WO2020088333A1 - Silane-crosslinked polyethylene insulation material used for heating cable, preparation method therefor and application thereof - Google Patents

Silane-crosslinked polyethylene insulation material used for heating cable, preparation method therefor and application thereof Download PDF

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WO2020088333A1
WO2020088333A1 PCT/CN2019/112900 CN2019112900W WO2020088333A1 WO 2020088333 A1 WO2020088333 A1 WO 2020088333A1 CN 2019112900 W CN2019112900 W CN 2019112900W WO 2020088333 A1 WO2020088333 A1 WO 2020088333A1
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parts
silane
density polyethylene
antioxidant
polyethylene
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PCT/CN2019/112900
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French (fr)
Chinese (zh)
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张丽本
涂必冬
钱其坤
杨俊�
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江苏德威新材料股份有限公司
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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

Definitions

  • the invention belongs to the field of heating cables, and in particular relates to a silane cross-linked polyethylene insulation material for heating cables and a preparation method and application thereof.
  • the heating cable is made of a cable structure, uses electricity as an energy source, and uses resistance wires to generate heat to achieve the effect of heating and insulation. It is widely used in floor heating, snow melting and ice melting.
  • the low-end products of the existing heating cable insulation layer are mainly non-crosslinked ordinary polyethylene and polyvinyl chloride, but the high temperature resistance is relatively poor, and polyvinyl chloride still lacks in environmental protection; high-end is now mainly used Although PTFE and silicone rubber have good heat resistance, they are expensive and not conducive to large-scale applications.
  • the current market needs an insulating material for heating cables that is suitable for the price, has good heat resistance, and meets the requirements of environmental protection.
  • Cross-linking modification is an important means to improve the heat resistance, weather resistance and other properties of polyethylene.
  • the silane cross-linking method is one of the cross-linking methods of polyethylene.
  • Some heating cable manufacturers have tried to use silane cross-linked polyethylene Insulation materials are used for the manufacture of heating cables.
  • the current silane cross-linked polyethylene insulation for cables has a temperature resistance of only about 90 ° C, which can only be applied to power cables and cannot meet the needs of heating cables.
  • Chinese utility model patent CN204145784U which discloses A single-conducting heating cable with a silane cross-linked polyethylene insulation layer has an alloy heating wire, the alloy heating wire is wrapped with a silane cross-linked polyethylene insulation layer, and the silane cross-linked polyethylene insulation layer is wrapped with a filler layer, Several metal grounding wires are evenly distributed in the filling layer, the metal electromagnetic shielding layer is wrapped around the filling layer, and the PVC sheath is wrapped around the metal electromagnetic shielding layer. It is mentioned in this patent that it can work for a long time at 100-120 ° C, but the actual production The silane crosslinked polyethylene commonly used in the process cannot achieve this effect, and the temperature resistance level is only about 90 ° C.
  • the technical problem to be solved by the present invention is to overcome the shortcomings in the prior art, and to provide an improved silane cross-linked polyethylene insulation material suitable for heating cables, which can be used for a long time at 125 °C and maintain excellent physical and mechanical properties , And safe and environmentally friendly, lower cost.
  • the invention also provides a preparation method of silane cross-linked polyethylene insulation material for heating cable.
  • the invention also provides the application of silane cross-linked polyethylene insulation material for heating cable in the production of heating cable.
  • a silane cross-linked polyethylene insulation material for heating cables is made of a mixture of silane graft material and cross-linking catalyst masterbatch.
  • the raw materials of the silane graft material include polyolefin resin, silane cross-linking agent, Graft initiator, first lubricant and first antioxidant
  • the raw material of the crosslinking catalyst masterbatch includes: crosslinking catalyst, second lubricant and second antioxidant
  • the polyolefin resin is composed of the first It is composed of high-density polyethylene, bimodal polyethylene and polypropylene, and the feeding mass ratio of the first high-density polyethylene, the bimodal polyethylene and the polypropylene is 1.5-6: 0.2-2: 1;
  • the raw material of the cross-linking catalyst mother particles further includes second high-density polyethylene and linear low-density polyethylene, and the feeding mass ratio of the second high-density polyethylene to the linear low-density polyethylene is 1-2: 1.
  • the first high-density polyethylene is 40-70 parts
  • the bimodal polyethylene is 5-30 parts
  • the polypropylene is 20-40 parts.
  • the first high-density polyethylene is 50-65 parts
  • the bimodal polyethylene is 10-25 parts
  • the polypropylene is 25-35 parts
  • the silane is crosslinked.
  • the second high-density polyethylene in terms of parts by weight, in the raw material of the crosslinking catalyst mother particles, the second high-density polyethylene is 50-60 parts, the linear low-density polyethylene is 40-50 parts, and the crosslinking catalyst is 0.5 -3 parts, 3-8 parts of the second lubricant and 0.5-2 parts of the second antioxidant. More preferably, in terms of parts by weight, among the raw materials of the crosslinking catalyst mother particles, the second high-density polyethylene is 50-55 parts, the linear low-density polyethylene is 45-50 parts, and the crosslinking catalyst is 1-3 parts. 3-6 parts of the second lubricant and 0.8-1.5 parts of the second antioxidant.
  • the first high density polyethylene has a melt index of 0.1-2.5 g / 10 min.
  • the tensile strength of the first high-density polyethylene is greater than or equal to 25 MPa.
  • the bimodal polyethylene has a melt index of 0.1-1 g / 10 min.
  • the polypropylene has a number average molecular weight of 80,000 to 150,000.
  • the melt index of the second high-density polyethylene is 2.0-10.0 g / 10 min. More preferably, the melt index of the second high-density polyethylene is 4.0-9.0 g / 10 min.
  • the linear low density polyethylene has a melt index of 10-30 g / 10 min. More preferably, the linear low density polyethylene has a melt index of 15-25 g / 10 min.
  • the feed mass ratio of the silane grafting material and the crosslinking catalyst mother particles is 15-23: 1.
  • the silane crosslinking agent is selected from vinyl-tris (2-methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane One or a combination of multiple.
  • the graft initiator is selected from dicumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane And one or more combinations of dibenzoyl peroxide.
  • the first lubricant is a combination of one or more selected from PE wax, EVA wax and PPA.
  • the first antioxidant is one selected from antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant DSTP and antioxidant 300, or Various combinations.
  • the crosslinking catalyst is one or a combination of one or more selected from p-toluenesulfonic acid, dodecylbenzenesulfonic acid, bismuth isooctanoate, and organic titanium.
  • the second lubricant is one or a combination of one or more selected from PE wax, EVA wax and PPA.
  • the second antioxidant is antioxidant 1024 and / or anti-aging agent TMQ.
  • a method for preparing the silane cross-linked polyethylene insulation material for a heating cable described above includes the following steps:
  • silane grafting material Weigh each raw material in proportion to the formula, mix the weighed silane crosslinking agent, graft initiator and first antioxidant to prepare a silane mixture; weigh the first High-density polyethylene, bimodal polyethylene and polypropylene are added to the extruder, the silane mixture is added, plasticized and grafted, granulated, and dried to prepare the silane grafting material;
  • silane graft material prepared in step (1) and the crosslinking catalyst masterbatch prepared in step (2) are packaged according to the formula ratio, that is, the silane crosslinked polyethylene insulation material for the heating cable is prepared .
  • the extruder is a reciprocating screw BUSS extruder, and the temperature is set to 150 ° C to 195 ° C in the compression section and 200 ° C to 220 ° C in the homogenization section.
  • step (2) the extruder adopts a twin-screw extruder, and the feed section, compression section, melting section and die temperature of the twin-screw extruder are sequentially set to 120 °C ⁇ 130 °C, 140 °C ⁇ 160 °C, 170 °C ⁇ 180 °C and 180 °C ⁇ 185 °C.
  • a heating cable including a heating cable insulation layer, the heating cable insulation layer is cross-linked in water by the above-mentioned heating cable silane cross-linked polyethylene insulation material production.
  • the melt index mentioned in the present invention is determined according to the ASTM D1238 standard under a test load of 2.16 kg at 190 ° C.
  • the present invention has the following advantages compared with the prior art:
  • the silane cross-linked polyethylene insulation material of the present invention adopts a specific polyolefin resin compounding system.
  • the silane graft material is composed of the first high-density polyethylene, bimodal polyethylene and polypropylene.
  • It can maintain excellent physical and mechanical properties for a long time, overcome the shortcomings of poor high temperature resistance existing in the prior art with polyethylene as the basic resin matrix, and at the same time, the insulation material for heating cables of the present invention is safe and environmentally friendly, the cost is low, suitable For large-scale applications.
  • This embodiment provides a silane cross-linked polyethylene insulation material for heating cables.
  • Table 1 For the raw materials and dosages used, see Table 1.
  • the first high-density polyethylene is the high-density polyethylene grade produced by Qilu Petrochemical: TR144, and the melt index is 0.3g / 10min;
  • Bimodal polyethylene is produced by the Nordic chemical industry, the brand is: FB2230, the melt index is 0.2g / 10min;
  • Polypropylene selects CNPC Dushanzi production grade as: EPF30R;
  • the silane crosslinking agent contains a mixture of vinyl trimethoxy silane, vinyl triethoxy silane, and vinyl-tri (2-methoxyethoxy) silane in a weight ratio of 1: 1: 2 ;
  • the graft initiator is dicumyl peroxide
  • the first lubricant is fluorine-containing rheological agent ppa, purchased from 3M company;
  • the first antioxidant is antioxidant 300;
  • the second high-density polyethylene was purchased from Dushanzi Petrochemical, the brand name was DMDA-8008, and the melt index was 7.5g / 10min;
  • the linear low-density polyethylene is produced by Sinopec Zhenhai Refining and Chemical Co., Ltd.
  • the linear low-density polyethylene grade is 8320, and the melt index is 20g / 10min;
  • the cross-linking catalyst is a mixture of dodecylbenzenesulfonic acid and organic titanium in a weight ratio of 1: 1;
  • the second lubricant is PE wax
  • the second antioxidant is antioxidant 1024;
  • the preparation method of silane cross-linked polyethylene insulation material for heating cable includes the following steps:
  • silane grafting material Preparation of silane grafting material: Weigh each raw material in the silane grafting material according to the formula ratio, mix the weighed silane crosslinking agent, graft initiator and first antioxidant to prepare a silane mixture; The weighed first high-density polyethylene, bimodal polyethylene and polypropylene are added to the BUSS extruder, and the silane mixture is added to the BUSS extruder with a computer-controlled liquid weigher. Granulation (the temperature in the compression section is 150-195 ° C and the temperature in the homogenization section is 200-220 ° C) are dehydrated and dried, that is, the silane graft material is prepared;
  • silane graft material prepared in step (1) and the crosslinking catalyst masterbatch prepared in step (2) are packaged in a formulation ratio of 95: 5, that is, the silane crosslinking polymer for the heating cable is prepared Vinyl insulation material.
  • the silane grafting material packaged in proportion with the crosslinking catalyst masterbatch When it is necessary to make the insulation layer of the heating cable, directly mix the silane grafting material packaged in proportion with the crosslinking catalyst masterbatch and extrude it in an extruder (the extrusion temperature is 165 ⁇ 5 °C in the feeding section, compressed Section 175 ⁇ 5 °C, homogenization break 190 ⁇ 5 °C, die head 200 ⁇ 5 °C), and then cross-link in water at a temperature of 90 °C, it can be made.
  • the extrusion temperature is 165 ⁇ 5 °C in the feeding section, compressed Section 175 ⁇ 5 °C, homogenization break 190 ⁇ 5 °C, die head 200 ⁇ 5 °C
  • This embodiment provides a silane cross-linked polyethylene insulation material for heating cables.
  • Table 1 For the raw materials and dosages used, see Table 1.
  • the first high-density polyethylene is the high-density polyethylene produced by NASA Chemical Co., Ltd. with the trade name of TR131, and the solution flow rate is 0.2g / 10min; the silane crosslinking agent is vinyl trimethoxysilane.
  • the other raw materials are the same as in Example 1.
  • This embodiment provides a silane cross-linked polyethylene insulation material for heating cables.
  • Table 1 For the raw materials and dosages used, see Table 1.
  • the first lubricant is a mixture of fluorine-containing rheological agent PPA and microcrystalline wax in a weight ratio of 1: 1, and the graft initiator is 1,1-di-tert-butyl peroxide-3,3,5 -Trimethylcyclohexane.
  • the other raw materials are the same as in Example 1.
  • This embodiment provides a silane cross-linked polyethylene insulation material for heating cables.
  • the raw materials and dosages used are shown in Table 1. The selection of raw materials is the same as in Example 1.
  • Example 2 It is basically the same as Example 1, except that the raw material of the silane graft material does not contain polypropylene, and the amount of the first high-density polyethylene is adjusted accordingly.
  • Example 2 It is basically the same as that in Example 1, except that the first high-density polyethylene is replaced with the same amount of linear low-density polyethylene, and bimodal polyethylene is not added, and the amount of polypropylene is adjusted accordingly.
  • Example 2 It is basically the same as Example 1, except that the second high-density polyethylene is not added, and the content of linear low-density polyethylene in the cross-linking catalyst master batch is adjusted accordingly.

Abstract

Disclosed in the present invention are a silane-crosslinked polyethylene insulation material used for a heating cable, a preparation method therefor and an application thereof; the insulation material is made by mixing a silane-grafted material and a crosslinking catalyst master batch; the raw materials of the silane-grafted material comprise a polyolefin resin, a silane crosslinking agent, a graft initiator, a first lubricant, and a first antioxidant; the raw materials of the crosslinking catalyst master batch comprise: a crosslinking catalyst, a second lubricant, and a second antioxidant; the polyolefin resin is composed of a first high-density polyethylene, a bimodal polyethylene, and polypropylene; the raw materials of the crosslinking catalyst master batch further comprise a second high-density polyethylene and a linear low-density polyethylene; the preparation method comprises: respectively preparing the silane-grafted material and the crosslinking catalyst master batch, and then packaging according to a ratio; and an application thereof in the production of heating cables. The present invention may be used for a long period of time at 125°C, maintains excellent physical and mechanical properties, is safe and environmentally friendly, and is low-cost.

Description

发热电缆用硅烷交联聚乙烯绝缘材料及其制备方法和应用Silane cross-linked polyethylene insulation material for heating cable and preparation method and application thereof 技术领域Technical field
本发明属于发热电缆领域，具体涉及一种发热电缆用硅烷交联聚乙烯绝缘材料及其制备方法和应用。The invention belongs to the field of heating cables, and in particular relates to a silane cross-linked polyethylene insulation material for heating cables and a preparation method and application thereof.
背景技术Background technique
发热电缆，是制成电缆结构，以电力为能源，利用电阻丝进行发热，从而达到采暖保温效果，在地暖、融雪融冰等方面有广泛应用。现有发热电缆绝缘层低端产品主要以非交联普通聚乙烯和聚氯乙烯为主，但是耐高温性能等比较差，而且聚氯乙烯在环保方面还有所欠缺；高端方面现在主要是采用聚四氟乙烯和硅橡胶，虽然具有较好的耐热性能，但是价格昂贵，不利于规模应用。The heating cable is made of a cable structure, uses electricity as an energy source, and uses resistance wires to generate heat to achieve the effect of heating and insulation. It is widely used in floor heating, snow melting and ice melting. The low-end products of the existing heating cable insulation layer are mainly non-crosslinked ordinary polyethylene and polyvinyl chloride, but the high temperature resistance is relatively poor, and polyvinyl chloride still lacks in environmental protection; high-end is now mainly used Although PTFE and silicone rubber have good heat resistance, they are expensive and not conducive to large-scale applications.
因此，目前市场需要一款价格适合，且耐热性能较好，符合环保要求的发热电缆用绝缘材料。交联改性是提高聚乙烯耐热性、耐候性等性能的重要手段，其中硅烷交联的方式作为聚乙烯的交联方法之一，已有部分发热电缆厂家在尝试使用硅烷交联聚乙烯绝缘材料用以发热电缆的制造，然而目前电缆用硅烷交联聚乙烯绝缘料耐温等级只有90℃左右，仅能适用于电力电缆，无法满足发热电缆的需求，中国实用新型专利CN204145784U，其公开了一种具有硅烷交联聚乙烯绝缘层的单导发热电缆，其具有合金发热丝，合金发热丝外包裹有硅烷交联聚乙烯绝缘层，硅烷交联聚乙烯绝缘层外包裹有填充层，填充层中均匀分布有若干金属接地线，填充层外包裹有金属电磁屏蔽层，金属电磁屏蔽层外包裹有PVC护套，此专利中提及可以在100-120℃下长期工作，然而实际生产过程中常用的硅烷交联聚乙烯并不能实现此效果，耐温等级也只有90℃左右。Therefore, the current market needs an insulating material for heating cables that is suitable for the price, has good heat resistance, and meets the requirements of environmental protection. Cross-linking modification is an important means to improve the heat resistance, weather resistance and other properties of polyethylene. The silane cross-linking method is one of the cross-linking methods of polyethylene. Some heating cable manufacturers have tried to use silane cross-linked polyethylene Insulation materials are used for the manufacture of heating cables. However, the current silane cross-linked polyethylene insulation for cables has a temperature resistance of only about 90 ° C, which can only be applied to power cables and cannot meet the needs of heating cables. Chinese utility model patent CN204145784U, which discloses A single-conducting heating cable with a silane cross-linked polyethylene insulation layer has an alloy heating wire, the alloy heating wire is wrapped with a silane cross-linked polyethylene insulation layer, and the silane cross-linked polyethylene insulation layer is wrapped with a filler layer, Several metal grounding wires are evenly distributed in the filling layer, the metal electromagnetic shielding layer is wrapped around the filling layer, and the PVC sheath is wrapped around the metal electromagnetic shielding layer. It is mentioned in this patent that it can work for a long time at 100-120 ° C, but the actual production The silane crosslinked polyethylene commonly used in the process cannot achieve this effect, and the temperature resistance level is only about 90 ° C.
发明内容Summary of the invention
本发明所要解决的技术问题是克服现有技术中的不足，提供一种改进的适用于发热电缆用的硅烷交联聚乙烯绝缘材料，其能够在125℃下长久使用，保持优异的物理力学性能，且安全环保，成本较低。The technical problem to be solved by the present invention is to overcome the shortcomings in the prior art, and to provide an improved silane cross-linked polyethylene insulation material suitable for heating cables, which can be used for a long time at 125 ℃ and maintain excellent physical and mechanical properties , And safe and environmentally friendly, lower cost.
本发明同时还提供了发热电缆用硅烷交联聚乙烯绝缘材料的制备方法。The invention also provides a preparation method of silane cross-linked polyethylene insulation material for heating cable.
本发明同时还提供了发热电缆用硅烷交联聚乙烯绝缘材料在生产发热电缆中的应用。The invention also provides the application of silane cross-linked polyethylene insulation material for heating cable in the production of heating cable.
为解决以上技术问题，本发明采取的一种技术方案如下：To solve the above technical problems, a technical solution adopted by the present invention is as follows:
一种发热电缆用硅烷交联聚乙烯绝缘材料，所述绝缘材料由硅烷接枝料和交联催化剂母粒混合制成，所述硅烷接枝料的原料包括聚烯烃树脂、硅烷交联剂、接枝引发剂、第一润滑剂和第一抗氧剂，所述交联催化剂母粒的原料包括：交联催化剂、第二润滑剂和第二抗氧剂，所述聚烯烃树脂由第一高密度聚乙烯、双峰聚乙烯和聚丙烯构成，所述第一高密度聚乙烯、所述双峰聚乙烯与所述聚丙烯的投料质量比为1.5-6︰0.2-2︰1；所述交联催化剂母粒的原料还包括第二高密度聚乙烯和线性低密度聚乙烯，所述第二高密度聚乙烯与所述线性低密度聚乙烯的投料质量比为1-2︰1。A silane cross-linked polyethylene insulation material for heating cables. The insulation material is made of a mixture of silane graft material and cross-linking catalyst masterbatch. The raw materials of the silane graft material include polyolefin resin, silane cross-linking agent, Graft initiator, first lubricant and first antioxidant, the raw material of the crosslinking catalyst masterbatch includes: crosslinking catalyst, second lubricant and second antioxidant, the polyolefin resin is composed of the first It is composed of high-density polyethylene, bimodal polyethylene and polypropylene, and the feeding mass ratio of the first high-density polyethylene, the bimodal polyethylene and the polypropylene is 1.5-6: 0.2-2: 1; The raw material of the cross-linking catalyst mother particles further includes second high-density polyethylene and linear low-density polyethylene, and the feeding mass ratio of the second high-density polyethylene to the linear low-density polyethylene is 1-2: 1.
根据本发明的一些优选方面，以重量份数计，所述硅烷接枝料的原料中，第一高密度聚乙烯40-70份、双峰聚乙烯5-30份、聚丙烯20-40份、硅烷交联剂0.5-2.0份、接枝引发剂0.5-2.5份、第一润滑剂0.5-3份和第一抗氧剂0.3-2.0份。更优选地，以重量份数计，所述硅烷接枝料的原料中，第一高密度聚乙烯50-65份、双峰聚乙烯10-25份、聚丙烯25-35份、硅烷交联剂0.8-1.5份、接枝引发剂1.5-2.5份、第一润滑剂1-3份和第一抗氧剂0.3-1.5份。According to some preferred aspects of the present invention, in terms of parts by weight, among the raw materials of the silane graft material, the first high-density polyethylene is 40-70 parts, the bimodal polyethylene is 5-30 parts, and the polypropylene is 20-40 parts. , 0.5-2.0 parts of silane crosslinking agent, 0.5-2.5 parts of graft initiator, 0.5-3 parts of the first lubricant and 0.3-2.0 parts of the first antioxidant. More preferably, in terms of parts by weight, among the raw materials of the silane graft material, the first high-density polyethylene is 50-65 parts, the bimodal polyethylene is 10-25 parts, the polypropylene is 25-35 parts, and the silane is crosslinked. Agent 0.8-1.5 parts, graft initiator 1.5-2.5 parts, first lubricant 1-3 parts and first antioxidant 0.3-1.5 parts.
根据本发明的一些优选方面，以重量份数计，所述交联催化剂母粒的原料中，第二高密度聚乙烯50-60份、线性低密度聚乙烯40-50份、交联催化剂0.5-3份、第二润滑剂3-8份和第二抗氧剂0.5-2份。更优选地，以重量份数计，所述交联催化剂母粒的原料中，第二高密度聚乙烯50-55份、线性低密度聚乙烯45-50份、交联催化剂1-3份、第二润滑剂3-6份和第二抗氧剂0.8-1.5份。According to some preferred aspects of the present invention, in terms of parts by weight, in the raw material of the crosslinking catalyst mother particles, the second high-density polyethylene is 50-60 parts, the linear low-density polyethylene is 40-50 parts, and the crosslinking catalyst is 0.5 -3 parts, 3-8 parts of the second lubricant and 0.5-2 parts of the second antioxidant. More preferably, in terms of parts by weight, among the raw materials of the crosslinking catalyst mother particles, the second high-density polyethylene is 50-55 parts, the linear low-density polyethylene is 45-50 parts, and the crosslinking catalyst is 1-3 parts. 3-6 parts of the second lubricant and 0.8-1.5 parts of the second antioxidant.
根据本发明的一些优选方面，所述第一高密度聚乙烯的熔融指数为0.1-2.5g/10min。According to some preferred aspects of the present invention, the first high density polyethylene has a melt index of 0.1-2.5 g / 10 min.
根据本发明的一些优选方面，所述第一高密度聚乙烯的拉伸强度大于等于25MPa。According to some preferred aspects of the present invention, the tensile strength of the first high-density polyethylene is greater than or equal to 25 MPa.
根据本发明的一些优选方面，所述双峰聚乙烯的熔融指数为0.1-1g/10min。According to some preferred aspects of the invention, the bimodal polyethylene has a melt index of 0.1-1 g / 10 min.
根据本发明的一些具体且优选的方面，所述聚丙烯的数均分子量为8-15万。According to some specific and preferred aspects of the present invention, the polypropylene has a number average molecular weight of 80,000 to 150,000.
根据本发明的一些优选方面，所述第二高密度聚乙烯的熔融指数为2.0-10.0g/10min。更优选地，所述第二高密度聚乙烯的熔融指数为4.0-9.0g/10min。According to some preferred aspects of the present invention, the melt index of the second high-density polyethylene is 2.0-10.0 g / 10 min. More preferably, the melt index of the second high-density polyethylene is 4.0-9.0 g / 10 min.
根据本发明的一些优选方面，所述线性低密度聚乙烯的熔融指数为10-30g/10min。更优选地，所述线性低密度聚乙烯的熔融指数为15-25g/10min。According to some preferred aspects of the invention, the linear low density polyethylene has a melt index of 10-30 g / 10 min. More preferably, the linear low density polyethylene has a melt index of 15-25 g / 10 min.
根据本发明的一些优选方面，所述硅烷接枝料和所述交联催化剂母粒的投料质量比为15-23︰1。According to some preferred aspects of the present invention, the feed mass ratio of the silane grafting material and the crosslinking catalyst mother particles is 15-23: 1.
根据本发明的一些具体且优选的方面，所述硅烷交联剂为选自乙烯基-三(2-甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷和乙烯基三甲氧基硅烷中的一种或者多种的组合。According to some specific and preferred aspects of the present invention, the silane crosslinking agent is selected from vinyl-tris (2-methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane One or a combination of multiple.
根据本发明的一些具体且优选的方面，所述接枝引发剂为选自过氧化二异丙苯、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷和过氧化二苯甲酰中的一种或者多种的组合。According to some specific and preferred aspects of the present invention, the graft initiator is selected from dicumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane And one or more combinations of dibenzoyl peroxide.
根据本发明的一些具体且优选的方面，所述第一润滑剂为选自PE蜡、EVA蜡和PPA中的一种或者多种的组合。According to some specific and preferred aspects of the invention, the first lubricant is a combination of one or more selected from PE wax, EVA wax and PPA.
根据本发明的一些具体且优选的方面，所述第一抗氧剂为选自抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂DSTP和抗氧剂300中的一种或者多种的组合。According to some specific and preferred aspects of the present invention, the first antioxidant is one selected from antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant DSTP and antioxidant 300, or Various combinations.
根据本发明的一些具体且优选的方面，所述交联催化剂为选自对甲苯磺酸、十二烷基苯磺酸、异辛酸铋和有机钛中的一种或者多种的组合。According to some specific and preferred aspects of the present invention, the crosslinking catalyst is one or a combination of one or more selected from p-toluenesulfonic acid, dodecylbenzenesulfonic acid, bismuth isooctanoate, and organic titanium.
根据本发明的一些具体且优选的方面，所述第二润滑剂为选自PE蜡、EVA蜡和PPA中的一种或者多种的组合。According to some specific and preferred aspects of the invention, the second lubricant is one or a combination of one or more selected from PE wax, EVA wax and PPA.
根据本发明的一些具体且优选的方面，所述第二抗氧剂为抗氧剂1024和/或防老剂TMQ。According to some specific and preferred aspects of the invention, the second antioxidant is antioxidant 1024 and / or anti-aging agent TMQ.
本发明提供的又一技术方案：一种上述所述的发热电缆用硅烷交联聚乙烯绝缘材料的制备方法，所述制备方法包括如下步骤：Another technical solution provided by the present invention: a method for preparing the silane cross-linked polyethylene insulation material for a heating cable described above, the preparation method includes the following steps:
(1)制备硅烷接枝料：按配方比例称取各原料，将称取的硅烷交联剂、接枝引发剂和第一抗氧剂混合，制得硅烷混合液；将称取的第一高密度聚乙烯、双峰聚乙烯和聚丙烯加入挤出机中，加入所述硅烷混合液，经塑化接枝，造粒，干燥，即制成所述硅烷接枝料；(1) Preparation of silane grafting material: Weigh each raw material in proportion to the formula, mix the weighed silane crosslinking agent, graft initiator and first antioxidant to prepare a silane mixture; weigh the first High-density polyethylene, bimodal polyethylene and polypropylene are added to the extruder, the silane mixture is added, plasticized and grafted, granulated, and dried to prepare the silane grafting material;
(2)制备交联催化剂母粒：按配方比例称取各原料，混合，加入挤出机中挤出造粒，干燥，即制成所述交联催化剂母粒；(2) Preparation of crosslinking catalyst masterbatch: weigh the raw materials according to the formula ratio, mix, add to the extruder and extrude and pelletize, and dry to prepare the crosslinking catalyst masterbatch;
(3)将步骤(1)制备的所述硅烷接枝料与步骤(2)制备的所述交联催化剂母粒按配方比例包装，即制成所述发热电缆用硅烷交联聚乙烯绝缘材料。(3) The silane graft material prepared in step (1) and the crosslinking catalyst masterbatch prepared in step (2) are packaged according to the formula ratio, that is, the silane crosslinked polyethylene insulation material for the heating cable is prepared .
根据本发明的一些优选方面，步骤(1)中，所述挤出机为往复式螺杆BUSS挤出机，温度设置为压缩段150℃～195℃，均化段200℃～220℃。According to some preferred aspects of the present invention, in step (1), the extruder is a reciprocating screw BUSS extruder, and the temperature is set to 150 ° C to 195 ° C in the compression section and 200 ° C to 220 ° C in the homogenization section.
根据本发明的一些优选方面，步骤(2)中，所述挤出机采用双螺杆挤出机，所述双螺杆挤出机的进料段、压缩段、熔融段及模头温度依次设置为120℃～130℃、140℃～160℃、170℃～180℃以及180℃～185℃。According to some preferred aspects of the present invention, in step (2), the extruder adopts a twin-screw extruder, and the feed section, compression section, melting section and die temperature of the twin-screw extruder are sequentially set to 120 ℃ ～ 130 ℃, 140 ℃ ～ 160 ℃, 170 ℃ ～ 180 ℃ and 180 ℃ ～ 185 ℃.
本发明提供的又一技术方案：一种发热电缆，所述发热电缆包括发热电缆绝缘层，所述发热电缆绝缘层由上述所述的发热电缆用硅烷交联聚乙烯绝缘材料在水中交联而制成。Another technical solution provided by the present invention: a heating cable including a heating cable insulation layer, the heating cable insulation layer is cross-linked in water by the above-mentioned heating cable silane cross-linked polyethylene insulation material production.
根据本发明，本发明中提及的熔融指数均为以ASTM D1238标准在190℃条件下按照测试载荷为2.16Kg时测定。According to the present invention, the melt index mentioned in the present invention is determined according to the ASTM D1238 standard under a test load of 2.16 kg at 190 ° C.
由于以上技术方案的采用，本发明与现有技术相比具有如下优点：Due to the adoption of the above technical solutions, the present invention has the following advantages compared with the prior art:
本发明的硅烷交联聚乙烯绝缘材料，采用特定的聚烯烃树脂配合体系，硅烷接枝料中，采用第一高密度聚乙烯、双峰聚乙烯和聚丙烯构成，交联催化剂母粒中，采用第二高密度聚乙烯和线性低密度聚乙烯构成树脂体系，进而实现了在125℃下长久使用(传统的硅烷交联绝缘材料长期使用温度为90℃左右，仅能适用电力电缆的使用)，能够长期保持优异的 物理力学性能，克服了现有技术中以聚乙烯为基本树脂基体而存在的耐高温性能差的缺陷，同时本发明的发热电缆用绝缘材料安全环保，成本较低，适于规模化应用。The silane cross-linked polyethylene insulation material of the present invention adopts a specific polyolefin resin compounding system. The silane graft material is composed of the first high-density polyethylene, bimodal polyethylene and polypropylene. In the cross-linking catalyst mother particles, Adopt the second high-density polyethylene and linear low-density polyethylene to form a resin system, and then achieve long-term use at 125 ℃ (traditional silane cross-linked insulating material long-term use temperature is about 90 ℃, only suitable for power cable use) It can maintain excellent physical and mechanical properties for a long time, overcome the shortcomings of poor high temperature resistance existing in the prior art with polyethylene as the basic resin matrix, and at the same time, the insulation material for heating cables of the present invention is safe and environmentally friendly, the cost is low, suitable For large-scale applications.
具体实施方式detailed description
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。The above solutions will be further described below in conjunction with specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features, and advantages of the present invention, but the present invention is not limited by the scope of the following embodiments; The implementation conditions can be further adjusted according to specific requirements. Unspecified implementation conditions are usually those in routine experiments.
下述实施例中未作特殊说明，所有原料均来自于商购或通过本领域的常规方法制备而得。In the following examples, without special description, all raw materials are commercially available or prepared by conventional methods in the art.
实施例1Example 1
本实施例提供一种发热电缆用硅烷交联聚乙烯绝缘材料，采用的原料与用量参见表1，其中，This embodiment provides a silane cross-linked polyethylene insulation material for heating cables. For the raw materials and dosages used, see Table 1.
硅烷接枝料的原料中：第一高密度聚乙烯为齐鲁石化产高密度聚乙烯牌号为：TR144，熔融指数为0.3g/10min； Among the raw materials of the silane grafting material: the first high-density polyethylene is the high-density polyethylene grade produced by Qilu Petrochemical: TR144, and the melt index is 0.3g / 10min;
双峰聚乙烯为北欧化工产，牌号为：FB2230，熔融指数为0.2g/10min；Bimodal polyethylene is produced by the Nordic chemical industry, the brand is: FB2230, the melt index is 0.2g / 10min;
聚丙烯选用中石油独山子生产牌号为：EPF30R；Polypropylene selects CNPC Dushanzi production grade as: EPF30R;
硅烷交联剂包含为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基-三(2-甲氧基乙氧基)硅烷三者按重量比1:1:2复配的混合物；The silane crosslinking agent contains a mixture of vinyl trimethoxy silane, vinyl triethoxy silane, and vinyl-tri (2-methoxyethoxy) silane in a weight ratio of 1: 1: 2 ;
接枝引发剂为过氧化二异丙苯；The graft initiator is dicumyl peroxide;
第一润滑剂为含氟流变剂ppa，购自3M公司；The first lubricant is fluorine-containing rheological agent ppa, purchased from 3M company;
第一抗氧剂为抗氧剂300；The first antioxidant is antioxidant 300;
交联催化剂母粒的原料中：第二高密度聚乙烯购自独山子石化，牌号为DMDA-8008，熔融指数为7.5g/10min； Among the raw materials for the crosslinking catalyst masterbatch: the second high-density polyethylene was purchased from Dushanzi Petrochemical, the brand name was DMDA-8008, and the melt index was 7.5g / 10min;
线性低密度聚乙烯为中石化镇海炼化产的线性低密度聚乙烯牌号为:8320，熔融指数为20g/10min；The linear low-density polyethylene is produced by Sinopec Zhenhai Refining and Chemical Co., Ltd. The linear low-density polyethylene grade is 8320, and the melt index is 20g / 10min;
交联催化剂为十二烷基苯磺酸与有机钛按重量比1:1的比例复配的混合物；The cross-linking catalyst is a mixture of dodecylbenzenesulfonic acid and organic titanium in a weight ratio of 1: 1;
第二润滑剂为PE蜡；The second lubricant is PE wax;
第二抗氧剂为抗氧剂1024；The second antioxidant is antioxidant 1024;
发热电缆用硅烷交联聚乙烯绝缘材料的制备方法包括如下步骤：The preparation method of silane cross-linked polyethylene insulation material for heating cable includes the following steps:
(1)制备硅烷接枝料：按配方比例称取硅烷接枝料中的各原料，将称取的硅烷交联剂、接枝引发剂和第一抗氧剂混合，制得硅烷混合液；将称取的第一高密度聚乙烯、双峰聚乙烯和聚丙烯加入BUSS挤出机中，并用电脑控制液体称向BUSS挤出机中加入所述硅烷混合液，经塑化接枝，挤出造粒(压缩段温度为150-195℃，均化段温度为200-220℃)脱水干燥，即制成所述硅烷接枝料；(1) Preparation of silane grafting material: Weigh each raw material in the silane grafting material according to the formula ratio, mix the weighed silane crosslinking agent, graft initiator and first antioxidant to prepare a silane mixture; The weighed first high-density polyethylene, bimodal polyethylene and polypropylene are added to the BUSS extruder, and the silane mixture is added to the BUSS extruder with a computer-controlled liquid weigher. Granulation (the temperature in the compression section is 150-195 ° C and the temperature in the homogenization section is 200-220 ° C) are dehydrated and dried, that is, the silane graft material is prepared;
(2)制备交联催化剂母粒：按配方比例称取各原料，混合，加入双螺杆挤出机中挤出造粒(双螺杆挤出机的进料段、压缩段、熔融段及模头温度依次设置为120℃～130℃、140℃～160℃、170℃～180℃以及180℃～185℃)，干燥，即制成所述交联催化剂母粒；(2) Preparation of cross-linked catalyst masterbatch: weigh the raw materials according to the formula ratio, mix, add to the twin-screw extruder for extrusion granulation (feeding section, compression section, melting section and die head of the twin screw extruder The temperature is sequentially set to 120 ° C to 130 ° C, 140 ° C to 160 ° C, 170 ° C to 180 ° C and 180 ° C to 185 ° C), and dried to prepare the cross-linked catalyst masterbatch;
(3)将步骤(1)制备的所述硅烷接枝料与步骤(2)制备的所述交联催化剂母粒按配方比例95∶5包装，即制成所述发热电缆用硅烷交联聚乙烯绝缘材料。(3) The silane graft material prepared in step (1) and the crosslinking catalyst masterbatch prepared in step (2) are packaged in a formulation ratio of 95: 5, that is, the silane crosslinking polymer for the heating cable is prepared Vinyl insulation material.
当需要制成发热电缆的绝缘层时，直接将按配比包装好的硅烷接枝料与交联催化剂母粒混合，在挤出机中挤出(挤出温度为加料段165±5℃、压缩段175±5℃、均化断190±5℃、模头200±5℃)，然后在温度为90℃的水中交联，即可制成。When it is necessary to make the insulation layer of the heating cable, directly mix the silane grafting material packaged in proportion with the crosslinking catalyst masterbatch and extrude it in an extruder (the extrusion temperature is 165 ± 5 ℃ in the feeding section, compressed Section 175 ± 5 ℃, homogenization break 190 ± 5 ℃, die head 200 ± 5 ℃), and then cross-link in water at a temperature of 90 ℃, it can be made.
实施例2Example 2
本实施例提供一种发热电缆用硅烷交联聚乙烯绝缘材料，采用的原料与用量参见表1，其中，This embodiment provides a silane cross-linked polyethylene insulation material for heating cables. For the raw materials and dosages used, see Table 1.
第一高密度聚乙烯为卡塔尔化工生产的高密度聚乙烯，牌号为TR131，溶体流动速率为0.2g/10min；硅烷交联剂为乙烯基三甲氧基硅烷。其他原料与实施例1相同。The first high-density polyethylene is the high-density polyethylene produced by Qatar Chemical Co., Ltd. with the trade name of TR131, and the solution flow rate is 0.2g / 10min; the silane crosslinking agent is vinyl trimethoxysilane. The other raw materials are the same as in Example 1.
制备方法同实施例1。制备 方法 同 实施 例 1。 Preparation method is the same as in Example 1.
实施例3Example 3
本实施例提供一种发热电缆用硅烷交联聚乙烯绝缘材料，采用的原料与用量参见表1，其中，This embodiment provides a silane cross-linked polyethylene insulation material for heating cables. For the raw materials and dosages used, see Table 1.
第一润滑剂采用含氟流变剂PPA和微晶蜡按1:1的重量比复配而成的混合物，接枝引发剂为1,1-二叔丁基过氧化-3,3,5-三甲基环己烷。其他原料与实施例1相同。The first lubricant is a mixture of fluorine-containing rheological agent PPA and microcrystalline wax in a weight ratio of 1: 1, and the graft initiator is 1,1-di-tert-butyl peroxide-3,3,5 -Trimethylcyclohexane. The other raw materials are the same as in Example 1.
制备方法同实施例1。制备 方法 同 实施 例 1。 Preparation method is the same as in Example 1.
实施例4Example 4
本实施例提供一种发热电缆用硅烷交联聚乙烯绝缘材料，采用的原料与用量参见表1，其中，原料选择与实施例1相同。This embodiment provides a silane cross-linked polyethylene insulation material for heating cables. The raw materials and dosages used are shown in Table 1. The selection of raw materials is the same as in Example 1.
制备方法同实施例1。制备 方法 同 实施 例 1。 Preparation method is the same as in Example 1.
对比例1Comparative Example 1
基本同实施例1，其区别仅在于硅烷接枝料的原料中不含聚丙烯，相应调整第一高密度聚乙烯的用量。It is basically the same as Example 1, except that the raw material of the silane graft material does not contain polypropylene, and the amount of the first high-density polyethylene is adjusted accordingly.
对比例2Comparative Example 2
基本同实施例1，其区别仅在于将第一高密度聚乙烯替换为同等用量的线性低密度聚乙烯，且不加双峰聚乙烯，相应调整聚丙烯的用量。It is basically the same as that in Example 1, except that the first high-density polyethylene is replaced with the same amount of linear low-density polyethylene, and bimodal polyethylene is not added, and the amount of polypropylene is adjusted accordingly.
对比例3Comparative Example 3
基本同实施例1，其区别仅在于不加第二高密聚乙烯，相应调整交联催化剂母粒中线性低密度聚乙烯的含量。It is basically the same as Example 1, except that the second high-density polyethylene is not added, and the content of linear low-density polyethylene in the cross-linking catalyst master batch is adjusted accordingly.
表1、实施例1-4以及对比例1-3中各原料的用量Table 1, the amount of each raw material in Examples 1-4 and Comparative Examples 1-3
Figure PCTCN2019112900-appb-000001
Figure PCTCN2019112900-appb-000001
Figure PCTCN2019112900-appb-000002
Figure PCTCN2019112900-appb-000002
性能测试Performance Testing
将上述实施例1-4以及对比例1-3所制备的材料制成测试样品(1mm厚度试样，在90℃热水恒温放置6h)，并对各项性能进行测试，测得各性能如下表2所示。The materials prepared in the above Examples 1-4 and Comparative Examples 1-3 were made into test samples (1mm thickness samples, placed in a constant temperature of 90 ° C hot water for 6h), and the properties were tested, and the properties were measured as follows Table 2 shows.
下述各性能测试标准如下：The following performance test standards are as follows:
拉伸强度：GB/T 1040.3-2006；Tensile strength: GB / T 1040.3-2006;
断裂伸长率：GB/T 1040.3-2006；Elongation at break: GB / T 1040.3-2006;
20℃体积电阻率：GB/T 1410-2006；20 ℃ volume resistivity: GB / T 1410-2006;
低温脆性实验(-76℃)：GB/T 5470-2008；Low temperature brittleness experiment (-76 ℃): GB / T 5470-2008;
凝胶含量：JB/T 10437-2004；Gel content: JB / T 10437-2004;
空气热老化158℃×168h：GB/T 2951.12-2008；Air thermal aging 158 ℃ × 168h: GB / T2951.12-2008;
热延伸250℃，0.2MPa，15min：GB/T 2951.21-2008(国标要求是200℃，本发明采用在250℃下测定)。Thermal extension 250 ℃, 0.2MPa, 15min: GB / T 2951.21-2008 (200 ℃ required by national standard, measured at 250 ℃ in the present invention).
表2Table 2
Figure PCTCN2019112900-appb-000003
Figure PCTCN2019112900-appb-000003
Figure PCTCN2019112900-appb-000004
Figure PCTCN2019112900-appb-000004
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above embodiments are only for explaining the technical concept and features of the present invention. The purpose is to enable those familiar with the technology to understand the contents of the present invention and implement it accordingly, and cannot limit the scope of protection of the present invention. The equivalent changes or modifications made by the spirit should be covered by the protection scope of the present invention.

Claims (21)

  1. 一种发热电缆用硅烷交联聚乙烯绝缘材料，所述绝缘材料由硅烷接枝料和交联催化剂母粒混合制成，所述硅烷接枝料的原料包括聚烯烃树脂、硅烷交联剂、接枝引发剂、第一润滑剂和第一抗氧剂，所述交联催化剂母粒的原料包括：交联催化剂、第二润滑剂和第二抗氧剂，其特征在于，所述聚烯烃树脂由第一高密度聚乙烯、双峰聚乙烯和聚丙烯构成，所述第一高密度聚乙烯、所述双峰聚乙烯与所述聚丙烯的投料质量比为1.5-6︰0.2-2︰1；所述交联催化剂母粒的原料还包括第二高密度聚乙烯和线性低密度聚乙烯，所述第二高密度聚乙烯与所述线性低密度聚乙烯的投料质量比为1-2︰1。A silane cross-linked polyethylene insulation material for heating cables. The insulation material is made of a mixture of silane graft material and cross-linking catalyst masterbatch. The raw materials of the silane graft material include polyolefin resin, silane cross-linking agent, Graft initiator, first lubricant and first antioxidant, the raw material of the crosslinking catalyst masterbatch includes: crosslinking catalyst, second lubricant and second antioxidant, characterized in that the polyolefin The resin is composed of first high-density polyethylene, bimodal polyethylene and polypropylene, and the mass ratio of the first high-density polyethylene, the bimodal polyethylene and the polypropylene is 1.5-6: 0.2-2 ： 1; The raw material of the crosslinking catalyst masterbatch also includes second high-density polyethylene and linear low-density polyethylene, the feeding mass ratio of the second high-density polyethylene to the linear low-density polyethylene is 1- 2: 1.
  2. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，以重量份数计，所述硅烷接枝料的原料中，第一高密度聚乙烯40-70份、双峰聚乙烯5-30份、聚丙烯20-40份、硅烷交联剂0.5-2.0份、接枝引发剂0.5-2.5份、第一润滑剂0.5-3份和第一抗氧剂0.3-2.0份。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, characterized in that, in terms of parts by weight, among the raw materials of the silane graft material, the first high-density polyethylene is 40-70 parts, double Peak polyethylene 5-30 parts, polypropylene 20-40 parts, silane crosslinking agent 0.5-2.0 parts, graft initiator 0.5-2.5 parts, first lubricant 0.5-3 parts and first antioxidant 0.3-2.0 Copies.
  3. 根据权利要求2所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，以重量份数计，所述硅烷接枝料的原料中，第一高密度聚乙烯50-65份、双峰聚乙烯10-25份、聚丙烯25-35份、硅烷交联剂0.8-1.5份、接枝引发剂1.5-2.5份、第一润滑剂1-3份和第一抗氧剂0.3-1.5份。The silane cross-linked polyethylene insulation material for heating cables according to claim 2, characterized in that, in terms of parts by weight, among the raw materials of the silane graft material, the first high-density polyethylene is 50-65 parts, double Peak polyethylene 10-25 parts, polypropylene 25-35 parts, silane crosslinking agent 0.8-1.5 parts, graft initiator 1.5-2.5 parts, first lubricant 1-3 parts and first antioxidant 0.3-1.5 Copies.
  4. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，以重量份数计，所述交联催化剂母粒的原料中，第二高密度聚乙烯50-60份、线性低密度聚乙烯40-50份、交联催化剂0.5-3份、第二润滑剂3-8份和第二抗氧剂0.5-2份。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, characterized in that, in terms of parts by weight, among the raw materials of the cross-linking catalyst mother particles, the second high-density polyethylene is 50-60 parts, Linear low-density polyethylene 40-50 parts, crosslinking catalyst 0.5-3 parts, second lubricant 3-8 parts and second antioxidant 0.5-2 parts.
  5. 根据权利要求4所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，以重量份数计，所述交联催化剂母粒的原料中，第二高密度聚乙烯50-55份、线性低密度聚乙烯45-50份、交联催化剂1-3份、第二润滑剂3-6份和第二抗氧剂0.8-1.5份。The silane cross-linked polyethylene insulation material for heating cables according to claim 4, characterized in that, in terms of parts by weight, among the raw materials of the cross-linking catalyst mother particles, the second high-density polyethylene is 50-55 parts, 45-50 parts of linear low density polyethylene, 1-3 parts of crosslinking catalyst, 3-6 parts of second lubricant and 0.8-1.5 parts of second antioxidant.
  6. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述第一高密度聚乙烯的熔融指数为0.1-2.5g/10min。The silane cross-linked polyethylene insulation material for a heating cable according to claim 1, wherein the first high-density polyethylene has a melt index of 0.1-2.5g / 10min.
  7. 根据权利要求1或6所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述第一高密度聚乙烯的拉伸强度大于等于25MPa。The silane cross-linked polyethylene insulation material for a heating cable according to claim 1 or 6, wherein the tensile strength of the first high-density polyethylene is greater than or equal to 25 MPa.
  8. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述双峰聚乙烯的熔融指数为0.1-1.0g/10min。The silane cross-linked polyethylene insulation material for a heating cable according to claim 1, wherein the melting index of the bimodal polyethylene is 0.1-1.0 g / 10min.
  9. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述聚丙烯的数均分子量为8-15万。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, wherein the number average molecular weight of the polypropylene is 80,000 to 150,000.
  10. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述第二高密度聚乙烯的熔融指数为2.0-10.0g/10min；优选地，所述第二高密度聚乙烯的熔融指数为4.0-9.0g/10min。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, wherein the melt index of the second high-density polyethylene is 2.0-10.0g / 10min; preferably, the second high-density polyethylene The melt index of polyethylene is 4.0-9.0 g / 10 min.
  11. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述线性低密度聚乙烯的熔融指数为10-30g/10min；优选地，所述线性低密度聚乙烯的熔融指数为15-25g/10min。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, characterized in that the melt index of the linear low-density polyethylene is 10-30g / 10min; preferably, the linear low-density polyethylene The melt index is 15-25g / 10min.
  12. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述硅烷接枝料和所述交联催化剂母粒的投料质量比为15-23︰1。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, characterized in that the feeding mass ratio of the silane graft material and the cross-linking catalyst mother particles is 15-23: 1.
  13. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述硅烷交联剂为选自乙烯基-三(2-甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷和乙烯基三甲氧基硅烷中的一种或者多种的组合；和/或，所述接枝引发剂为选自过氧化二异丙苯、1,1-二叔丁基过氧化-3,3,5-三甲基环己烷和过氧化二苯甲酰中的一种或者多种的组合。The silane cross-linked polyethylene insulation material for a heating cable according to claim 1, wherein the silane cross-linking agent is selected from vinyl-tris (2-methoxyethoxy) silane, vinyl tris One or more combinations of ethoxysilane and vinyltrimethoxysilane; and / or, the graft initiator is selected from dicumyl peroxide, 1,1-di-tert-butyl peroxide One or more combinations of oxy-3,3,5-trimethylcyclohexane and dibenzoyl peroxide.
  14. 根据权利要求1或13所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述第一润滑剂为选自PE蜡、EVA蜡和PPA中的一种或者多种的组合；和/或，所述第一抗氧剂为选自抗氧剂1010、抗氧剂168、抗氧剂1076、抗氧剂DSTP和抗氧剂300中的一种或者多种的组合。The silane cross-linked polyethylene insulation material for heating cables according to claim 1 or 13, wherein the first lubricant is one or a combination of one or more selected from PE wax, EVA wax and PPA; And / or, the first antioxidant is one or a combination of one or more selected from the group consisting of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant DSTP, and antioxidant 300.
  15. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，所述交联催化剂为选自对甲苯磺酸、十二烷基苯磺酸、异辛酸铋和有机钛中的一种或者多种的组合；和/或，所述第二润滑剂为选自PE蜡、EVA蜡和PPA中的一种或者多种的组合；和/或，所述第二抗氧剂为抗氧剂1024和/或防老剂TMQ。The silane crosslinked polyethylene insulation material for heating cables according to claim 1, wherein the crosslinking catalyst is selected from p-toluenesulfonic acid, dodecylbenzenesulfonic acid, bismuth isooctanoate, and organic titanium One or more combinations; and / or, the second lubricant is one or more combinations selected from PE wax, EVA wax and PPA; and / or, the second antioxidant It is antioxidant 1024 and / or antioxidant TMQ.
  16. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，以重量份数计，所述硅烷接枝料的原料中，第一高密度聚乙烯40-70份、双峰聚乙烯5-30份、聚丙烯20-40份、硅烷交联剂0.5-2.0份、接枝引发剂0.5-2.5份、第一润滑剂0.5-3份和第一抗氧剂0.3-2.0份；以重量份数计，所述交联催化剂母粒的原料中，第二高密度聚乙烯50-60份、线性低密度聚乙烯40-50份、交联催化剂0.5-3份、第二润滑剂3-8份和第二抗氧剂0.5-2份；所述第一高密度聚乙烯的熔融指数为0.1-2.5g/10min，所述双峰聚乙烯的熔融指数为0.1-1.0g/10min，所述聚丙烯的数均分子量为8-15万，所述第二高密度聚乙烯的熔融指数为2.0-10.0g/10min，所述线性低密度聚乙烯的熔融指数为10-30g/10min，所述硅烷接枝料和所述交联催化剂母粒的投料质量比为15-23︰1。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, characterized in that, in terms of parts by weight, among the raw materials of the silane graft material, the first high-density polyethylene is 40-70 parts, double Peak polyethylene 5-30 parts, polypropylene 20-40 parts, silane crosslinking agent 0.5-2.0 parts, graft initiator 0.5-2.5 parts, first lubricant 0.5-3 parts and first antioxidant 0.3-2.0 Parts; in parts by weight, in the raw material of the crosslinking catalyst masterbatch, 50-60 parts of the second high density polyethylene, 40-50 parts of the linear low density polyethylene, 0.5-3 parts of the crosslinking catalyst, the second 3-8 parts of lubricant and 0.5-2 parts of second antioxidant; the melt index of the first high-density polyethylene is 0.1-2.5g / 10min, and the melt index of the bimodal polyethylene is 0.1-1.0g / 10min, the number average molecular weight of the polypropylene is 80,000-150,000, the melt index of the second high density polyethylene is 2.0-10.0g / 10min, the melt index of the linear low density polyethylene is 10-30g / 10min, the feeding mass ratio of the silane grafting material and the crosslinking catalyst masterbatch is 15-23: 1.
  17. 根据权利要求1所述的发热电缆用硅烷交联聚乙烯绝缘材料，其特征在于，以重量份数计，所述硅烷接枝料的原料中，第一高密度聚乙烯50份、双峰聚乙烯20份、聚丙烯30份、硅烷交联剂1份、接枝引发剂2.2份、第一润滑剂2份和第一抗氧剂0.8份；以重量份数计，所述交联催化剂母粒的原料中，第二高密度聚乙烯50份、线性低密度聚乙烯50份、交联催化剂2份、第二润滑剂4份和第二抗氧剂1.2份；所述第一高密度聚乙烯为齐鲁石化产高密度聚乙烯牌号为：TR144，熔融指数为0.3g/10min；所述双峰聚乙烯为北欧化工产，牌号为：FB2230，熔融指数为0.2g/10min；所述聚丙烯选用中石油独山子生产牌号为：EPF30R；硅烷交联剂包含为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基-三(2-甲氧基乙氧基)硅烷三者按重量比1:1:2复配的混合物；接枝引发剂为过氧化二异丙苯；第一润滑剂为含氟流变剂ppa，购自3M公司；第一抗氧剂为抗氧剂300；所述第二高密度聚乙烯购自独山子石化，牌号为DMDA-8008，熔融指数为7.5g/10min；所述线性低密度聚乙烯为中石化镇海炼化产的线性低密度聚乙烯牌号为:8320，熔融指数为20g/10min；所述交联催化剂为十二烷基苯磺酸与有机钛按重量比1:1的比例复配的混合物；第二润滑剂为PE蜡；第二抗氧剂为抗氧剂1024；所述硅烷接枝料和所述交联催化剂母粒的投料质量比为95∶5。The silane cross-linked polyethylene insulation material for heating cables according to claim 1, characterized in that, in terms of parts by weight, among the raw materials of the silane graft material, 50 parts of the first high-density polyethylene, bimodal polymer 20 parts of ethylene, 30 parts of polypropylene, 1 part of silane crosslinking agent, 2.2 parts of graft initiator, 2 parts of first lubricant and 0.8 parts of first antioxidant; in terms of parts by weight, the crosslinking catalyst master Among the raw materials of the pellets, 50 parts of the second high-density polyethylene, 50 parts of the linear low-density polyethylene, 2 parts of the cross-linking catalyst, 4 parts of the second lubricant, and 1.2 parts of the second antioxidant; Ethylene is a high-density polyethylene grade produced by Qilu Petrochemical: TR144, with a melt index of 0.3g / 10min; the bimodal polyethylene is produced by Nordic Chemicals, with a grade: FB2230, and a melt index of 0.2g / 10min; The selected production grade of PetroChina Dushanzi is: EPF30R; the silane crosslinking agent includes vinyl trimethoxysilane, vinyl triethoxysilane, vinyl-tris (2-methoxyethoxy) silane by weight Ratio 1: 1: 2 compounded mixture; the graft initiator is dicumyl peroxide; Lubricant is fluorine-containing rheological agent ppa, purchased from 3M Company; the first antioxidant is antioxidant 300; the second high-density polyethylene is purchased from Dushanzi Petrochemical, brand is DMDA-8008, melt index is 7.5 g / 10min; the linear low-density polyethylene is a linear low-density polyethylene produced by Sinopec Zhenhai Refining & Chemical Co., Ltd .: 8320, and the melt index is 20g / 10min; the cross-linking catalyst is dodecylbenzenesulfonic acid and organic A mixture of titanium compounded in a weight ratio of 1: 1; the second lubricant is PE wax; the second antioxidant is antioxidant 1024; the feeding quality of the silane graft material and the crosslinking catalyst master batch The ratio is 95: 5.
  18. 一种权利要求1-17中任一项权利要求所述的发热电缆用硅烷交联聚乙烯绝缘材料的制备方法，其特征在于，所述制备方法包括如下步骤：A method for preparing a silane cross-linked polyethylene insulation material for a heating cable according to any one of claims 1-17, characterized in that the preparation method includes the following steps:
    (1)制备硅烷接枝料：按配方比例称取各原料，将称取的硅烷交联剂、接枝引发剂和第一抗氧剂混合，制得硅烷混合液；将称取的第一高密度聚乙烯、双峰聚乙烯和聚丙烯加入挤出机中，加入所述硅烷混合液，经塑化接枝，造粒，干燥，即制成所述硅烷接枝料；(1) Preparation of silane grafting material: Weigh each raw material in proportion to the formula, mix the weighed silane crosslinking agent, graft initiator and first antioxidant to prepare a silane mixture; weigh the first High-density polyethylene, bimodal polyethylene and polypropylene are added to the extruder, the silane mixture is added, plasticized and grafted, granulated, and dried to prepare the silane grafting material;
    (2)制备交联催化剂母粒：按配方比例称取各原料，混合，加入挤出机中挤出造粒，干燥，即制成所述交联催化剂母粒；(2) Preparation of crosslinking catalyst masterbatch: weigh the raw materials according to the formula ratio, mix, add to the extruder and extrude and pelletize, and dry to prepare the crosslinking catalyst masterbatch;
    (3)将步骤(1)制备的所述硅烷接枝料与步骤(2)制备的所述交联催化剂母粒按配方比例包装，当需要制成发热电缆的绝缘层时，直接将按配比包装好的硅烷接枝料与交联催化剂母粒混合，在挤出机中挤出，挤出温度为加料段165±5℃、压缩段175±5℃、均化断190±5℃、模头200±5℃，然后在温度为90℃的水中交联，即可制成。(3) Pack the silane grafting material prepared in step (1) and the crosslinking catalyst masterbatch prepared in step (2) according to the formula ratio. When it is necessary to make the insulating layer of the heating cable, it will be directly in proportion The packaged silane grafting material is mixed with the crosslinking catalyst masterbatch and extruded in an extruder. The extrusion temperature is 165 ± 5 ° C in the feeding section, 175 ± 5 ° C in the compression section, 190 ± 5 ° C in the homogenization break, die The head is 200 ± 5 ℃, and then cross-linked in water at a temperature of 90 ℃, it can be made.
  19. 根据权利要求18所述的制备方法，其特征在于，步骤(1)中，所述挤出机为往复式螺杆BUSS挤出机，温度设置为压缩段150℃～195℃，均化段200℃～220℃。The preparation method according to claim 18, characterized in that, in step (1), the extruder is a reciprocating screw BUSS extruder, the temperature is set to 150 ° C to 195 ° C in the compression section and 200 ° C in the homogenization section ~ 220 ℃.
  20. 根据权利要求18所述的制备方法，其特征在于，步骤(2)中，所述挤出机采用双螺杆挤出机，所述双螺杆挤出机的进料段、压缩段、熔融段及模头温度依次设置为120℃～130℃、140℃～160℃、170℃～180℃以及180℃～185℃。The preparation method according to claim 18, characterized in that, in step (2), the extruder adopts a twin-screw extruder, and the feed section, compression section, melting section and The die temperature is sequentially set to 120 ° C to 130 ° C, 140 ° C to 160 ° C, 170 ° C to 180 ° C, and 180 ° C to 185 ° C.
  21. 一种发热电缆，所述发热电缆包括发热电缆绝缘层，其特征在于，所述发热电缆绝缘层由权利要求1-17中任一项权利要求所述的发热电缆用硅烷交联聚乙烯绝缘材料在水中交联而制成。A heating cable, the heating cable includes an insulating layer of a heating cable, characterized in that the insulating layer of the heating cable is made of silane cross-linked polyethylene insulation material for the heating cable of any one of claims 1-17 Made by crosslinking in water.
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