⁇ m
  • Hollow mullite microspheres 1 particle size 30 microns, density 0.3g/cm 3 , pressure 15000PSI;
  • Hollow mullite microspheres 2 particle size 15 microns, density 0.6 g/cm 3 , pressure 25000 PSI;
  • Heat distortion temperature ISO75-2 test, test condition 1.82MPa.
  • Embodiment 1-7 and comparative example 1-3 are identical to Embodiment 1-7 and comparative example 1-3:
  • Comparative Example 1 it can be seen from Comparative Example 1 that only the reinforcing fibers are added, although the strength of the material is significantly improved, but its density is high and the wave transmission performance is poor.
  • Comparative Example 3 only hollow mullite microspheres were added, although the density decreased and the wave-transmitting performance was significantly improved, but its strength was poor.
  • Comparative Example 2 when the ratio of reinforcing fibers and hollow mullite microspheres is not within the preferred range, it is difficult for the material to have the characteristics of high heat resistance, high strength, low density and high wave transmittance.
  • the present invention adds reinforcing fibers and hollow mullite microspheres to the polyolefin material, and the two have a synergistic effect, which can not only significantly reduce the density of the material, improve the wave transmission performance of the material, but also improve the material
  • the strength and heat resistance of the material make the material have the advantages of high heat resistance, high strength, low density and high wave transmission.

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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

本发明公开了一种聚烯烃材料及其制备方法和应用，包括组分：聚烯烃树脂15-95份；增强纤维5-60份；相容剂0.5-10份；中空莫来石微球5-60份。本发明通过在聚烯烃材料中添加增强纤维和中空莫来石微球，二者协同增效，不仅可以显著降低材料的密度，提高材料的透波性能，同时能提高材料的强度和耐热性，使制备得到的聚烯烃材料兼具高耐热、高强度、低密度和高透波的优点。

Description

一种聚烯烃材料及其制备方法和应用 技术领域
本发明属于高分子材料领域，具体涉及一种聚烯烃材料及其制备方法和应用。
背景技术
聚烯烃材料由于原料丰富、价格低廉、容易加工成型、综合性能优良等特点，在现实生活中应用最为广泛。
目前，常规聚烯烃的增强方法主要是使用玻纤作为增强介质，利用玻纤的高强度高刚性提高产品强度和耐热性能。但是采用这种方法，加入玻纤后的玻纤增强聚烯烃存在密度高，透波性能(介电常数和介电损耗大)差，韧性不好等缺陷，无法在对重量或者透波性能要求高的场合使用。为改善聚烯烃材料的透波性能，有研究采用加入低介电玻纤或者石英纤维的方法，该方法虽然能做到较好的透波性能，但是同样存在密度大，成本高等缺陷。
因此，研究一种兼具高耐热、高强度、低密度和高透波的聚烯烃材料具有较好的市场前景。
发明内容
为了克服上述现有技术存在的不足，本发明的首要目的在于提供一种聚烯烃材料，该材料兼具高耐热、高强度、低密度和高透波的优点。
本发明的另一目的在于提供上述聚烯烃材料的制备方法。
本发明是通过以下技术方案实现的：
一种聚烯烃材料，按重量份计，包括以下组份：
Figure PCTCN2021072997-appb-000001
优选的，所述聚烯烃树脂选自聚丙烯、聚乙烯、聚丁烯中的一种或几种的混合。
优选的，所述相容剂为极性单体与聚烯烃的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸、丙烯酸酯类衍生物中的一种或几种的混合物，聚烯烃选自聚丙烯、聚乙烯中的一种或两种的混合。
优选的，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或几种的混合，优选玻璃纤维，所述玻璃纤维的平均直径为5-20μm。
本发明所述中空莫来石微球内含空气，透波能力强，密度低，轻量化，硬度比玻璃大，耐压性更强。优选的，所述中空莫来石微球的粒径D50为10-50微米，优选15-30微米，密度为0.2-0.9g/cm 3，优选0.3-0.5g/cm 3，承压5000PSI-50000PSI，优选10000-30000PSI；如果承压太差，在挤出过程中容易碎掉，本发明所述的承压是指中空莫来石微球的抗压强度，采用水等静压检测法测试得到。优选的，所述增强纤维与中空莫来石微球的质量比为1:5-5:1，优选为1:2-2:1。
本发明还提供了上述聚烯烃材料的制备方法，包括如下步骤：
按配比，将聚烯烃树脂和相容剂混合，加入挤出机的主喂料系统，同时将增强纤维和中空莫来石微球加入侧喂系统，所有组分通过挤出机混合挤出造粒即得聚烯烃材料。
本发明还提供了上述聚烯烃材料在家用电器、汽车或通讯领域中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明通过在聚烯烃材料中添加增强纤维和中空莫来石微球，二者协同增效，不仅可以显著降低材料的密度，提高材料的透波性能，同时能提高材料的强度和耐热性，使制备得到的聚烯烃材料密度小于1.0g/cm 3，甚至低于0.9g/cm 3，介电常数小于2.6；介电损耗小于0.005，热变形温度大于100度，兼具高耐热、高强度、低密度和高透波的优点。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明所用的原料均来源于市购，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：
聚丙烯树脂：PP SP179；
聚乙烯树脂：HDPE 5000S；
相容剂：PP-g-MAH、HDPE-g-MAH；
增强纤维：
玻璃纤维1，平均直径为10μm；
玻璃纤维2，平均直径为22μm；
玄武岩纤维、石英纤维，市购；
中空莫来石微球1：粒径30微米，密度0.3g/cm 3，承压15000PSI；
中空莫来石微球2：粒径15微米，密度0.6g/cm 3，承压25000PSI；
相关性能的测试标准或方法如下：
密度：按照ISO1183标准测试；
介电常数和介电损耗：按照GB12636测试频率：10GHz；
弯曲强度：按照ISO178测试；
热变形温度：ISO75-2测试，测试条件1.82MPa。
实施例1-7与对比例1-3：
按表1配比，将聚烯烃树脂和相容剂混合，加入挤出机的主喂料系统，同时将增强纤维和中空莫来石微球加入侧喂系统，所有组分通过挤出机混合挤出造粒即得聚烯烃材料。测试结果如表1所示。
表1 实施例和对比例中各组分配比(重量份)
Figure PCTCN2021072997-appb-000002
续表1：
Figure PCTCN2021072997-appb-000003
由对比例1看出，只添加增强纤维，虽然材料的强度显著提高，但其密度较大，透波性能较差。对比例3中，只添加中空莫来石微球，虽然其密度下降和透波性能显著提高，但其强度较差。对比例2中，当增强纤维和中空莫来石微球的配比不在优选范围内时，材料也难以兼具高耐热、高强度、低密度和高透波的特点。由此看出，本发明通过聚烯烃材料中添加增强纤维和中空莫来石微球，二者具有协同增效作用，不仅可以显著降低材料的密度，提高材料的透波性能，同时能提高材料的强度和耐热性，使材料兼具高耐热、高强度、低密度和高透波的优点。

Claims (8)

  1. 一种聚烯烃材料，其特征在于，按重量份计，包括以下组份：
    Figure PCTCN2021072997-appb-100001
  2. 根据权利要求1所述的聚烯烃材料，其特征在于，其特征在于，所述聚烯烃树脂选自聚丙烯、聚乙烯、聚丁烯中的一种或几种的混合。
  3. 根据权利要求1所述的聚烯烃材料，其特征在于，所述相容剂为极性单体与聚烯烃的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸、丙烯酸酯类衍生物中的一种或几种的混合物，所述聚烯烃选自聚丙烯、聚乙烯中的一种或两种的混合。
  4. 根据权利要求1所述的聚烯烃材料，其特征在于，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或几种的混合，优选玻璃纤维，所述玻璃纤维的平均直径为5-20μm。
  5. 根据权利要求1所述的聚烯烃材料，其特征在于，所述中空莫来石微球的粒径D50为10-50微米，优选15-30微米，密度为0.2-0.9g/cm 3，优选0.3-0.5g/cm 3，承压5000PSI-50000PSI，优选10000-30000PSI。
  6. 根据权利要求1所述的聚烯烃材料，其特征在于，所述增强纤维与中空莫来石微球的质量比为1:5-5:1，优选为1:2-2:1。
  7. 根据权利要求1-6任一项所述的聚烯烃材料的制备方法，其特征在于，包括如下步骤：
    按配比，将聚烯烃树脂和相容剂混合，加入挤出机的主喂料系统，同时将增强纤维和中空莫来石微球加入侧喂系统，所有组分通过挤出机混合挤出造粒即得聚烯烃材料。
  8. 根据权利要求1-6任一项所述的聚烯烃材料在家用电器、汽车或通讯领域中的应用。
PCT/CN2021/072997 2020-09-16 2021-01-21 一种聚烯烃材料及其制备方法和应用 WO2022057181A1 (zh)

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