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WO2025112331A1 - 聚丙烯复合材料及其制备方法和应用 - Google Patents

聚丙烯复合材料及其制备方法和应用 Download PDF

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Publication number
WO2025112331A1
WO2025112331A1 PCT/CN2024/093959 CN2024093959W WO2025112331A1 WO 2025112331 A1 WO2025112331 A1 WO 2025112331A1 CN 2024093959 W CN2024093959 W CN 2024093959W WO 2025112331 A1 WO2025112331 A1 WO 2025112331A1
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Prior art keywords
polypropylene
parts
composite material
elastomer
propylene
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PCT/CN2024/093959
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English (en)
French (fr)
Inventor
展云鹏
侯帅
惠宝军
朱闻博
冯宾
陈云
傅明利
陈喜鹏
贾磊
樊灵孟
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CSG Electric Power Research Institute
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CSG Electric Power Research Institute
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/10—Peculiar tacticity

Definitions

  • the invention relates to the technical field of polymer functional materials, and in particular to a polypropylene composite material and a preparation method and application thereof.
  • high-voltage cables play an important role in the current and future global energy Internet.
  • the core will generate heat and produce high temperatures.
  • some areas are in the high-cold zone, and the temperature in winter is often below -50°C. Therefore, how to improve the reliability of high-voltage cables in high and low temperature environments has become an important technical problem that needs to be solved urgently.
  • Polypropylene-based thermoplastic insulated high-voltage cables have the characteristics of low production energy consumption and recyclability, which are more suitable for the development of future power grids. Replacing traditional cross-linked polyethylene insulated thermoplastic insulated high-voltage cables with them is the future development direction of the cable industry. Therefore, in order to improve the performance deficiencies of cables in actual extreme environment operation, it is necessary to improve the polypropylene cable composite materials and improve the mechanical and electrical performance stability of polypropylene-based composite materials in high and low temperature environments to meet the development needs of power grids.
  • a polypropylene composite material wherein the raw materials thereof include the following components in parts by weight:
  • the vinyl elastomer comprises at least one of the following features:
  • the propylene-based elastomer includes at least one of the following features:
  • Crystallinity is 10% to 15%
  • the raw materials for preparing the polypropylene-based in-kettle alloy resin include a polypropylene matrix and an elastomer
  • the polypropylene matrix comprises a homopolymer polypropylene matrix
  • the elastomer includes one or more of a random copolymer of ethylene-propylene and a random copolymer of ethylene-propylene-butene.
  • the content of the elastomer in the polypropylene-based in-kettle alloy resin is 20 wt % to 25 wt %.
  • the raw material of the polypropylene composite material further includes 0.1 to 1.0 parts of antioxidant by weight;
  • the antioxidant includes antioxidant 1010 .
  • a second aspect of the present invention provides a method for preparing the polypropylene composite material as described above, comprising the following steps:
  • the raw materials are added and melt-blended to prepare a polypropylene-based composite material.
  • the melt blending process satisfies at least one of the following conditions:
  • the mixing temperature is 180°C to 200°C;
  • the mixing speed is 60 r/min to 80 r/min.
  • the mixing method is internal mixing or extrusion.
  • an insulating material comprising the polypropylene composite material as described above.
  • a fourth aspect of the present invention provides a high-voltage cable, comprising the polypropylene composite material as described above or the insulating material as described above.
  • the present invention uses polypropylene-based in-autoclave alloy resin as a matrix, and uses vinyl elastomer and propylene-based elastomer in combination.
  • the components are matched with each other according to specific weight portions to prepare a polypropylene-based composite material with excellent high and low temperature resistance stability, electrical properties and mechanical properties.
  • the modified polypropylene-based composite material combines the performance advantages of vinyl elastomer and propylene elastomer, while taking into account the mechanical toughness, electrical properties and heat resistance of the polypropylene matrix:
  • the vinyl elastomer has high toughness and small modulus in a low-temperature environment, and can provide an octene flexible segment, which improves the mechanical toughness of the polypropylene matrix while ensuring that the mechanical toughness is maintained in a low-temperature environment;
  • the propylene elastomer has isotactic stereogenic characteristics, contains 10-15% crystallinity, has good interface compatibility with the polypropylene matrix, can effectively balance the mechanical toughness and electrical properties of polypropylene insulation, and the high-temperature resistant crystal structure can maintain the thermal conductivity of the polypropylene matrix to a certain extent. Maintain the high temperature resistance of polypropylene composite materials.
  • the present invention utilizes a multi-component elastomer having excellent compatibility with a polypropylene matrix as a modified raw material to balance the mechanical toughness and electrical properties of the polypropylene composite material, so that the prepared polypropylene composite material has both excellent mechanical properties and electrical properties while having good high and low temperature resistance, thereby enhancing the adaptability of the cable insulation layer under harsh conditions, ensuring the stability of the polypropylene insulation structure, and having a good application prospect in the preparation of high-voltage cables.
  • polypropylene composite material of the present invention and its preparation method and application are further described in detail below in conjunction with specific examples.
  • the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.
  • first aspect”, second aspect, “third aspect”, etc. are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features.
  • first”, “second”, “third”, etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity. Therefore, the features defined as “first” and “second” may explicitly or implicitly include at least one of the features.
  • the meaning of “multiple” is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.
  • severeal is at least one, such as one, two, etc., unless otherwise clearly and specifically defined.
  • the numerical range is deemed to be continuous and includes the minimum and maximum values of the range, as well as every value between the minimum and maximum values. Further, when a range refers to an integer, it includes every integer between the minimum and maximum values of the range. In addition, when multiple ranges are provided to describe a feature or In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
  • the percentage content involved in the present invention refers to mass percentage for solid-liquid mixing and solid-solid mixing, and refers to volume percentage for liquid-liquid mixing.
  • the percentage concentrations involved in the present invention refer to the final concentration.
  • the final concentration refers to the proportion of the added component in the system after the addition of the component.
  • the temperature parameters in the present invention allow both constant temperature treatment and treatment within a certain temperature range.
  • the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ⁇ 5°C, ⁇ 2°C, ⁇ 1°C, ⁇ 0.5°C, ⁇ 0.4°C, ⁇ 0.3°C, ⁇ 0.2°C, ⁇ 0.1°C are allowed.
  • Normal temperature in the present invention refers to no temperature control operation, generally refers to 4°C to 35°C, preferably refers to 20 ⁇ 5°C.
  • the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.
  • Blending refers to mixing together. It is a physical method that makes several materials evenly mixed to improve the performance of materials. Blending can improve the physical and mechanical properties and processing properties of polymer materials, reduce costs and expand the scope of use. Blending is one of the important ways to achieve polymer modification and produce high-performance new materials.
  • melt blending also known as melt blending, refers to the method of using a mixing equipment to prepare a uniform polymer co-melt above their viscosity flow temperature for the polymer components required for blending, and then cooling and granulating.
  • the advantage of melt blending is that the requirements for the particle size and uniformity of the raw materials are not as strict as those for dry powder blending, so the raw material preparation operation is relatively simple. In the molten state, the mutual diffusion and strengthening between the molecular chains of heterogeneous polymers, coupled with the strong shear/stretching effect of the mixing equipment, make the mixing effect significantly higher than that of dry powder blending.
  • the alloy resin in the polypropylene kettle directly generates a polypropylene multiphase blend through a multi-stage reaction in the reactor.
  • propylene is polymerized in the first-stage reactor to obtain homopolypropylene; then the homopolypropylene is transferred to the next-stage reactor, and ethylene and propylene monomers are introduced at the same time for copolymerization to generate ethylene-propylene random copolymer in the homopolypropylene. Since the copolymer has a low glass transition temperature, it can be dispersed in the matrix of polypropylene as a rubber phase to give polypropylene good low-temperature properties.
  • the molecular structure of polyolefin elastomers does not have unsaturated double bonds, has a very narrow molecular weight distribution and a short branched structure, and the short branches are evenly distributed, so it has excellent physical and mechanical properties such as high elasticity, high strength, high elongation, and excellent low-temperature resistance.
  • a modified polypropylene-based composite material can be prepared, which can solve the problem that it is difficult to balance the mechanical properties of polypropylene insulating materials in high and low temperature environments, thereby preparing a polypropylene-based composite material with excellent electrical and mechanical properties.
  • a polypropylene composite material wherein the raw materials thereof include the following components in parts by weight:
  • the amount of the polypropylene-based alloy resin in the kettle includes but is not limited to: 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 53 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts and 60 parts.
  • the amount of the vinyl elastomer includes but is not limited to: 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts and 35 parts.
  • the number of parts of the propylene-based elastomer includes, but is not limited to, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts and 35 parts.
  • This application uses the alloy resin in the polypropylene autoclave as the matrix, and uses a compound of vinyl elastomer and propylene-based elastomer to fully combine the performance advantages of the two.
  • the vinyl elastomer provides an octene flexible segment, which improves the mechanical toughness of the polypropylene matrix while ensuring that the mechanical toughness is maintained in a low-temperature environment.
  • the propylene-based elastomer has isotactic characteristics, contains 10-15% crystallinity, has good interfacial compatibility with the polypropylene matrix, and can effectively balance the mechanical toughness and electrical properties of polypropylene insulation.
  • the high-temperature resistant crystal structure can maintain the high-temperature resistance of polypropylene insulation to a certain extent.
  • the present invention uses a multi-component elastomer as a modified raw material, has excellent compatibility with the polypropylene segment, balances the mechanical toughness and electrical properties of polypropylene insulation, has good high and low temperature resistance, enhances the adaptability of the cable insulation layer under harsh conditions, and ensures the stability of the polypropylene insulation structure.
  • the density of the vinyl elastomer is 0.88 g/cm 3 to 0.92 g/cm 3 . It can be understood that the density of the vinyl elastomer includes but is not limited to: 0.88 g/cm 3 , 0.89 g/cm 3 , 0.90 g/cm 3 , 0.91 g/cm 3 , and 0.92 g/cm 3 .
  • the melt index of the vinyl elastomer is 2.2 g/10 min to 2.8 g/10 min. It can be understood that at 230°C and 2.16 kg, the melt index of the vinyl elastomer is 2.2 g/10 min to 2.8 g/10 min.
  • the numbers include but are not limited to: 2.2g/10min, 2.3g/10min, 2.4g/10min, 2.5g/10min, 2.6g/10min, 2.7g/10min, and 2.8g/10min.
  • the vinyl elastomer is a thermoplastic elastomer produced by copolymerization of ethylene and octene catalyzed by metallocene.
  • the crystallinity of the propylene-based elastomer is 10% to 15%. In one specific example, the crystallinity of the propylene-based elastomer includes but is not limited to: 10%, 11%, 12%, 13%, 14%, 15%.
  • the propylene content of the propylene-based elastomer is greater than 80 wt %.
  • the propylene-based elastomer has isotactic properties.
  • Propylene-based elastomers are produced by combining metallocene catalysis technology and solution polymerization process. They are unique propylene-ethylene semi-crystalline copolymers with unique high elasticity, flexibility and low-temperature impact resistance. This application uses a special propylene-ethylene elastomer, that is, at a high ethylene content, it still retains some of the crystalline properties of polypropylene.
  • the raw materials for preparing the polypropylene-based in-kettle alloy resin include a polypropylene matrix and an elastomer.
  • the polypropylene matrix includes a homopolymer polypropylene matrix.
  • the elastomer includes one or more of a random copolymer of ethylene-propylene and a random copolymer of ethylene-propylene-butene.
  • the content of the elastomer in the polypropylene-based in-kettle alloy resin is 20 wt % to 25 wt %.
  • the raw materials for preparing the polypropylene-based in-vessel alloy resin include a homopolymer polypropylene matrix and an ethylene-propylene random copolymer.
  • the content of the ethylene-propylene random copolymer is 20 wt % to 25 wt %.
  • the raw materials of the polypropylene composite material further include 0.1 to 1.0 parts of antioxidant by weight.
  • the antioxidant includes antioxidant 1010 .
  • a second aspect of the present invention provides a method for preparing the polypropylene composite material as described above, comprising the following steps:
  • the raw materials are added and melt-blended to prepare a polypropylene-based composite material.
  • the mixing temperature is 180°C to 200°C. It can be understood that the mixing temperature includes but is not limited to: 180°C, 181°C, 182°C, 183°C, 184°C, 185°C, 186°C, 187 °C, 188°C, 189°C, 190°C, 191°C, 192°C, 193°C, 194°C, 195°C, 196°C, 197°C, 198°C, 199°C and 200°C.
  • the mixing time is 10 min to 15 min. It can be understood that the mixing time includes but is not limited to: 10 min, 11 min, 12 min, 13 min, 14 min, 15 min.
  • the mixing speed is 60r/min to 80r/min. It can be understood that the mixing speed includes but is not limited to: 60r/min, 61r/min, 62r/min, 63r/min, 64r/min, 65r/min, 66r/min, 67r/min, 68r/min, 69r/min, 70r/min, 71r/min, 72r/min, 73r/min, 74r/min, 75r/min, 76r/min, 77r/min, 78r/min, 79r/min, 80r/min.
  • the mixing method in the melt blending process, is internal mixing or extrusion.
  • an insulating material comprising the polypropylene composite material as described above.
  • a fourth aspect of the present invention provides a high-voltage cable, comprising the polypropylene composite material as described above or the insulating material as described above.
  • the invention couples the in-reactor alloy modification and physical blending modification technologies, adopts olefin elastomer as the modification material, and introduces different components of vinyl and propylene elastomers to solve the problem that the mechanical properties of polypropylene insulation materials are difficult to balance under high and low temperature environments.
  • the prepared modified polypropylene-based composite material has excellent high and low temperature resistance stability, electrical properties and mechanical properties, and at the same time ensures the stability of the insulation structure, and can be suitable for use in high-voltage cables for preparing cable composite materials and other related products.
  • the alloy resin in the polypropylene kettle used in Examples 1 to 5 and Comparative Examples 1 to 2 is an elastomer introduced in situ into the homopolypropylene matrix in the polymerization reactor, wherein the elastomer is a random copolymer of ethylene-propylene with a content of 25wt%; the antioxidant used is antioxidant 100.
  • polypropylene alloy resin 50 parts of polypropylene alloy resin in a kettle, 15 parts of vinyl elastomer (density 0.90 g/cm 3 , melt index 2.5 g/10 min), 35 parts of propylene elastomer (with isotactic characteristics, propylene content of 89 wt%, crystallinity of 12%), and 0.3 parts of antioxidant were weighed as raw materials, placed in an internal mixer for melt blending to obtain a polypropylene-based composite material.
  • the melt blending process is: temperature 190°C, time 15 minutes, speed 80 r/min.
  • polypropylene alloy resin 50 parts of polypropylene alloy resin in a kettle, 25 parts of vinyl elastomer (density 0.90 g/cm 3 , melt index 2.5 g/10 min), 25 parts of propylene elastomer (with isotactic characteristics, propylene content of 89 wt%, crystallinity of 12%), and 0.3 parts of antioxidant were weighed as raw materials, placed in an internal mixer for melt blending to obtain a polypropylene-based composite material.
  • the melt blending process is: temperature 190°C, time 15 minutes, speed 80 r/min.
  • polypropylene alloy resin 50 parts of polypropylene alloy resin in a kettle, 35 parts of vinyl elastomer (density 0.90 g/cm 3 , melt index 2.5 g/10 min), 15 parts of propylene elastomer (with isotactic characteristics, propylene content of 89 wt%, crystallinity of 12%), and 0.3 parts of antioxidant were weighed as raw materials, placed in an internal mixer for melt blending to obtain a polypropylene-based composite material.
  • the melt blending process is: temperature 190°C, time 15 minutes, speed 80 r/min.
  • polypropylene alloy resin 60 parts of polypropylene alloy resin in a kettle, 20 parts of vinyl elastomer (density 0.88 g/cm 3 , melt index 2.2 g/10 min), 20 parts of propylene elastomer (with isotactic characteristics, propylene content of 89 wt%, crystallinity of 12%), and 0.1 parts of antioxidant were weighed as raw materials, placed in an internal mixer for melt blending to obtain a polypropylene-based composite material.
  • the melt blending process is: temperature 190°C, time 15 minutes, speed 80 r/min.
  • polypropylene alloy resin 40 parts of polypropylene alloy resin in a kettle, 30 parts of vinyl elastomer (density 0.92 g/cm 3 , melt index 2.8 g/10 min), 30 parts of propylene elastomer (with isotactic characteristics, propylene content of 89 wt%, crystallinity of 12%), and 0.5 parts of antioxidant were weighed as raw materials, placed in an internal mixer for melt blending to obtain a polypropylene-based composite material.
  • the melt blending process is: temperature 190°C, time 15 minutes, speed 80 r/min.
  • polypropylene alloy resin in a polypropylene kettle, 50 parts of propylene-based elastomer (with isotactic characteristics, propylene content of 89wt%, crystallinity of 12%), and 0.5 parts of antioxidant are weighed as raw materials, placed in an internal mixer for melt blending to obtain a polypropylene-based composite material.
  • the melt blending process is: temperature 190°C, time 15 minutes, speed 80r/min.
  • the polypropylene composite materials prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were characterized and tested for room temperature flexural modulus, electrical properties, crystal structure, heat resistance, and temperature dependence of storage modulus. The test results are shown in Table 2 below.
  • test method or standard is:
  • the polypropylene composite material prepared in Comparative Example 1 exhibits a low room temperature storage modulus, good heat resistance and suitable breakdown field strength, but the storage modulus at low temperature is as high as 625.3 MPa, and there is a certain risk in using it in cold areas; while the polypropylene composite material prepared in Comparative Example 2 exhibits relatively excellent mechanical toughness, and even under low temperature conditions, the storage modulus is still low, but the deformation amount of the composite material under load is large, the heat resistance is poor, and it is difficult to meet the use requirements.
  • the present invention utilizes a multi-component elastomer having excellent compatibility with the polypropylene segment as a modified raw material to balance the mechanical toughness and electrical properties of the polypropylene composite material, so that the prepared polypropylene composite material has good high and low temperature resistance while having excellent mechanical properties and electrical properties, thereby enhancing the adaptability of the cable insulation layer under harsh conditions and ensuring the stability of the polypropylene insulation structure, further indicating that the polypropylene composite material provided by the present invention has a good application prospect in the preparation of high-voltage cable related products.

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Abstract

本发明涉及一种聚丙烯复合材料及其制备方法和应用，以聚丙烯基釜内合金树脂为基体，复配使用乙烯基弹性体和丙烯基弹性体，各组分按照特定的重量份数相互搭配，可制备得到聚丙烯基复合材料。所述改性聚丙烯基复合材料充分结合与聚丙烯基体具有优良的相容性的多组份弹性体的性能优势，同时兼顾聚丙烯基体的力学韧性、电气性能和耐热性能，使得制得的聚丙烯复合材料在具备较好的耐高低温能力的同时兼具优异的力学性能和电学性能，增强了电缆绝缘层在恶劣条件下的适应力，保证了聚丙烯绝缘结构的稳定性，在制备高压电缆中具有很好的应用前景。

Description

聚丙烯复合材料及其制备方法和应用 技术领域
本发明涉及高分子功能材料技术领域，特别是涉及一种聚丙烯复合材料及其制备方法和应用。
背景技术
高压电缆作为输配电系统的“动脉”和“神经”，在当今和未来的全球能源互联网中扮演重要角色。在高压电缆运行过程中，线芯会发热产生较高温度。此外，部分地区处于高寒带，冬季气温常低于-50℃。因此，如何提高高压电缆在高低温环境下的可靠性成为亟待解决的一项重要技术问题。
聚丙烯基热塑绝缘高压电缆具备低生产能耗、可回收利用等特性，更加适应未来电网的发展要，以其替代传统的交联聚乙烯绝缘的热塑绝缘高压电缆，是电缆行业未来发展的方向。因此，为了改善电缆在实际极端环境运行过程中出现的性能不足，需要对聚丙烯电缆复合材料进行改进，提高聚丙烯基复合材料在高低温环境下的力学、电气性能稳定性，以满足电网发展需求。
发明内容
基于此，有必要提供一种具有优异的耐高低温稳定性、电学性能稳定性和力学性能稳定性的聚丙烯复合材料及其制备方法和应用。
本发明的第一方面，提供一种聚丙烯复合材料，其原料按重量份数计包括如下组分：
聚丙烯基釜内合金树脂40份～60份；
乙烯基弹性体         15份～35份；
丙烯基弹性体         15份～35份。
在其中一个实施例中，所述乙烯基弹性体包括如下特征的至少一种：
(1)密度为0.88g/cm3～0.92g/cm3；
(2)在230℃、2.16kg条件下的熔融指数为2.2g/10min～2.8g/10min。
在其中一个实施例中，所述丙烯基弹性体包括如下特征的至少一种：
(1)结晶度为10％～15％；
(2)丙烯含量大于80wt％；
(3)具有等规立构特性。
在其中一个实施例中，所述聚丙烯基釜内合金树脂的制备原料包括聚丙烯基体和弹性体；
可选地，所述聚丙烯基体包括均聚聚丙烯基体；
可选地，所述弹性体包括乙烯-丙烯的无规共聚物和乙烯-丙烯-丁烯的无规共聚物中的一种或多种。
在其中一个实施例中，在所述聚丙烯基釜内合金树脂中，所述弹性体的含量为20wt％～25wt％。
在其中一个实施例中，所述的聚丙烯复合材料的原料按重量份数比计还包括抗氧剂0.1份～1.0份；
可选地，所述抗氧剂包括抗氧剂1010。
本发明的第二方面，提供一种如上所述的聚丙烯复合材料的制备方法，包括如下步骤：
添加各所述原料，熔融共混，制备聚丙烯基复合材料。
在其中一个实施例中，所述熔融共混工艺满足如下条件中的至少一个：
(1)混炼温度为180℃～200℃；
(2)混炼时间为10min～15min；
(3)混炼转速为60r/min～80r/min。
(4)混炼方式为密炼或挤出。
本发明第三方面，提供一种绝缘材料，包括如上所述的聚丙烯复合材料。
本发明的第四方面，提供一种高压电缆，包括如上所述的聚丙烯复合材料或如上所述的绝缘材料。
本发明具有如下有益效果：
本发明以聚丙烯基釜内合金树脂为基体，复配使用乙烯基弹性体和丙烯基弹性体，各组分按照特定的重量份数相互搭配，可制备得到具有优异的耐高低温稳定性、电学性能和力学性能的聚丙烯基复合材料。
所述改性聚丙烯基复合材料通过结合乙烯基弹性体和丙烯基弹性体的性能优势，同时兼顾聚丙烯基体的力学韧性、电气性能和耐热性能：乙烯基弹性体在低温环境中韧性高、模量小，可提供辛烯柔性段，在改善聚丙烯基体力学韧性的同时保证力学韧性在低温环境中的保持；丙烯基弹性体具有等规立构特性，含有10～15％的结晶度，与聚丙烯基体有较好的界面相容性，能有效平衡聚丙烯绝缘的力学韧性和电气性能，且耐高温晶体结构能一定程度上维 持聚丙烯复合材料的耐高温性能。
综上，本发明利用与聚丙烯基体具有优良的相容性的多组份弹性体作为改性原料，平衡聚丙烯复合材料的力学韧性和电气性能，使得制得的聚丙烯复合材料在具备较好的耐高低温能力的同时兼具优异的力学性能和电学性能，增强了电缆绝缘层在恶劣条件下的适应力，保证了聚丙烯绝缘结构的稳定性，在制备高压电缆中具有很好的应用前景。
具体实施方式
以下结合具体实施例对本发明的聚丙烯复合材料及其制备方法和应用作进一步详细的说明。本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明公开内容理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
除非另外说明或存在矛盾之处，本文中使用的术语或短语具有以下含义：
本文中，“一种或多种”指所列项目的任一种、任两种或任两种以上。
本文中，“和/或”、“或/和”、“及/或”的可选范围包括两个或两个以上相关所列项目中任一个项目，也包括相关所列项目的任意的和所有的组合，所述任意的和所有的组合包括任意的两个相关所列项目、任意的更多个相关所列项目、或者全部相关所列项目的组合。
本文中，“进一步”、“更进一步”、“特别”等用于描述目的，表示内容上的差异，但并不应理解为对本发明保护范围的限制。
本文中，“第一方面”、“第二方面”、“第三方面”等仅用于描述目的，不能理解为指示或暗示相对重要性或数量，也不能理解为隐含指明所指示的技术特征的重要性或数量。此外，“第一”、“第二”、“第三”等仅起到非穷举式的列举描述目的，应当理解并不构成对数量的封闭式限定。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。在本发明的描述中，“若干”的含义是至少一个，例如一个，两个等，除非另有明确具体的限定。
本发明中，涉及到数值区间，如无特别说明，上述数值区间内视为连续，且包括该范围的最小值及最大值，以及这种最小值与最大值之间的每一个值。进一步地，当范围是指整数时，包括该范围的最小值与最大值之间的每一个整数。此外，当提供多个范围描述特征或 特性时，可以合并该范围。换言之，除非另有指明，否则本文中所公开之所有范围应理解为包括其中所归入的任何及所有的子范围。
本发明中涉及的百分比含量，如无特别说明，对于固液混合和固相-固相混合均指质量百分比，对于液相-液相混合指体积百分比。
本发明中涉及的百分比浓度，如无特别说明，均指终浓度。所述终浓度，指添加成分在添加该成分后的体系中的占比。
本发明中的温度参数，如无特别限定，既允许为恒温处理，也允许在一定温度区间内进行处理。所述的恒温处理允许温度在仪器控制的精度范围内进行波动。允许在如±5℃、±2℃、±1℃、±0.5℃、±0.4℃、±0.3℃、±0.2℃、±0.1℃的范围内波动。本发明中的常温指不施加温度控制操作，一般指4℃～35℃，较佳地指20±5℃。
本发明中，以开放式描述的技术特征中，包括所列举特征组成的封闭式技术方案，也包括包含所列举特征的开放式技术方案。
目前，聚丙烯电缆的发展还处于起步阶段，主要通过共混改性、共聚改性、接枝改性、纳米改性及晶型调控等手段对聚丙烯绝缘的性能进行改进和提升。共混是指共同混合，是一种物理方法，是使几种材料均匀混合，以提高材料性能的方法，通过共混可提高高分子材料的物理力学性能、加工性能，降低成本，扩大使用范围。共混是实现聚合物改性和生产高性能新材料的重要途径之一。
熔融共混又称熔体共混，是指将共混所需的聚合物组分在它们的黏流温度以上用混炼设备制取均匀聚合物共熔体，然后再冷却、造粒的方法。熔融共混的优点是对原料在粒度大小和均一性方面的要求不像干粉共混法那样严格，所以原料准备操作较简单。熔融状态下，异种聚合物分子链之间相互扩散强化，加之混炼设备的强剪切/拉伸作用，使得混合效果显著高于干粉共混。
聚丙烯釜内合金树脂是在反应器中通过多级反应直接生成聚丙烯多相共混物，首先在第一级反应器中进行丙烯聚合，得到均聚聚丙烯；然后将均聚聚丙烯转移到下一级反应器中，同时通入乙烯和丙烯单体进行共聚，在均聚聚丙烯中生成乙烯-丙烯无规共聚物。由于共聚物具有较低的玻璃化转变温度，作为橡胶相分散在聚丙烯的基体中可以赋予聚丙烯良好的低温性能。而聚烯烃弹性体分子结构中没有不饱和双键，具有很窄的分子量分布和短支链结构，且短支链分布均匀，因而具有高弹性、高强度、高伸长率等优异的物理机械性能和的优异的耐低温性能。
本申请的技术人员在实验过程中意外地发现，通过耦合不同化学结构的聚烯烃弹性体的性能优势，即利用乙烯基弹性体在低温环境中韧性高、模量小的特点，并与耐高温形变的丙烯基弹性体熔融共混，能制备得到改性聚丙烯基复合材料，可解决聚丙烯绝缘材料在高温与低温环境下力学性能难以兼顾的问题，从而制备具有优异的电学性能和机械性能的聚丙烯基复合材料。
本发明的第一方面，提供一种聚丙烯复合材料，其原料按重量份数计包括如下组分：
聚丙烯基釜内合金树脂40份～60份；
乙烯基弹性体         15份～35份；
丙烯基弹性体         15份～35份。
可以理解地，所述聚丙烯基釜内合金树脂的份数包括但不限于：40份、41份、42份、43份、44份、45份、46份、47份、48份、49份、50份、51份、52份、53份、53份、55份、56份、57份、58份、59份和60份。所述乙烯基弹性体的份数包括但不限于：15份、16份、17份、18份、19份、20份、21份、22份、23份、24份、25份、26份、27份、28份、29份、30份、31份、32份、33份、34份和35份。所述丙烯基弹性体的份数包括但不限于：15份、16份、17份、18份、19份、20份、21份、22份、23份、24份、25份、26份、27份、28份、29份、30份、31份、32份、33份、34份和35份。
本申请以聚丙烯釜内合金树脂为基体，复配使用乙烯基弹性体和丙烯基弹性体，充分结合二者的性能优势。其中，乙烯基弹性体提供辛烯柔性段，改善聚丙烯基体力学韧性的同时，并保证力学韧性在低温环境中的保持。丙烯基弹性体具有等规立构特性，含有10～15％结晶度，与聚丙烯基体有较好的界面相容性，能有效平衡聚丙烯绝缘的力学韧性和电气性能。耐高温晶体结构能一定程度上维持聚丙烯绝缘耐高温性能。本发明利用多组份弹性体作为改性原料，与聚丙烯链段具有优良的相容性，平衡聚丙烯绝缘的力学韧性和电气性能，具备较好的耐高低温能力，增强电缆绝缘层在恶劣条件下的适应力，保证了聚丙烯绝缘结构的稳定性。
在其中一个具体示例中，所述乙烯基弹性体的密度为0.88g/cm3～0.92g/cm3。可以理解地，所述乙烯基弹性体的密度包括但不限于：0.88g/cm3、0.89g/cm3、0.90g/cm3、0.91g/cm3、0.92g/cm3。
在其中一个具体示例中，在230℃、2.16kg条件下，所述乙烯基弹性体的熔融指数为2.2g/10min～2.8g/10min。可以理解地，在230℃、2.16kg条件下，所述乙烯基弹性体的熔融指 数包括但不限于：2.2g/10min、2.3g/10min、2.4g/10min、2.5g/10min、2.6g/10min、2.7g/10min、2.8g/10min。
可以理解地，所述乙烯基弹性体是由茂金属催化的乙烯与辛烯共聚生成的热塑性弹性体。
在其中一个具体示例中，所述丙烯基弹性体的结晶度为10％～15％。在其中一个具体示例中，所述丙烯基弹性体的结晶度包括但不限于：10％、11％、12％、13％、14％、15％。
在其中一个具体示例中，所述丙烯基弹性体的丙烯含量大于80wt％。
在其中一个具体示例中，所述丙烯基弹性体具有等规立构特性。
丙烯基弹性体是用茂金属催化技术和溶液聚合工艺组合生产所得，是独特的丙烯-乙烯半结晶共聚物，具有独特的高弹性、柔韧性和低温耐冲击性。本申请通过特殊的丙烯-乙烯的弹性体，即在高乙烯含量下，依然保留了部分聚丙烯的结晶性能。
在其中一个具体示例中，所述聚丙烯基釜内合金树脂的制备原料包括聚丙烯基体和弹性体。
在其中一个具体示例中，所述聚丙烯基体包括均聚聚丙烯基体。
在其中一个具体示例中，所述弹性体包括乙烯-丙烯的无规共聚物和乙烯-丙烯-丁烯的无规共聚物中的一种或多种。
在其中一个具体示例中，在所述聚丙烯基釜内合金树脂中，所述弹性体的含量为20wt％～25wt％。
在其中一个具体示例中，所述聚丙烯基釜内合金树脂的制备原料包括均聚聚丙烯基体和乙烯-丙烯的无规共聚物。
在其中一个具体示例中，在所述聚丙烯基釜内合金树脂中，所述乙烯-丙烯的无规共聚物的含量为20wt％～25wt％。
在其中一个具体示例中，所述的聚丙烯复合材料的原料按重量份数比计还包括抗氧剂0.1份～1.0份。
在其中一个具体示例中，所述抗氧剂包括抗氧剂1010。
本发明的第二方面，提供一种如上所述的聚丙烯复合材料的制备方法，包括如下步骤：
添加各所述原料，熔融共混，制备聚丙烯基复合材料。
在其中一个具体示例中，所述熔融共混工艺中，混炼温度为180℃～200℃。可以理解地，所述混炼温度包括但不限于：180℃、181℃、182℃、183℃、184℃、185℃、186℃、187 ℃、188℃、189℃、190℃、191℃、192℃、193℃、194℃、195℃、196℃、197℃、198℃、199℃和200℃。
在其中一个具体示例中，所述熔融共混工艺中，混炼时间为10min～15min。可以理解地，所述混炼时间包括但不限于：10min、11min、12min、13min、14min、15min。
在其中一个具体示例中，所述熔融共混工艺中，混炼转速为60r/min～80r/min。可以理解地，所述混炼转速包括但不限于：60r/min、61r/min、62r/min、63r/min、64r/min、65r/min、66r/min、67r/min、68r/min、69r/min、70r/min、71r/min、72r/min、73r/min、74r/min、75r/min、76r/min、77r/min、78r/min、79r/min、80r/min。
在其中一个具体示例中，所述熔融共混工艺中，混炼方式为密炼或挤出。
本发明第三方面，提供一种绝缘材料，包括如上所述的聚丙烯复合材料。
本发明的第四方面，提供一种高压电缆，包括如上所述的聚丙烯复合材料或如上所述的绝缘材料。
本发明耦合釜内合金改性和物理共混改性技术，采用烯烃弹性体作为改性材料，通过引入不同组分乙烯基与丙烯基弹性体，解决聚丙烯绝缘材料在高温与低温环境下力学性能难以兼顾的问题，制得的改性聚丙烯基复合材料具有优异的耐高低温稳定性，电学性能和机械性能，同时保证了绝缘结构的稳定，可适合应用于高压电缆中用于制备电缆复合材料等相关产品。
以下结合具体实施例对本发明做进一步详细的说明。以下具体实施例中未写明的实验参数，优先参考本申请文件中给出的指引，还可以参考本领域的实验手册或本领域已知的其它实验方法，或者参考厂商推荐的实验条件。可理解，以下实施例所用的仪器和原料较为具体，在其他具体实施例中，可不限于此。
实施例1～5和对比例1～2中采用的聚丙烯釜内合金树脂是聚合反应釜中在均聚聚丙烯基体中原位引入弹性体，其中，弹性体为乙烯-丙烯的无规共聚物，含量为25wt％；采用的抗氧剂为抗氧剂100。
实施例1
称取50份聚丙烯釜内合金树脂、15份乙烯基弹性体(密度0.90g/cm3，熔融指数2.5g/10min)、35份丙烯基弹性体(具有等规立构特性、丙烯含量为89wt％、结晶度为12％)、0.3份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
实施例2
称取50份聚丙烯釜内合金树脂、25份乙烯基弹性体(密度0.90g/cm3，熔融指数2.5g/10min)、25份丙烯基弹性体(具有等规立构特性、丙烯含量为89wt％、结晶度为12％)、0.3份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
实施例3
称取50份聚丙烯釜内合金树脂、35份乙烯基弹性体(密度0.90g/cm3，熔融指数2.5g/10min)、15份丙烯基弹性体(具有等规立构特性、丙烯含量为89wt％、结晶度为12％)、0.3份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
实施例4
称取60份聚丙烯釜内合金树脂、20份乙烯基弹性体(密度0.88g/cm3，熔融指数2.2g/10min)、20份丙烯基弹性体(具有等规立构特性、丙烯含量为89wt％、结晶度为12％)、0.1份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
实施例5
称取40份聚丙烯釜内合金树脂、30份乙烯基弹性体(密度0.92g/cm3，熔融指数2.8g/10min)、30份丙烯基弹性体(具有等规立构特性、丙烯含量为89wt％、结晶度为12％)、0.5份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
对比例1
称取50份聚丙烯釜内合金树脂、50份丙烯基弹性体(具有等规立构特性、丙烯含量为89wt％、结晶度为12％)、0.5份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
对比例2
称取50份聚丙烯釜内合金树脂、50份乙烯基弹性体(密度为0.90g/cm3，在230℃、2.16kg条件下熔融指数为2.5g/10min)、0.5份抗氧剂作为原料，置于密炼机中熔融共混，得到聚丙烯基复合材料。所述熔融共混工艺为：温度190℃下，时间为15分钟，转速为80r/min。
实施例1～5及对比例1～2的制备方法中各原料(以重量份数计)及熔融共混等工艺参数列表如下表1：
表1
将实施例1～5及对比例1～2制得的聚丙烯复合材料进行室温弯曲模量、电气性能、晶体结构、耐热性能以及储能模量对温度的依赖性的表征和测试，测试结果如下表2所示。
测试方法或标准为：
(1)弯曲模量：基于GB/T9341-2008进行测试；
(2)电气性能：基于GB/T 1408.1-2016对击穿场强进行测试；
(3)晶体结构：采用差示扫描量热仪(TA Q250)，将约5mg样品置于密闭坩埚中，在氮气氛围下，以10℃/min的升温速率从室温升温至200℃，记录热流信号随温度的变化。
(4)耐热性能试验：为评价绝缘材料在期望的过载温度下是否能保持必要的力学强度，按拉伸性能测试方法准备试样。采用热延伸试验的标准测试方法。将试样一端悬挂于烘箱中，烘箱温度设置为150℃，另一端加以按试样截面施以0.2MPa拉力换算质量的砝码，经设定时间15min后，测量试样的伸长率，定义为负荷下伸长率。冷却后的伸长率，定义为永久形变率。
(5)储能模量对温度的依赖性：为评价聚丙烯复合材料的耐低温性能，利用动态力学分析仪(TQ850)拉伸模式表征了实施例1～5和对比例1～2的聚丙烯复合材料样品在0℃的储能模型。采用振荡模式：频率为1Hz，振幅为15μm。
表2
从上表2可知，对比例1制备得到的聚丙烯复合材料表现有较低的室温储能模量、良好的耐热性能和合适的击穿场强，但低温下储能模量高达625.3MPa，在寒冷地区使用存在一定的风险；而对比例2制备得到的聚丙烯复合材料表现出较为优异的力学韧性，即使低温条件下，储能模量依然较低，但该复合材料负荷下的形变量较大，耐热性较差，难以满足使用要求。
本申请经过采用聚丙烯釜内合金树脂，耦合乙烯基和丙烯基弹性体的性能优势，兼顾聚丙烯绝缘的力学韧性、电气性能和耐热性能。实施例1～实施例5制得的聚丙烯复合材料熔融温度高，有较稳定的聚丙烯晶体骨架，保证材料在高温下有较好的尺寸稳定性，表现出较好的耐热性能；丙烯基弹性体与聚丙烯基体界面相容性较好，在改善韧性的同时，保证了材料有较高的击穿场强和电气稳定性；此外，聚丙烯绝缘中包含多种弹性体，兼顾其优势，表现出适宜的室温弯曲模量，且低温储能模量也较好，保证绝缘材料有更宽泛使用温度范围，且较好的环境适应性。
综上，本发明利用与聚丙烯链段具有优良的相容性的多组份弹性体作为改性原料，平衡聚丙烯复合材料的力学韧性和电气性能，使得制得的聚丙烯复合材料在具备较好的耐高低温能力的同时兼具优异的力学性能和电学性能，增强电缆绝缘层在恶劣条件下的适应力，保证了聚丙烯绝缘结构的稳定性，进一步表明本发明提供的聚丙烯复合材料在制备高压电缆相关产品中具有很好的应用前景。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾， 都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于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。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种聚丙烯复合材料，其特征在于，其原料按重量份数计包括如下组分：
    聚丙烯基釜内合金树脂 40份～60份；
    乙烯基弹性体         15份～35份；
    丙烯基弹性体         15份～35份。
  2. 根据权利要求1所述的聚丙烯复合材料，其特征在于，所述乙烯基弹性体包括如下特征的至少一种：
    (1)密度为0.88g/cm3～0.92g/cm3；
    (2)在230℃、2.16kg条件下的熔融指数为2.2g/10min～2.8g/10min。
  3. 根据权利要求1所述的聚丙烯复合材料，其特征在于，所述丙烯基弹性体包括如下特征的至少一种：
    (1)结晶度为10％～15％；
    (2)丙烯含量大于80wt％；
    (3)具有等规立构特性。
  4. 根据权利要求1所述的聚丙烯复合材料，其特征在于，所述聚丙烯基釜内合金树脂的制备原料包括聚丙烯基体和弹性体；
    可选地，所述聚丙烯基体包括均聚聚丙烯基体；
    可选地，所述弹性体包括乙烯-丙烯的无规共聚物和乙烯-丙烯-丁烯的无规共聚物中的一种或多种。
  5. 根据权利要求4所述的聚丙烯复合材料，其特征在于，在所述聚丙烯基釜内合金树脂中，所述弹性体的含量为20wt％～25wt％。
  6. 根据权利要求1～5任一项所述的聚丙烯复合材料，其特征在于，其原料按重量份数比计还包括抗氧剂0.1份～1.0份；
    可选地，所述抗氧剂包括抗氧剂1010。
  7. 一种如权利要求1～5任一项所述的聚丙烯复合材料的制备方法，其特征在于，包括如下步骤：
    添加各所述原料，熔融共混，制备聚丙烯基复合材料。
  8. 根据权利要求7所述的聚丙烯复合材料的制备方法，其特征在于，所述熔融共混工艺 满足如下条件中的至少一个：
    (1)混炼温度为180℃～200℃；
    (2)混炼时间为10min～15min；
    (3)混炼转速为60r/min～80r/min；
    (4)混炼方式为密炼或挤出。
  9. 一种绝缘材料，其特征在于，包括权利要求1～6任一项所述的聚丙烯复合材料。
  10. 一种高压电缆，其特征在于，包括权利要求1～6任一项所述的聚丙烯复合材料或权利要求9所述的绝缘材料。
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