WO2021114758A1 - Flame-retardant tpe sheath material, preparation method therefor and application thereof - Google Patents

Flame-retardant tpe sheath material, preparation method therefor and application thereof Download PDF

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WO2021114758A1
WO2021114758A1 PCT/CN2020/113336 CN2020113336W WO2021114758A1 WO 2021114758 A1 WO2021114758 A1 WO 2021114758A1 CN 2020113336 W CN2020113336 W CN 2020113336W WO 2021114758 A1 WO2021114758 A1 WO 2021114758A1
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flame
parts
sheath material
retardant
tpe sheath
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PCT/CN2020/113336
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French (fr)
Chinese (zh)
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蔺兴清
靖吉旭
张刚
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上海凯波特种电缆料厂有限公司
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Publication of WO2021114758A1 publication Critical patent/WO2021114758A1/en

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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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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

Definitions

  • the invention relates to the technical field of halogen-free flame-retardant materials, in particular to a flame-retardant TPE sheath material and a preparation method and application thereof.
  • Thermoplastic elastomer TPE not only has the high elasticity, high strength, high resilience of rubber, but also has excellent coloring, weather resistance, fatigue resistance and temperature resistance, and is environmentally friendly, non-toxic and safe, and has a wide range of hardness, which can be recycled and reduced. cost.
  • relevant environmental protection regulations such as EU RoHS standards and REACH regulations have been gradually implemented in the electronic and electrical fields.
  • the demand for green and environmentally friendly thermoplastic materials is increasing, and TPE with both plastic and rubber characteristics Halogen-free flame-retardant cable materials have become the focus of research and development.
  • the TPE material with SEBS as the matrix increases the flame retardancy by adding a large amount of organic flame retardant, but at the same time, there are phenomena such as easy scratching, easy precipitation, low mechanical properties, poor resilience, poor weather resistance and fatigue resistance.
  • the reduction of these comprehensive properties affects the service life and operational safety of the product, and limits the application of low-smoke, halogen-free and flame-retardant TPE materials in the fields of electronic and electrical connection lines, especially the materials for new energy charging pile cables.
  • the present invention provides a flame-retardant TPE sheath material.
  • a flame-retardant TPE sheath material made of the following raw materials: SEBS 25-30 parts, POE 8-12 parts, polypropylene 8-12 parts, and organic flame retardant 20-30 parts , 5-10 parts of flame retardant synergist, 3-5 parts of anti-scratch agent, 0.1-0.3 parts of antioxidant, 10-15 parts of extender oil, 1-3 parts of processing aids, the balance of deionized water.
  • a flame-retardant TPE sheath material is made from the following raw materials in parts by weight: 30 parts of SEBS, 10 parts of POE, 10 parts of polypropylene, 30 parts of organic flame retardant, 30 parts of flame retardant 10 parts of effect agent, 5 parts of scratch-resistant agent, 0.3 part of antioxidant, 10 parts of extender oil, 2 parts of processing aid, the balance of deionized water.
  • the flame-retardant TPE sheath material disclosed in the present invention can effectively solve the contradiction between flame retardancy and physical and mechanical properties of existing halogen-free flame-retardant TPE materials, because it has high flame retardancy, scratch resistance, and no precipitation. , Good mechanical performance, and excellent performance such as resistance to stress fatigue and weathering, and is effectively used in the field of new energy electric vehicle charging pile cable materials.
  • the SEBS is a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butene copolymer obtained by hydrogenation of polybutadiene as the middle elastic block;
  • the melt index of the polypropylene is 3-8 g/min, and
  • the thermoplastic elastomer is at least one of ethylene-octene copolymer and/or ethylene acrylic acid copolymer.
  • the POE plastic is a thermoplastic elastomer that uses metallocene catalysts to realize in-situ polymerization of ethylene and octene;
  • the two ends are non-polar long-chain alkyl groups, and the middle is polar bisamide groups.
  • This symmetrical neutral polar structure gives EBS excellent wetting and penetrating capabilities. It has significant wetting and dispersing effects on various pigments and filler powders.
  • the good match of the polar group and the non-polar group in the EBS molecule and the higher molecular weight make it insoluble in alcohols and oils. This balanced nature makes it moderately compatible in most resins and exhibits excellent internal and external lubrication effects.
  • EBS as a lubricant, viscosity reducer, and release agent, widely used in PE, PP, PS, PBT, PET, PMMA, PC, PVC, ABS, AS, PA, PF, UF and other resins, and EBS is smooth
  • the characteristics make it have the function of a slip agent, and can be used as a slip agent in the production of blown film to improve the opening between the film surfaces.
  • the organic flame retardant is one or a combination of aluminum hypophosphite, diethyl aluminum hypophosphite, and pentaerythritol polyphosphate melamine salt.
  • the flame retardant synergist is one or a combination of melamine cyanurate, nano silica, and nano calcium carbonate.
  • the scratch resistant agent is talc and/or talc polyolefin blended scratch resistant masterbatch; and the antioxidant is tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxyl Phenyl) propionic acid) pentaerythritol ester, tris[2,4-di-tert-butylphenyl] phosphite, ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl One or a combination of alcohol ester and N,N'-bis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
  • the extender oil is selected from one of paraffin-based white oil and naphthenic white oil; the processing aid is at least one of titanium dioxide, EBS, and silicone masterbatch.
  • Another object of the present invention is to provide a method for preparing a flame-retardant TPE sheath material.
  • a method for preparing a flame-retardant TPE sheath material specifically includes the following steps:
  • the melt extrusion granulation process in the step (2) specifically includes: adding the raw materials into a twin-screw extruder through an automatic weightlessness metering scale for melting and mixing, and then extruding through a single screw and pelletizing with a water ring.
  • the temperature of each section of the screw is: 160 ⁇ 175°C in the upper feeding section, 180 ⁇ 190°C in the conveying section, 195 ⁇ 210°C in the melting section, 190 ⁇ 200°C in the upper and lower connecting section, and 180 ⁇ 200 in the lower stage. 185°C, head 170 ⁇ 180°C.
  • the melt extrusion granulation process in step (2) can also be replaced by the following steps: adding raw materials into a twin-screw extruder through automatic weight loss metering for melt extrusion, water-cooled stranding and pelletizing, and then Spin drying and boiling drying; wherein the length to diameter ratio of the twin-screw extruder is 44:1, the temperature of each section of the twin-screw is: 160-175°C in the feeding section, 180-190°C in the conveying section, and 195-210°C in the melting section.
  • the machine head is 190 ⁇ 200°C.
  • the present invention provides a simple and easy method for preparing a flame-retardant TPE sheath material.
  • the reason why the stirring rate and the stirring time in each step are set in this way is that only within the range of the stirring rate and the stirring time can the excellent
  • the dispersing effect is not wasteful of excess power and energy; and the process parameters of the melt extrusion granulation stage are selected by the inventor through creative experiments, and the final preparation can be obtained by selecting appropriate process parameters and combining appropriate raw material ratios. Flame-retardant TPE jacket material with excellent performance.
  • the invention also provides the application of the above-mentioned flame-retardant TPE sheath material in the charging pile cable of a new energy electric vehicle.
  • the present disclosure provides a flame-retardant TPE sheath material and its preparation method and application. Compared with the prior art, the present invention has the following advantages:
  • the scratch-resistant and precipitation-resistant TPE material for charging pile cables of new energy electric vehicles is based on selected thermoplastic elastomer SEBS, thermoplastic elastomer POE and polypropylene blend modified polyolefin as the base material , A certain amount of intumescent aluminum hypophosphite organic flame retardant and flame retardant synergist are appropriately added, and combined with specific processing aids.
  • the raw material formula disclosed in the present invention achieves low filling content. Efficient compounding, with excellent physical and mechanical properties, scratch resistance and precipitation resistance.
  • the wire or cable extruded by the product of the present invention can pass the VW-1 wire flame resistance requirement of 0.40mm thick thin-walled insulation, which not only solves the problem of precipitation and combustion dripping, but also has a combustion light transmittance of more than 85% ,
  • the invented product can be better suitable for new energy electric vehicle charging pile cable materials.
  • the environmental protection TPE material for charging pile cables of new energy electric vehicles provided by the present invention meets the requirements of EU RoHS and meets the requirements of EU standard EN50620, and adapts to the global environmental protection situation.
  • the flame-retardant TPE sheath material prepared by the present invention not only has superior flame retardancy and high mechanical properties, but also has scratch resistance and precipitation resistance, and its extrusion speed can reach 150-200m/ min, and the material density is low, it can be re-processed and utilized, which is environmentally friendly and economical, and is suitable for market promotion and application.
  • the embodiment of the present invention discloses a flame-retardant TPE sheath material and its preparation method and application.
  • the flame-retardant TPE sheath material prepared by the present invention has excellent flame retardancy and high mechanical properties, and is resistant to scratches and precipitation. It can effectively solve the contradiction between flame retardancy and physical and mechanical properties of existing halogen-free flame retardant TPE sheath materials, and can be better used as materials for charging pile cables for new energy electric vehicles, which has great market application and promotion value .
  • the invention discloses a flame-retardant TPE sheath material, which is calculated in parts by weight and is made of the following raw materials in proportions: 25-30 parts of SEBS, 8-12 parts of POE, 8-12 parts of polypropylene, and organic flame retardant 20-30 parts, flame retardant synergist 5-10 parts, scratch-resistant agent 3-5 parts, antioxidant 0.1-0.3 parts, extender oil 10-15 parts, processing aids 1-3 parts, deionized water the amount.
  • the melt index of polypropylene is 3-8 g/min
  • the thermoplastic elastomer is at least one of ethylene-octene copolymer and/or ethylene acrylic acid copolymer.
  • the organic flame retardant is one or a combination of aluminum hypophosphite, diethyl aluminum hypophosphite, and pentaerythritol polyphosphate melamine salt.
  • the flame retardant synergist is one or a combination of melamine cyanurate, nano silica, and nano calcium carbonate.
  • the anti-scratch agent is talc and/or talc polyolefin blended anti-scratch masterbatch;
  • the antioxidant is tetra[ ⁇ -(3,5-di-tert-butyl-4- (Hydroxyphenyl) propionic acid) pentaerythritol ester, tris[2,4-di-tert-butylphenyl] phosphite, ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate
  • the extender oil is selected from one of paraffin-based white oil and naphthenic white oil; the processing aid is at least one of titanium dioxide, EBS, and silicone masterbatch.
  • the invention also discloses a preparation method of the flame-retardant TPE sheath material, which specifically includes the following steps:
  • the melt extrusion granulation process in step (2) specifically includes: adding the raw materials into a twin-screw extruder through an automatic weightlessness metering scale for melting and mixing, and then extruding through a single screw, water Ring pelletizing, followed by spin drying and boiling drying; the temperature of each section of the screw is: the upper feeding section is 160 ⁇ 175°C, the conveying section is 180 ⁇ 190°C, the melting section is 195 ⁇ 210°C, and the upper and lower connecting sections are 190 ⁇ 200°C. The next stage is 180 ⁇ 185°C, and the machine head is 170 ⁇ 180°C.
  • the melt extrusion granulation process in step (2) can also be replaced by the following steps: the raw materials are added to the twin-screw extruder through automatic weight loss metering for melt extrusion and water-cooled drawing. Cut into pellets, then spin and boil and dry; wherein the length to diameter ratio of the twin-screw extruder is 44:1, the temperature of each section of the twin-screw is: the feeding section is 160 ⁇ 175°C, the conveying section is 180 ⁇ 190°C, and the melting section is 195 ⁇ 210°C, head 190 ⁇ 200°C.
  • a flame-retardant TPE sheath material made of the following raw materials: 30 parts of SEBS, 10 parts of POE, 10 parts of polypropylene, 30 parts of aluminum hypophosphite, 5 parts of melamine cyanurate, 5 parts of nano-silica, 5 parts of scratch-resistant agent, 0.3 parts of antioxidant, 10 parts of filler oil, 0.5 parts of EBS, the balance of deionized water.
  • a flame-retardant TPE sheath material made of the following raw materials: 30 parts of SEBS, 10 parts of POE, 10 parts of polypropylene, 20 parts of aluminum hypophosphite, and 10 parts of aluminum diethylphosphinate Parts, 7 parts of melamine cyanurate, 3 parts of nano calcium carbonate, 5 parts of scratch-resistant agent, 0.3 parts of antioxidant, 10 parts of filler oil, 2 parts of silicone, the balance of deionized water.
  • a flame-retardant TPE sheath material based on parts by weight, made of the following raw materials: SEBS 30 parts, POE 10 parts, polypropylene 10 parts, pentaerythritol polyphosphate melamine salt 25 parts, nano silica 10 parts, 5 parts of nano calcium carbonate, 5 parts of anti-scratch agent, 0.3 parts of antioxidant, 10 parts of filler oil, 2 parts of silicone, the balance of deionized water.
  • the raw materials disclosed in Examples 1 to 3 of the present invention are prepared by the same preparation method as a flame-retardant TPE sheath material.
  • the specific implementation process is as follows:
  • each raw material into the corresponding silo set the program according to the mass parts of the component ratio, add the automatic weightless metering electronic scale to the twin-screw extruder for melting and mixing, and then granulate by single-screw extrusion.
  • the temperature of each section of the screw is: upper feeding section 160 ⁇ 175°C, conveying section 180 ⁇ 190°C, melting section 195 ⁇ 210°C, upper and lower connecting section 190 ⁇ 200°C, lower stage 180 ⁇ 185°C, head 170 ⁇ 180 °C; Afterwards, water ring pelletizing, centrifugal drying machine to dry, and finally boiling and drying, the environmental protection TPE material for charging pile cables of new energy electric vehicles is prepared.
  • step (2) can also be replaced by the following steps:
  • the automatic weight-loss metering is added to a twin-screw extruder for melt extrusion, water-cooled stretched strips and pelletized, followed by spin drying and boiling drying to prepare environmentally-friendly TPE materials for charging pile cables for new energy electric vehicles.
  • the length-diameter ratio of the twin-screw extruder is 44:1
  • the temperature of each section of the twin-screw is: the feeding section is 160-175°C, the conveying section is 180-190°C, the melting section is 195-210°C, and the die head is 190-200°C.
  • the inventors used the flame-retardant TPE sheath materials prepared in Example 1 and Example 2 for charging In the pile cable, the performance of the cabled product is measured, and the specific measurement results are shown in Table 2 below:
  • the TPE sheath material developed and developed by the present invention has high flame retardancy, scratch resistance, no precipitation, good mechanical properties, and excellent performance such as stress fatigue resistance and weathering resistance, which can effectively solve the existing halogen-free resistance.
  • the contradiction between the flame retardancy and the physical and mechanical properties of the flame-retardant TPE sheath material can be better used as a material for charging pile cables for new energy electric vehicles, which has great market application and promotion value.

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Abstract

A flame-retardant TPE sheath material, a preparation method therefor, and application thereof, relating to the technical field of halogen-free flame retardant materials. The flame-retardant TPE sheath material is prepared by the following raw material ratios: 25-30 parts of SEBS, 8-12 parts of POE, 8-12 parts of polypropylene, 20-30 parts of organic flame retardant, 5-10 parts of flame retardant synergist, 3-5 parts of scratch resistance agent, 0.1-0.3 parts of antioxidant, 10-15 parts of extender oil, 1-3 parts of processing aid, and the balance of deionized water. The TPE sheath material has the characteristics of high flame retardant properties, scratch resistance, no precipitation, and good mechanical properties, and has excellent properties of stress fatigue resistance, weather-ageing resistance, and the like, thus, the contradiction between the flame retardancy and the physical and mechanical properties, existing in the existing halogen-free flame retardant TPE sheath material, can be effectively solved, and the TPE sheath material can better serve as cable materials for charging piles of new energy electric automobiles.

Description

一种阻燃TPE护套料及其制备方法与应用A flame-retardant TPE sheath material and its preparation method and application 技术领域Technical field
本发明涉及无卤阻燃材料技术领域，尤其涉及一种阻燃TPE护套料及其制备方法与应用。The invention relates to the technical field of halogen-free flame-retardant materials, in particular to a flame-retardant TPE sheath material and a preparation method and application thereof.
背景技术Background technique
热塑性弹性体TPE既具有橡胶的高弹性、高强度、高回弹性，又具有优良的着色性、耐候性、抗疲劳性和耐温性，且环保无毒安全，硬度范围广，可以循环使用降低成本。随着整个社会环保意识的不断增强，欧盟RoHS标准和REACH法规等有关的环保规定已在电子、电气领域中逐步执行，绿色环保的热塑性材料的需求日益增加，而兼具塑料和橡胶特性的TPE无卤阻燃电缆料成为研发的重点。Thermoplastic elastomer TPE not only has the high elasticity, high strength, high resilience of rubber, but also has excellent coloring, weather resistance, fatigue resistance and temperature resistance, and is environmentally friendly, non-toxic and safe, and has a wide range of hardness, which can be recycled and reduced. cost. With the increasing awareness of environmental protection in the entire society, relevant environmental protection regulations such as EU RoHS standards and REACH regulations have been gradually implemented in the electronic and electrical fields. The demand for green and environmentally friendly thermoplastic materials is increasing, and TPE with both plastic and rubber characteristics Halogen-free flame-retardant cable materials have become the focus of research and development.
目前以SEBS为基体的TPE材料，通过添加大量有机阻燃剂提高阻燃性的同时，出现易刮白、易析出、机械性能低、回弹性差、耐候性和耐疲劳性差等现象。这些综合性能的降低，影响了产品的使用寿命和运行安全性，限制了低烟无卤阻燃TPE材料在电子、电气连接线领域的应用，特别是新能源充电桩电缆用料。At present, the TPE material with SEBS as the matrix increases the flame retardancy by adding a large amount of organic flame retardant, but at the same time, there are phenomena such as easy scratching, easy precipitation, low mechanical properties, poor resilience, poor weather resistance and fatigue resistance. The reduction of these comprehensive properties affects the service life and operational safety of the product, and limits the application of low-smoke, halogen-free and flame-retardant TPE materials in the fields of electronic and electrical connection lines, especially the materials for new energy charging pile cables.
因此，如何提供一种性能优异，可用作新能源电动汽车充电桩电缆用料的阻燃TPE护套料是本领域技术人员亟待解决的技术难题。Therefore, how to provide a flame-retardant TPE sheath material with excellent performance that can be used as a material for charging pile cables for new energy electric vehicles is a technical problem to be solved by those skilled in the art.
发明内容Summary of the invention
有鉴于此，本发明提供了一种阻燃TPE护套料。In view of this, the present invention provides a flame-retardant TPE sheath material.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above objectives, the present invention adopts the following technical solutions:
一种阻燃TPE护套料，按重量份数计，由以下原料配比制成：SEBS 25-30份、POE 8-12份、聚丙烯8-12份、有机阻燃剂20-30份、阻燃协效剂5-10份、耐刮擦剂3-5份、抗氧化剂0.1-0.3份、填充油10-15份、加工助剂1-3份、去离子水余量。A flame-retardant TPE sheath material, calculated in parts by weight, made of the following raw materials: SEBS 25-30 parts, POE 8-12 parts, polypropylene 8-12 parts, and organic flame retardant 20-30 parts , 5-10 parts of flame retardant synergist, 3-5 parts of anti-scratch agent, 0.1-0.3 parts of antioxidant, 10-15 parts of extender oil, 1-3 parts of processing aids, the balance of deionized water.
进一步优选的，一种阻燃TPE护套料，按重量份数计，由以下原料配比制成：SEBS 30份、POE 10份、聚丙烯10份、有机阻燃剂30份、阻燃协效剂10份、耐刮擦剂5份、抗氧化剂0.3份、填充油10份、加工助剂2份、去离子水余量。More preferably, a flame-retardant TPE sheath material is made from the following raw materials in parts by weight: 30 parts of SEBS, 10 parts of POE, 10 parts of polypropylene, 30 parts of organic flame retardant, 30 parts of flame retardant 10 parts of effect agent, 5 parts of scratch-resistant agent, 0.3 part of antioxidant, 10 parts of extender oil, 2 parts of processing aid, the balance of deionized water.
通过采用上述技术方案得到的阻燃TPE护套料，优异效果如下：The flame-retardant TPE sheath material obtained by adopting the above technical scheme has excellent effects as follows:
本发明公开的阻燃TPE护套料能有效解决现有无卤阻燃TPE材料所存在的阻燃性、物理机械性能之间的矛盾，因其具有阻燃性能高、耐刮擦、无析出，机械性能好，且耐应力疲劳、耐气候老化等优异性能，而被有效用于新能源电动汽车充电桩电缆用料领域。The flame-retardant TPE sheath material disclosed in the present invention can effectively solve the contradiction between flame retardancy and physical and mechanical properties of existing halogen-free flame-retardant TPE materials, because it has high flame retardancy, scratch resistance, and no precipitation. , Good mechanical performance, and excellent performance such as resistance to stress fatigue and weathering, and is effectively used in the field of new energy electric vehicle charging pile cable materials.
优选的，所述SEBS是以聚苯乙烯为末端段，以聚丁二烯加氢得到的乙烯-丁烯共聚物为中间弹性嵌段的线性三嵌共聚物；所述聚丙烯的熔融指数为3～8g/min，且所述热塑性弹性体至少为乙烯-辛烯共聚物和/或乙烯丙烯酸共聚物中的一种。Preferably, the SEBS is a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butene copolymer obtained by hydrogenation of polybutadiene as the middle elastic block; the melt index of the polypropylene is 3-8 g/min, and the thermoplastic elastomer is at least one of ethylene-octene copolymer and/or ethylene acrylic acid copolymer.
此外，所述POE塑料是采用茂金属催化剂的乙烯和辛烯实现原位聚合的热塑性弹性体；In addition, the POE plastic is a thermoplastic elastomer that uses metallocene catalysts to realize in-situ polymerization of ethylene and octene;
并且EBS分子结构中，两端为非极性长链烷基，中间是极性双酰胺基，这种对称中位极性结构，赋予EBS优良的润湿和渗透能力。对各类颜料和填充剂粉体有显着的润湿和分散作用。EBS分子中的极性基和非极性基的良好匹配和较高分子量，使它既不溶于醇类，又不溶于油类。这种均衡性质使它在大多数树脂中具有适中的相容性，并呈现出优良的内部和外部润滑效果。将EBS作为润滑剂、降粘剂、脱模剂，广泛适用于PE、PP、PS、PBT、PET、 PMMA、PC、PVC、ABS、AS、PA、PF、UF等树脂中，并且EBS的滑腻特性，使它具有爽滑剂功能，在吹塑薄膜生产中可作为爽滑剂用，改进膜面间的开口性。And in the EBS molecular structure, the two ends are non-polar long-chain alkyl groups, and the middle is polar bisamide groups. This symmetrical neutral polar structure gives EBS excellent wetting and penetrating capabilities. It has significant wetting and dispersing effects on various pigments and filler powders. The good match of the polar group and the non-polar group in the EBS molecule and the higher molecular weight make it insoluble in alcohols and oils. This balanced nature makes it moderately compatible in most resins and exhibits excellent internal and external lubrication effects. Use EBS as a lubricant, viscosity reducer, and release agent, widely used in PE, PP, PS, PBT, PET, PMMA, PC, PVC, ABS, AS, PA, PF, UF and other resins, and EBS is smooth The characteristics make it have the function of a slip agent, and can be used as a slip agent in the production of blown film to improve the opening between the film surfaces.
优选的，所述有机阻燃剂为次磷酸铝、二乙基次磷酸铝、季戊四醇多聚磷酸酯三聚氰胺盐中的一种或两种组合。Preferably, the organic flame retardant is one or a combination of aluminum hypophosphite, diethyl aluminum hypophosphite, and pentaerythritol polyphosphate melamine salt.
优选的，所述阻燃协效剂为三聚氰胺氰尿酸酯、纳米二氧化硅、纳米碳酸钙中的一种或两种组合。Preferably, the flame retardant synergist is one or a combination of melamine cyanurate, nano silica, and nano calcium carbonate.
优选的，所述耐刮擦剂为滑石粉和/或滑石粉聚烯烃共混耐刮擦母粒；且所述抗氧化剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、三[2,4-二叔丁基苯基]亚磷酸酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、N,N'-双[β-(3,5-二叔丁基-4-羟基苯基)丙酰]肼中的一种或两种组合。Preferably, the scratch resistant agent is talc and/or talc polyolefin blended scratch resistant masterbatch; and the antioxidant is tetra[β-(3,5-di-tert-butyl-4-hydroxyl Phenyl) propionic acid) pentaerythritol ester, tris[2,4-di-tert-butylphenyl] phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl One or a combination of alcohol ester and N,N'-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
优选的，所述填充油选自石蜡基白油、环烷基白油中的一种；所述加工助剂至少为二氧化钛、EBS、硅酮母料中的一种。Preferably, the extender oil is selected from one of paraffin-based white oil and naphthenic white oil; the processing aid is at least one of titanium dioxide, EBS, and silicone masterbatch.
本发明的另一个目的在于提供一种阻燃TPE护套料的制备方法。Another object of the present invention is to provide a method for preparing a flame-retardant TPE sheath material.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above objectives, the present invention adopts the following technical solutions:
一种阻燃TPE护套料的制备方法，所述方法具体包括如下步骤：A method for preparing a flame-retardant TPE sheath material, the method specifically includes the following steps:
(1)将SEBS和填充油按照配方比例低速搅拌1～3min后，静置待用；(1) Stir the SEBS and filler oil at low speed according to the formula ratio for 1 to 3 minutes, and then let it stand for use;
(2)将原料POE、聚丙烯、有机阻燃剂、阻燃协效剂、耐刮擦剂、抗氧化剂和加工助剂分别加入料仓中，并按照原料组分配比进行程序设定，自动配料、混合后熔融挤出造粒，最终制得阻燃TPE护套料。(2) Add the raw materials POE, polypropylene, organic flame retardant, flame retardant synergist, scratch resistant agent, antioxidant and processing aid to the silo, and set the program according to the raw material composition ratio, automatically After ingredients and mixing, melt extrusion granulation, and finally prepare flame-retardant TPE sheath material.
优选的，所述步骤(2)中的熔融挤出造粒工艺具体为：将原料通过自动失重计量秤加入双螺杆挤出机中进行熔融混合，再经单螺杆挤出、水环切粒，随后甩干、沸腾干燥；其中螺杆各段温度为：上阶加料段160～175℃，输送段180～190℃，熔融段195～210℃，上下阶连接段190～200℃，下阶段180～185℃，机头170～180℃。Preferably, the melt extrusion granulation process in the step (2) specifically includes: adding the raw materials into a twin-screw extruder through an automatic weightlessness metering scale for melting and mixing, and then extruding through a single screw and pelletizing with a water ring. The temperature of each section of the screw is: 160～175℃ in the upper feeding section, 180～190℃ in the conveying section, 195～210℃ in the melting section, 190～200℃ in the upper and lower connecting section, and 180～200 in the lower stage. 185℃, head 170～180℃.
优选的，所述步骤(2)中的熔融挤出造粒工艺还可为以下步骤替代：将原料通过自动失重计量称加入双螺杆挤出机中进行熔融挤出、水冷拉条切粒，随后甩干、沸腾干燥；其中所述双螺杆挤出机长径比为44:1，双螺杆各段温度为：加料段160～175℃，输送段180～190℃，熔融段195～210℃，机头190～200℃。Preferably, the melt extrusion granulation process in step (2) can also be replaced by the following steps: adding raw materials into a twin-screw extruder through automatic weight loss metering for melt extrusion, water-cooled stranding and pelletizing, and then Spin drying and boiling drying; wherein the length to diameter ratio of the twin-screw extruder is 44:1, the temperature of each section of the twin-screw is: 160-175℃ in the feeding section, 180-190℃ in the conveying section, and 195-210℃ in the melting section. The machine head is 190～200℃.
本发明提供了一种简单易行的阻燃TPE护套料的制备方法，其中各步骤中搅拌速率和搅拌时间如此设定的原因是只有在该搅拌速率和搅拌时间的范围内才能既达到优良的分散效果，又不会浪费多余的动力能源；并且熔融挤出造粒阶段的工艺参数选取是发明人经过创造性试验而得，通过选取恰当的工艺参数及结合合适的原料配比才能最终制备得到性能优异的阻燃TPE护套料。The present invention provides a simple and easy method for preparing a flame-retardant TPE sheath material. The reason why the stirring rate and the stirring time in each step are set in this way is that only within the range of the stirring rate and the stirring time can the excellent The dispersing effect is not wasteful of excess power and energy; and the process parameters of the melt extrusion granulation stage are selected by the inventor through creative experiments, and the final preparation can be obtained by selecting appropriate process parameters and combining appropriate raw material ratios. Flame-retardant TPE jacket material with excellent performance.
本发明还提供了上述阻燃TPE护套料在新能源电动汽车充电桩电缆中的应用。The invention also provides the application of the above-mentioned flame-retardant TPE sheath material in the charging pile cable of a new energy electric vehicle.
经由上述的技术方案可知，与现有技术相比，本发明公开提供了一种阻燃TPE护套料及其制备方法与应用，与现有技术相比，本发明具有如下优点:According to the above technical solutions, compared with the prior art, the present disclosure provides a flame-retardant TPE sheath material and its preparation method and application. Compared with the prior art, the present invention has the following advantages:
首先，本发明提供的新能源电动汽车充电桩电缆用耐刮擦、耐析出TPE材料，是以甄选的热塑性弹性体SEBS、热塑性弹性体POE和聚丙烯共混改性所得的聚烯烃为基料，恰当地添加了一定量的膨胀型次磷酸铝类有机阻燃剂和阻燃协效剂，并结合使用特定的加工助剂复合而成，本发明公开的原料配方实现了低填充量下的高效复合，具有优良的物理机械性能、耐刮擦和耐析出性能。First of all, the scratch-resistant and precipitation-resistant TPE material for charging pile cables of new energy electric vehicles provided by the present invention is based on selected thermoplastic elastomer SEBS, thermoplastic elastomer POE and polypropylene blend modified polyolefin as the base material , A certain amount of intumescent aluminum hypophosphite organic flame retardant and flame retardant synergist are appropriately added, and combined with specific processing aids. The raw material formula disclosed in the present invention achieves low filling content. Efficient compounding, with excellent physical and mechanical properties, scratch resistance and precipitation resistance.
此外，通过本发明产品挤制成的电线或电缆，0.40mm厚度的薄壁绝缘可通过VW-1的电线耐燃要求，不仅解决了析出和燃烧滴落问题，而且燃烧透光率达到85％以上，该发明产品能够更好的适用于新能源电动汽车充电桩电缆用料。In addition, the wire or cable extruded by the product of the present invention can pass the VW-1 wire flame resistance requirement of 0.40mm thick thin-walled insulation, which not only solves the problem of precipitation and combustion dripping, but also has a combustion light transmittance of more than 85% , The invented product can be better suitable for new energy electric vehicle charging pile cable materials.
另外，本发明所提供的新能源电动汽车充电桩电缆用环保TPE材料，环保符合欧盟RoHS要求和满足欧盟标准EN50620要求，适应于全球环保局势。In addition, the environmental protection TPE material for charging pile cables of new energy electric vehicles provided by the present invention meets the requirements of EU RoHS and meets the requirements of EU standard EN50620, and adapts to the global environmental protection situation.
最后，本发明公开制备的阻燃TPE护套料与现有技术相比，不仅具有优越的阻燃性和高机械性，而且耐刮擦、耐析出，其挤出速度可达150-200m/min，并且材料密度低，可重复加工利用，既环境友好又经济，适于市面推广与应用。Finally, compared with the prior art, the flame-retardant TPE sheath material prepared by the present invention not only has superior flame retardancy and high mechanical properties, but also has scratch resistance and precipitation resistance, and its extrusion speed can reach 150-200m/ min, and the material density is low, it can be re-processed and utilized, which is environmentally friendly and economical, and is suitable for market promotion and application.
具体实施方式Detailed ways
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following describes the technical solutions in the embodiments of the present invention clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
本发明实施例公开了一种阻燃TPE护套料及其制备方法与应用，通过本发明制备的阻燃TPE护套料具有优异的阻燃性和高机械性，且耐刮擦、耐析出，可有效解决现有无卤阻燃TPE护套料存在的阻燃性与物理机械性能之间的矛盾，能更好的用作新能源电动汽车充电桩电缆用料，极具市场应用与推广价值。The embodiment of the present invention discloses a flame-retardant TPE sheath material and its preparation method and application. The flame-retardant TPE sheath material prepared by the present invention has excellent flame retardancy and high mechanical properties, and is resistant to scratches and precipitation. It can effectively solve the contradiction between flame retardancy and physical and mechanical properties of existing halogen-free flame retardant TPE sheath materials, and can be better used as materials for charging pile cables for new energy electric vehicles, which has great market application and promotion value .
为更好地理解本发明，下面通过以下实施例对本发明作进一步具体的阐述，但不可理解为对本发明的限定，对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整，也视为落在本发明的保护范围内。In order to better understand the present invention, the following examples will further illustrate the present invention in detail, but it should not be construed as a limitation of the present invention. For those skilled in the art, some non-essential improvements and adjustments made based on the above-mentioned content of the invention, It is also deemed to fall within the protection scope of the present invention.
本发明公开了一种阻燃TPE护套料，按重量份数计，由以下原料配比制成：SEBS 25-30份、POE 8-12份、聚丙烯8-12份、有机阻燃剂20-30份、阻燃协效剂5-10份、耐刮擦剂3-5份、抗氧化剂0.1-0.3份、填充油10-15份、加工助剂1-3份、去离子水余量。The invention discloses a flame-retardant TPE sheath material, which is calculated in parts by weight and is made of the following raw materials in proportions: 25-30 parts of SEBS, 8-12 parts of POE, 8-12 parts of polypropylene, and organic flame retardant 20-30 parts, flame retardant synergist 5-10 parts, scratch-resistant agent 3-5 parts, antioxidant 0.1-0.3 parts, extender oil 10-15 parts, processing aids 1-3 parts, deionized water the amount.
为了进一步实现本发明的技术效果，聚丙烯的熔融指数为3～8g/min，且热塑性弹性体至少为乙烯-辛烯共聚物和/或乙烯丙烯酸共聚物中的一种。In order to further realize the technical effect of the present invention, the melt index of polypropylene is 3-8 g/min, and the thermoplastic elastomer is at least one of ethylene-octene copolymer and/or ethylene acrylic acid copolymer.
为了进一步实现本发明的技术效果，有机阻燃剂为次磷酸铝、二乙基次磷酸铝、季戊四醇多聚磷酸酯三聚氰胺盐中的一种或两种组合。In order to further realize the technical effect of the present invention, the organic flame retardant is one or a combination of aluminum hypophosphite, diethyl aluminum hypophosphite, and pentaerythritol polyphosphate melamine salt.
为了进一步实现本发明的技术效果，阻燃协效剂为三聚氰胺氰尿酸酯、纳米二氧化硅、纳米碳酸钙中的一种或两种组合。In order to further realize the technical effect of the present invention, the flame retardant synergist is one or a combination of melamine cyanurate, nano silica, and nano calcium carbonate.
为了进一步实现本发明的技术效果，耐刮擦剂为滑石粉和/或滑石粉聚烯烃共混耐刮擦母粒；抗氧化剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、三[2,4-二叔丁基苯基]亚磷酸酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、N,N'-双[β-(3,5-二叔丁基-4-羟基苯基)丙酰]肼中的一种或两种组合。In order to further realize the technical effect of the present invention, the anti-scratch agent is talc and/or talc polyolefin blended anti-scratch masterbatch; the antioxidant is tetra[β-(3,5-di-tert-butyl-4- (Hydroxyphenyl) propionic acid) pentaerythritol ester, tris[2,4-di-tert-butylphenyl] phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate One or a combination of carbon alcohol ester and N,N'-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.
为了进一步实现本发明的技术效果，填充油选自石蜡基白油、环烷基白油中的一种；所述加工助剂至少为二氧化钛、EBS、硅酮母料中的一种。In order to further realize the technical effect of the present invention, the extender oil is selected from one of paraffin-based white oil and naphthenic white oil; the processing aid is at least one of titanium dioxide, EBS, and silicone masterbatch.
本发明还公开一种阻燃TPE护套料的制备方法，具体包括如下步骤：The invention also discloses a preparation method of the flame-retardant TPE sheath material, which specifically includes the following steps:
(1)将SEBS和填充油按照配方比例低速搅拌1～3min后，静置待用；(1) Stir the SEBS and filler oil at low speed according to the formula ratio for 1 to 3 minutes, and then let it stand for use;
(2)将原料POE、聚丙烯、有机阻燃剂、阻燃协效剂、耐刮擦剂、抗氧化剂和加工助剂分别加入料仓中，并按照原料组分配比进行程序设定，自动配料、混合后熔融挤出造粒，最终制得阻燃TPE护套料。(2) Add the raw materials POE, polypropylene, organic flame retardant, flame retardant synergist, scratch resistant agent, antioxidant and processing aid to the silo, and set the program according to the raw material composition ratio, automatically After ingredients and mixing, melt extrusion granulation, and finally prepare flame-retardant TPE sheath material.
为了进一步实现本发明的技术效果，步骤(2)中的熔融挤出造粒工艺具体为：将原料通过自动失重计量秤加入双螺杆挤出机中进行熔融混合，再经单螺杆挤出、水环切粒，随后甩干、沸腾干燥；其中螺杆各段温度为：上阶加料段160～175℃，输送段180～190℃，熔融段195～210℃，上下阶连接段190～200℃，下阶段180～185℃，机头170～180℃。In order to further realize the technical effect of the present invention, the melt extrusion granulation process in step (2) specifically includes: adding the raw materials into a twin-screw extruder through an automatic weightlessness metering scale for melting and mixing, and then extruding through a single screw, water Ring pelletizing, followed by spin drying and boiling drying; the temperature of each section of the screw is: the upper feeding section is 160～175℃, the conveying section is 180～190℃, the melting section is 195～210℃, and the upper and lower connecting sections are 190～200℃. The next stage is 180～185℃, and the machine head is 170～180℃.
为了进一步实现本发明的技术效果，步骤(2)中的熔融挤出造粒工艺还可为以下步骤替代：将原料通过自动失重计量称加入双螺杆挤出机中进行熔融挤出、水冷拉条切粒，随后甩干、沸腾干燥；其中所述双螺杆挤出机长径 比为44:1，双螺杆各段温度为：加料段160～175℃，输送段180～190℃，熔融段195～210℃，机头190～200℃。In order to further realize the technical effect of the present invention, the melt extrusion granulation process in step (2) can also be replaced by the following steps: the raw materials are added to the twin-screw extruder through automatic weight loss metering for melt extrusion and water-cooled drawing. Cut into pellets, then spin and boil and dry; wherein the length to diameter ratio of the twin-screw extruder is 44:1, the temperature of each section of the twin-screw is: the feeding section is 160～175℃, the conveying section is 180～190℃, and the melting section is 195 ～210℃, head 190～200℃.
下面，将结合具体实施例，对本发明的技术方案进行进一步的说明。In the following, the technical solution of the present invention will be further described in conjunction with specific embodiments.
实施例1：Example 1:
一种阻燃TPE护套料，按重量份数计，由以下原料配比制成：SEBS 30份、POE 10份、聚丙烯10份、次磷酸铝30份、三聚氰胺氰尿酸酯5份、纳米二氧化硅5份、耐刮擦剂5份、抗氧化剂0.3份、填充油10份、EBS 0.5份、去离子水余量。A flame-retardant TPE sheath material, calculated in parts by weight, made of the following raw materials: 30 parts of SEBS, 10 parts of POE, 10 parts of polypropylene, 30 parts of aluminum hypophosphite, 5 parts of melamine cyanurate, 5 parts of nano-silica, 5 parts of scratch-resistant agent, 0.3 parts of antioxidant, 10 parts of filler oil, 0.5 parts of EBS, the balance of deionized water.
实施例2：Example 2:
一种阻燃TPE护套料，按重量份数计，由以下原料配比制成：SEBS 30份、POE 10份、聚丙烯10份、次磷酸铝20份、二乙基次膦酸铝10份、三聚氰胺氰尿酸酯7份、纳米碳酸钙3份、耐刮擦剂5份、抗氧化剂0.3份、填充油10份、硅酮2份、去离子水余量。A flame-retardant TPE sheath material, calculated in parts by weight, made of the following raw materials: 30 parts of SEBS, 10 parts of POE, 10 parts of polypropylene, 20 parts of aluminum hypophosphite, and 10 parts of aluminum diethylphosphinate Parts, 7 parts of melamine cyanurate, 3 parts of nano calcium carbonate, 5 parts of scratch-resistant agent, 0.3 parts of antioxidant, 10 parts of filler oil, 2 parts of silicone, the balance of deionized water.
实施例3：Example 3:
一种阻燃TPE护套料，按重量份数计，由以下原料配比制成：SEBS 30份、POE 10份、聚丙烯10份、季戊四醇多聚磷酸酯三聚氰胺盐25份、纳米二氧化硅10份、纳米碳酸钙5份、耐刮擦剂5份、抗氧化剂0.3份、填充油10份、硅酮2份、去离子水余量。A flame-retardant TPE sheath material, based on parts by weight, made of the following raw materials: SEBS 30 parts, POE 10 parts, polypropylene 10 parts, pentaerythritol polyphosphate melamine salt 25 parts, nano silica 10 parts, 5 parts of nano calcium carbonate, 5 parts of anti-scratch agent, 0.3 parts of antioxidant, 10 parts of filler oil, 2 parts of silicone, the balance of deionized water.
首先，对本发明实施例1～3公开的的原料通过相同的制备方法制备阻燃TPE护套料，具体实施工艺如下所述：First, the raw materials disclosed in Examples 1 to 3 of the present invention are prepared by the same preparation method as a flame-retardant TPE sheath material. The specific implementation process is as follows:
1)将SEBS和环烷油按照配方比例投入低速搅拌机中搅拌1～3min，静置4h后待用，使SEBS充分充油溶胀；1) Put the SEBS and naphthenic oil into a low-speed mixer according to the formula ratio and stir for 1 to 3 minutes, and let it stand for 4 hours before use, so that the SEBS is fully filled with oil and swelled;
2)将各原料加入相应料仓，按照组份配比的质量份数进行程序设定，自动失重计量电子秤加入双螺杆挤出机中进行熔融混合，再经单螺杆挤出造粒，其中螺杆各段温度为：上阶加料段160～175℃，输送段180～190℃，熔融段 195～210℃，上下阶连接段190～200℃，下阶段180～185℃，机头170～180℃；随后水环切粒，离心甩干机甩干，最后沸腾干燥，制得新能源电动汽车充电桩电缆用环保TPE材料。2) Put each raw material into the corresponding silo, set the program according to the mass parts of the component ratio, add the automatic weightless metering electronic scale to the twin-screw extruder for melting and mixing, and then granulate by single-screw extrusion. The temperature of each section of the screw is: upper feeding section 160～175℃, conveying section 180～190℃, melting section 195～210℃, upper and lower connecting section 190～200℃, lower stage 180～185℃, head 170～180 ℃; Afterwards, water ring pelletizing, centrifugal drying machine to dry, and finally boiling and drying, the environmental protection TPE material for charging pile cables of new energy electric vehicles is prepared.
或步骤(2)还可用以下步骤替代：Or step (2) can also be replaced by the following steps:
由自动失重计量称加入双螺杆挤出机中进行熔融挤出，水冷拉条切粒，随后甩干、沸腾干燥制得新能源电动汽车充电桩电缆用环保TPE材料。其中，双螺杆挤出机长径比为44:1，双螺杆各段温度为：加料段160～175℃，输送段180～190℃，熔融段195～210℃，机头190～200℃。The automatic weight-loss metering is added to a twin-screw extruder for melt extrusion, water-cooled stretched strips and pelletized, followed by spin drying and boiling drying to prepare environmentally-friendly TPE materials for charging pile cables for new energy electric vehicles. Among them, the length-diameter ratio of the twin-screw extruder is 44:1, and the temperature of each section of the twin-screw is: the feeding section is 160-175°C, the conveying section is 180-190°C, the melting section is 195-210°C, and the die head is 190-200°C.
将实施例1～3公开的原料分别通过上述制备方法得到的TPE电缆料进行性能检测，测得的各项技术指标参见下表。The raw materials disclosed in Examples 1 to 3 were respectively tested for performance of the TPE cable material obtained by the above preparation method, and the measured technical indicators are shown in the following table.
表1Table 1
Figure PCTCN2020113336-appb-000001
Figure PCTCN2020113336-appb-000001
通过对比表1中实施例1、2和实施例3性能测定结果可知，各组分配比的改变会对所得TPE材料的物理机械性能和阻燃性能等产生显著影响。By comparing the performance measurement results of Examples 1, 2 and 3 in Table 1, it can be seen that the change of the distribution ratio of each group will have a significant impact on the physical and mechanical properties and flame retardancy of the obtained TPE material.
为了进一步验证本发明制备得到的阻燃TPE护套料在新能源电动汽车充电桩电缆中具有优异的性质，发明人将实施例1和实施例2公开制备的阻燃 TPE护套料用于充电桩电缆中，并对成缆后的产品进行性能测定，具体测定结果如下表2所示：In order to further verify that the flame-retardant TPE sheath material prepared by the present invention has excellent properties in new energy electric vehicle charging pile cables, the inventors used the flame-retardant TPE sheath materials prepared in Example 1 and Example 2 for charging In the pile cable, the performance of the cabled product is measured, and the specific measurement results are shown in Table 2 below:
表2Table 2
Figure PCTCN2020113336-appb-000002
Figure PCTCN2020113336-appb-000002
综合以上测试结果分析可知，因表面析出和耐刮擦，主要是通过个人现场操作，肉眼观察。而产品1和产品2的线缆护套表面均无白色雾状析出，且用手指刮擦无明显白色刮痕。以及成缆后产品的拉伸强度要比试验料的低，伸率会高一点。Based on the analysis of the above test results, it can be seen that due to the surface precipitation and scratch resistance, it is mainly through personal on-site operation and naked eye observation. However, there is no white misty precipitation on the surface of the cable sheath of product 1 and product 2, and there is no obvious white scratch when scratched with fingers. And the tensile strength of the cabled product is lower than that of the test material, and the elongation rate will be higher.
综上，本发明开发和研制的TPE护套料具有阻燃性能高、耐刮擦、无析出，机械性能好，且耐应力疲劳、耐气候老化等优异性能，可以有效解决现有无卤阻燃TPE护套料存在的阻燃性与物理机械性能之间的矛盾，能更好的用作新能源电动汽车充电桩电缆用料，极具市场应用与推广价值。In summary, the TPE sheath material developed and developed by the present invention has high flame retardancy, scratch resistance, no precipitation, good mechanical properties, and excellent performance such as stress fatigue resistance and weathering resistance, which can effectively solve the existing halogen-free resistance. The contradiction between the flame retardancy and the physical and mechanical properties of the flame-retardant TPE sheath material can be better used as a material for charging pile cables for new energy electric vehicles, which has great market application and promotion value.
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。The various embodiments in this specification are described in a progressive manner. Each embodiment focuses on the differences from other embodiments, and the same or similar parts between the various embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the description of the method part.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下， 在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (10)

  1. 一种阻燃TPE护套料，其特征在于，按重量份数计，由以下原料配比制成：SEBS 25-30份、POE 8-12份、聚丙烯8-12份、有机阻燃剂20-30份、阻燃协效剂5-10份、耐刮擦剂3-5份、抗氧化剂0.1-0.3份、填充油10-15份、加工助剂1-3份、去离子水余量。A flame-retardant TPE sheath material, which is characterized in that it is made from the following raw materials in parts by weight: 25-30 parts of SEBS, 8-12 parts of POE, 8-12 parts of polypropylene, and organic flame retardant 20-30 parts, flame retardant synergist 5-10 parts, scratch-resistant agent 3-5 parts, antioxidant 0.1-0.3 parts, extender oil 10-15 parts, processing aids 1-3 parts, deionized water the amount.
  2. 根据权利要求1所述的一种阻燃TPE护套料，其特征在于，所述聚丙烯的熔融指数为3～8g/min，且所述热塑性弹性体至少为乙烯-辛烯共聚物和/或乙烯丙烯酸共聚物中的一种。The flame-retardant TPE sheath material according to claim 1, wherein the melt index of the polypropylene is 3-8 g/min, and the thermoplastic elastomer is at least an ethylene-octene copolymer and/ Or one of ethylene acrylic acid copolymers.
  3. 根据权利要求1所述的一种阻燃TPE护套料，其特征在于，所述有机阻燃剂为次磷酸铝、二乙基次磷酸铝、季戊四醇多聚磷酸酯三聚氰胺盐中的一种或两种组合。A flame-retardant TPE sheath material according to claim 1, wherein the organic flame retardant is one of aluminum hypophosphite, diethyl aluminum hypophosphite, pentaerythritol polyphosphate melamine salt or Two combinations.
  4. 根据权利要求1所述的一种阻燃TPE护套料，其特征在于，所述阻燃协效剂为三聚氰胺氰尿酸酯、纳米二氧化硅、纳米碳酸钙中的一种或两种组合。The flame-retardant TPE sheath material according to claim 1, wherein the flame-retardant synergist is one or a combination of melamine cyanurate, nano silica, and nano calcium carbonate .
  5. 根据权利要求1所述的一种阻燃TPE护套料，其特征在于，所述耐刮擦剂为滑石粉和/或滑石粉聚烯烃共混耐刮擦母粒；所述抗氧化剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、三[2,4-二叔丁基苯基]亚磷酸酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、N,N'-双[β-(3,5-二叔丁基-4-羟基苯基)丙酰]肼中的一种或两种组合。A flame-retardant TPE sheath material according to claim 1, wherein the scratch resistant agent is talc and/or talc polyolefin blended scratch resistant masterbatch; the antioxidant is four [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, tris[2,4-di-tert-butylphenyl] phosphite, β-(3,5-di Tert-butyl-4-hydroxyphenyl) octadecyl propionate, N,N'-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine One or two combinations.
  6. 根据权利要求1所述的一种阻燃TPE护套料，其特征在于，所述填充油选自石蜡基白油、环烷基白油中的一种；所述加工助剂至少为二氧化钛、EBS、硅酮母料中的一种。The flame-retardant TPE sheath material according to claim 1, wherein the extender oil is selected from one of paraffin-based white oil and naphthenic white oil; and the processing aid is at least titanium dioxide, One of EBS, silicone masterbatch.
  7. 如权利要求1所述一种阻燃TPE护套料的制备方法，其特征在于，所述方法具体包括如下步骤：The method for preparing a flame-retardant TPE sheath material according to claim 1, wherein the method specifically includes the following steps:
    (1)将SEBS和填充油按照配方比例低速搅拌1～3min后，静置待用；(1) Stir the SEBS and filler oil at low speed according to the formula ratio for 1 to 3 minutes, and then let it stand for use;
    (2)将原料POE、聚丙烯、有机阻燃剂、阻燃协效剂、耐刮擦剂、抗氧化剂和加工助剂分别加入料仓中，并按照原料组分配比进行程序设定，自动配料、混合后熔融挤出造粒，最终制得阻燃TPE护套料。(2) Add the raw materials POE, polypropylene, organic flame retardant, flame retardant synergist, scratch resistant agent, antioxidant and processing aid to the silo, and set the program according to the raw material composition ratio, automatically After ingredients and mixing, melt extrusion granulation, and finally prepare flame-retardant TPE sheath material.
  8. 根据权利要求7所述的一种阻燃TPE护套料的制备方法，其特征在于，所述步骤(2)中的熔融挤出造粒工艺具体为：将原料通过自动失重计量秤加入双螺杆挤出机中进行熔融混合，再经单螺杆挤出、水环切粒，随后甩干、沸腾干燥；其中螺杆各段温度为：上阶加料段160～175℃，输送段180～190℃，熔融段195～210℃，上下阶连接段190～200℃，下阶段180～185℃，机头170～180℃。The method for preparing a flame-retardant TPE sheath material according to claim 7, wherein the melt extrusion granulation process in the step (2) specifically includes: adding the raw material to the twin screw through an automatic weight loss metering scale The extruder is melted and mixed, then extruded by a single screw, pelletized by a water ring, then spin-dried, and boil-dried; the temperature of each section of the screw is: the upper feeding section is 160～175℃, and the conveying section is 180～190℃. The melting section is 195～210℃, the upper and lower stage connecting section is 190～200℃, the lower stage is 180～185℃, and the head is 170～180℃.
  9. 根据权利要求8所述的一种阻燃TPE护套料的制备方法，其特征在于，所述步骤(2)中的熔融挤出造粒工艺还可为以下步骤替代：将原料通过自动失重计量称加入双螺杆挤出机中进行熔融挤出、水冷拉条切粒，随后甩干、沸腾干燥；其中所述双螺杆挤出机长径比为44:1，双螺杆各段温度为：加料段160～175℃，输送段180～190℃，熔融段195～210℃，机头190～200℃。The method for preparing a flame-retardant TPE sheath material according to claim 8, wherein the melt extrusion granulation process in the step (2) can also be replaced by the following step: the raw materials are measured by automatic weight loss Weigh into the twin-screw extruder for melt extrusion, water-cooled stranding and pelletizing, followed by spin-drying and boiling drying; wherein the length-to-diameter ratio of the twin-screw extruder is 44:1, and the temperature of each section of the twin-screw is: feeding The section is 160～175℃, the conveying section is 180～190℃, the melting section is 195～210℃, and the head is 190～200℃.
  10. 一种如权利要求1所述阻燃TPE护套料或如权利要求7所述方法制备的阻燃TPE护套料在新能源电动汽车充电桩电缆中的应用。An application of the flame-retardant TPE sheath material according to claim 1 or the flame-retardant TPE sheath material prepared by the method according to claim 7 in a new energy electric vehicle charging pile cable.
PCT/CN2020/113336 2019-12-11 2020-09-03 Flame-retardant tpe sheath material, preparation method therefor and application thereof WO2021114758A1 (en)

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