CN108239315B - Halogen-free thermoplastic elastomer cable material for electric vehicle charging pile cable and preparation method thereof - Google Patents
Halogen-free thermoplastic elastomer cable material for electric vehicle charging pile cable and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
- H01B3/448—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 other vinyl compounds
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- C08L2203/00—Applications
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- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- 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
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention relates to a halogen-free thermoplastic elastomer cable material, which comprises the following raw material components in parts by weight: 20-40 parts by weight of elastomer resin; 3-25 parts by weight of polypropylene; 10-40 parts by weight of polyolefin resin; 10-25 parts by weight of a compatilizer; 20-40 parts of a halogen-free flame retardant; 0.5-2.0 parts by weight of an antioxidant; 10 parts of a processing aid; 5-20 parts by weight of a lubricant. The halogen-free thermoplastic elastomer cable material is provided by the invention. The halogen-free flame-retardant cable does not contain halogen, heavy metal elements and the like, is harmless to the environment, can be recycled, has good flame retardant property and mechanical property, and is suitable for being used for electric automobile charging pile cables.
Description
Technical Field
The invention relates to a cable material, in particular to a thermoplastic elastomer cable material and a preparation method thereof.
Background
Hydrogenated polystyrene- (ethylene butylene random copolymer) -polystyrene triblock copolymer (SEBS) is a thermoplastic elastomer with excellent performance, has excellent performances of weather resistance, ageing resistance, heat resistance, compression deformation resistance, recyclability and the like, and is widely applied to the fields of electric cables, automobile manufacturing, buildings and the like. But the inflammability restricts the wide application of the SEBS, so that the excellent flame retardant property can be achieved under the condition of less using amount of the flame retardant by utilizing the mechanism of the expansion flame retardance of the novel halogen-free expansion type flame retardant after combustion, and the excellent mechanical property and the flexibility of the SEBS are kept.
The traditional PVC and bromine-containing flame-retardant wire and cable and the electronic connector generate a large amount of toxic dense smoke and corrosive gas due to the occurrence of carcinogen dioxin and the generation of a large amount of toxic dense smoke and corrosive gas in the combustion process, so that the suffocation of personnel on the fire scene is accelerated, and the rescue difficulty of rescue personnel is increased; and the released corrosive gas can corrode and scrap electrical appliances at and near the fire scene; in addition, halogen-based flame retardants accumulate toxicity and produce carcinogenic substances during production, transportation, storage, use, and recycling of waste products. All of the materials make the market urgently need a novel material which is environment-friendly, has low smoke amount, is free from halogen and corrosive gas and can reach the UL-94V-0 flame retardant level.
Energy and environmental protection problems become the most prominent problems in the development of the world at present and are one of the most important factors influencing the sustainable development strategy of China. In recent years, with the increasingly reduced international energy resources and the emerging of the problem of environmental pollution caused by automobile exhaust, the development of the traditional automobile is hindered, and instead, the development of new energy automobiles is more and more emphasized. At present, new energy automobiles are highly concerned by various countries, and governments in China give great support. The method has important practical significance for the development of new energy automobiles by analyzing and researching the development environment of new energy automobiles in China.
Meanwhile, in recent years, the global environmental protection consciousness is increased, the wire and cable industry has stricter restrictions on the use of halogen-containing materials, and the european union has formulated a directive (ROHS) on the prohibition of the use of certain harmful substances in electronic and electrical equipment in 2002. Meanwhile, in the beginning of 2004, the national information industry ministry formulated the pollution prevention and control management method of electronic information products. Electronic products entering China are regulated not to contain harmful substances such as lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers and the like, so that the research and development of the halogen-free flame-retardant cable material without the above six harmful substances have great significance, the consumption of new energy automobile industry and consumer electronic products in the market is continuously increased at present, and a great space is provided for the development of elastomer cable materials.
Chinese patent 200610115439.4 discloses a method for producing a halogen-free flame-retardant thermoplastic elastomer mixture containing 40 to 80 parts by weight of rubber, (B) 60 to 20 parts by weight of crystalline polyolefin resin, and (C) 40 to 250 parts by weight of metal hydroxide per 100 parts by weight of the total of (a) and (B), wherein the rubber is silane-crosslinked. The non-halogen flame retardant thermoplastic elastomer mixture has disadvantages in that: 1. in order to keep the hardness of the mixture relatively low, the amount of the inorganic hydroxide flame retardant added to the mixture is not high, but the flame retardant property is not good, and the mixture cannot be used for wires and cables which have high flame retardant requirements. 2. In order to improve the mechanical properties of the mixture, the mixture is silane-crosslinked, cannot be recycled, and once the material is discarded, the environment is polluted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a halogen-free thermoplastic elastomer cable material which is used for overcoming the defects that the cable material is not environment-friendly and can not be recycled, and the flame retardant property and the mechanical property are not suitable for being used for electric automobile charging piles in the prior art.
To achieve the above and other objects, the present application includes the following technical solutions.
The invention discloses a halogen-free thermoplastic elastomer cable material, which comprises the following raw material components in parts by weight:
preferably, the elastomer resin is a styrene-ethylene-butylene-styrene block copolymer (SEBS for short). Further preferably, the elastomer-based resin is SEBS resin of 2315 model in angni italy or SEBS resin of G1651 model in kraton usa.
Preferably, the polypropylene is a homopolypropylene.
Preferably, the polyolefin resin is a resin prepared by copolymerizing ethylene and any two selected from the group consisting of propylene, butene, hexene, and octene. Such as ethylene copolymerized with butene and octene resins. Preferably, the polyolefin resin is one or more selected from DF810 resin in TAFMER series, 5062 resin in Exact series, DF640 resin in TAFMER series, and DF810 resin in AFMER series, 5062 resin in Exact series and DF640 resin in TAFMER series.
Preferably, the compatilizer is one or more of ethylene-octene copolymer grafted maleic anhydride copolymer, ethylene-propylene copolymer grafted maleic anhydride copolymer and SEBS grafted maleic anhydride copolymer. More preferably, the melt index of the compatilizer at 190 ℃ multiplied by 2.16kg is 1-10 g/10 min. Preferably, the grafting rate in the compatilizer is 1.2-1.5%.
Preferably, the halogen-free flame retardant is a phosphorus-nitrogen flame retardant, and the mass fraction of phosphorus is 5-15% and the mass fraction of nitrogen is 20-40% based on the total weight of the phosphorus-nitrogen flame retardant. Preferably, the average particle size of the flame retardant is 10 μm. The flame retardant is an intumescent flame retardant and has a good flame retardant effect. More preferably, the phosphorus-nitrogen flame retardant is selected from: the phosphorus-nitrogen flame retardant PNA200 of Hangzhou Jie Si chemical industry and the thermoplastic elastomer halogen-free flame retardant SIFR-1 of Jiangsu Siwei chemical industry Co.
Preferably, the antioxidant is a combination of antioxidant 1010 and antioxidant 168, wherein the weight percentage of the antioxidant 1010 is 40-60%. The antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the antioxidant 168 is tris (2, 4-di-tert-butylphenyl) phosphite.
Preferably, the processing aid is selected from one or more of stearic acid, calcium stearate, magnesium stearate, polyethylene wax, paraffin, silicone processing aid, and silane coupling agent. Preferably, the processing aid is a combination of calcium stearate, polyethylene wax, silane coupling agent, more preferably, the type of silane coupling agent is selected from one or more of silane KH173 and KH 172.
Preferably, the lubricant is aromatic oil,Naphthenic oil and paraffin oil. Preferably a combination of white oil and silicone oil. More preferably, the white oil has a kinematic viscosity at 40 ℃ of 15 to 22(cSt), a flash point of 200 ℃ or higher, and a specific gravity of 0.8283g/cm3. More preferably, the silicone oil has a viscosity ranging from 45 to 50(cSt), a density of 0.963, a melting point of-50 ℃, a refractive index of 1.403 to 1.406, and a flash point of 300 ℃.
The invention also provides a preparation method of the halogen-free thermoplastic elastomer TPE cable material, which comprises the following steps:
adding elastomer resin, polypropylene, polyolefin resin, compatilizer, halogen-free flame retardant, antioxidant, processing aid and lubricant into a mixer for mixing; and feeding the mixture into a double-screw extruder for extrusion granulation, and drying the granules in a hot air dryer to obtain the halogen-free thermoplastic elastomer TPE cable material.
Preferably, the twin screw extruder temperature is: the feeding section is 120-130 ℃, the melting section is 175-185 ℃, the melt conveying section is 180-190 ℃, the mixing section is 190-210 ℃, the homogenizing section is 185-195 ℃ and the machine head metering section is 185-195 ℃.
The halogen-free thermoplastic elastomer cable material is provided by the invention. The halogen-free flame-retardant cable does not contain halogen, heavy metal elements and the like, is harmless to the environment, can be recycled, has good flame retardant property and mechanical property, and is suitable for being used for electric automobile charging pile cables.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
Embodiments 1 to 6 disclose a preparation method of a halogen-free thermoplastic elastomer cable material, comprising the following steps of mixing 20 to 40 parts by weight of elastomer resin; 3-25 parts by weight of polypropylene; 10-40 parts by weight of polyolefin resin; 10-25 parts by weight of a compatilizer; 20-40 parts by weight of a halogen-free flame retardant; 0.5-2.0 parts by weight of an antioxidant; 2-10 parts of a processing aid; mixing 5-20 parts by weight of a lubricant in a high-speed mixer; and after mixing for 3-5 minutes, forcibly feeding the mixture into a double-screw extruder for extrusion granulation, and drying the granules in a hot air dryer to obtain the halogen-free thermoplastic elastomer TPE cable material.
Among them, the SEBS resin in examples 1 to 3 was eini 2315 in italy, and the SEBS resin in examples 4 to 6 was G1651 in cotem, usa.
Wherein the polypropylene in examples 1-6 is a homo-type polypropylene
Wherein, the polyolefin resin in the embodiments 1 to 2 is DF810 resin in TAFMER series and 5062 resin in Exact series, and the mixture ratio is 50: 50; the polyolefin resin in example 3 is DF640 resin and DF810 in TAFMER series, the ratio is 80: 20; the polyolefin resin of example 4 was 5062 resin of Exact series; the polyolefin resin in examples 5-6 was DF640 resin in TAFMER series.
Wherein, the compatilizer in examples 1 to 2 is an ethylene-octene copolymer grafted maleic anhydride copolymer, the compatilizer in examples 3 to 4 is an ethylene-propylene copolymer grafted maleic anhydride copolymer, and the compatilizer in examples 5 to 6 is an SEBS grafted maleic anhydride copolymer. In examples 1 to 6, the melt index of the compatibilizer at 190 ℃ under 2.16kg was 1 to 10g/10 min. The grafting rate in the compatilizer is 1.2-1.5%.
The halogen-free intumescent flame retardant in the embodiments 1 to 6 comprises 5 to 15 mass percent of phosphorus and 20 to 40 mass percent of nitrogen, based on the total weight of the phosphorus-nitrogen flame retardant, and the average particle size of the flame retardant is 10 μm.
Wherein, the antioxidants in the embodiments 1 to 2 are antioxidant 1010 and antioxidant 168, wherein the weight percentage of the antioxidant 1010 is 40%, and the weight percentage of the antioxidant 168 is 60%. The antioxidants of examples 3 to 4 were antioxidant 1010 and antioxidant 168, wherein the weight percentage of antioxidant 1010 was 50%, and the weight percentage of antioxidant 168 was 50%. The antioxidants of examples 5 to 6 were antioxidant 1010 and antioxidant 168, wherein the weight percentage of antioxidant 1010 was 60% and the weight percentage of antioxidant 168 was 40%.
The processing aids in examples 1 to 3 are calcium stearate and polyethylene wax. The mixing ratio was 1: 1. The processing aid in example 4 was calcium stearate, polyethylene wax and a silane coupling agent, mixed in a ratio of 1:1: 1. The processing aids in examples 5 to 6 were magnesium stearate and a silane coupling agent, mixed in a ratio of 1: 1.
Wherein the lubricants in examples 1-3 were paraffinic oils and the lubricants in examples 4-5 were naphthenic oils. The lubricant in example 6 was white oil and silicone oil, 20% by weight of silicone oil. Wherein the white oil has a kinematic viscosity of 15-22(cSt) at 40 deg.C, a flash point of 210 deg.C, and a specific gravity of 0.8283g/cm3. The viscosity range of the organic silicone oil is 45-50 (cSt), the density is 0.963, the melting point is-50 ℃, the refractive index is 1.403-1.406, and the flash point is 300 ℃.
The temperature of the double-screw extruder during the production of the materials is set as follows: the feeding section is 120-130 ℃, the melting section is 175-185 ℃, the melt conveying section is 180-190 ℃, the mixing section is 190-210 ℃, the homogenizing section is 185-195 ℃, and the head metering section is 185-195 ℃.
The results of the tests conducted in example 4 are shown in Table 1.
Table 1 results of testing the properties of the cable materials prepared in examples 1 to 6
From the data in table 1, it can be seen that: the halogen-free thermoplastic elastomer cable material prepared in the embodiment of the invention does not contain halogen, heavy metal elements and the like, is harmless to the environment, can be recycled, has good flame retardant property and mechanical property, and is suitable for being used for charging pile cables of electric automobiles.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (4)
1. The halogen-free thermoplastic elastomer cable material is characterized by comprising the following raw material components in parts by weight:
20-40 parts by weight of elastomer resin;
3-25 parts by weight of polypropylene;
10-40 parts by weight of polyolefin resin;
10-25 parts by weight of a compatilizer;
20-40 parts of a halogen-free flame retardant;
0.5-2.0 parts by weight of an antioxidant;
2-10 parts of a processing aid;
5-20 parts by weight of a lubricant;
the polyolefin resin is selected from one or more of DF810 resin in TAFMER series, 5062 resin in Exact series and DF640 resin in TAFMER series, the halogen-free flame retardant is a phosphorus-nitrogen flame retardant, and the phosphorus accounts for 5-15% of the total weight of the phosphorus-nitrogen flame retardant, and the nitrogen accounts for 20-40% of the total weight of the phosphorus-nitrogen flame retardant; the phosphorus-nitrogen flame retardant is selected from PNA200 or SIFR-1; the lubricant is a combination of white oil and organic silicone oil, wherein the white oil has a kinematic viscosity of 15-22 cSt at 40 ℃, a flash point of more than 200 ℃ and a specific gravity of 0.8283g/cm3(ii) a The viscosity range of the organic silicone oil is 45-50 cSt, and the density is highThe degree is 0.963 g/cm3The melting point is-50 ℃, the refractive index is 1.403-1.406, and the flash point is 300 ℃; the elastomer resin is a 2315 type or G1651 type styrene-ethylene-butylene-styrene block copolymer;
the compatilizer is one or more of ethylene-octene copolymer grafted maleic anhydride copolymer, ethylene-propylene copolymer grafted maleic anhydride copolymer and SEBS grafted maleic anhydride copolymer; the melt index of the compatilizer at 190 ℃ multiplied by 2.16kg is 1-10 g/10 min; the grafting rate in the compatilizer is 1.2-1.5%;
the processing aid is a combination of two or more selected from calcium stearate, polyethylene wax and a silane coupling agent.
2. The halogen-free thermoplastic elastomer cable material as claimed in claim 1, wherein the antioxidant is a combination of antioxidant 1010 and antioxidant 168, wherein the weight percentage of the antioxidant 1010 is 40-60%.
3. A method for preparing the halogen-free thermoplastic elastomer cable material as defined in any one of claims 1-2, comprising the following steps: adding elastomer resin, polypropylene, polyolefin resin, compatilizer, halogen-free flame retardant, antioxidant, processing aid and lubricant into a mixer for mixing; and feeding the mixture into a double-screw extruder for extrusion granulation, and drying the granules in a hot air dryer to obtain the halogen-free thermoplastic elastomer cable material.
4. The use of the halogen-free thermoplastic elastomer cable material according to any one of claims 1-2 as an electric vehicle charging pile cable.
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| CN109181122B (en) * | 2018-09-29 | 2021-04-06 | 中广核高新核材科技（苏州）有限公司 | Crosslinked elastomer cable material for high-voltage cable in vehicle, cable and preparation method of cable |
| CN110527237A (en) * | 2018-12-19 | 2019-12-03 | 上海凯波特种电缆料厂有限公司 | A kind of halogen-free flame-retardant thermoplastic elastomer protective cover material and preparation method thereof |
| CN110527236A (en) * | 2018-12-19 | 2019-12-03 | 上海凯波特种电缆料厂有限公司 | A kind of Halogen thermoplastic elastomer (TPE) Insulation Material and preparation method thereof |
| CN109851976B (en) * | 2019-01-25 | 2021-10-12 | 江西博硕电子有限公司 | Halogen-free modified TPE flame-retardant cable material and preparation method thereof |
| CN113549270A (en) * | 2021-08-11 | 2021-10-26 | 重庆科聚孚新材料有限责任公司 | High-toughness weather-resistant efficient halogen-free flame-retardant material for cables |
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| CN102295818A (en) * | 2010-06-24 | 2011-12-28 | 上海凯波特种电缆料厂有限公司 | Zero-halogen, low-smoke and flame-retardant TPE (Thermoplastic Elastomer) cable material and preparation method thereof |
| CN101955626A (en) * | 2010-10-12 | 2011-01-26 | 江苏安格特新材料科技有限公司 | Cable thermoplastic elastomer composition and preparation method thereof |
| CN103435955A (en) * | 2013-08-13 | 2013-12-11 | 东莞市安拓普塑胶聚合物科技有限公司 | Halogen-free flame retardant thermoplastic elastomer composite material and preparation method thereof |
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