CN111690200A - 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for UL3266 electronic wire and preparation method thereof - Google Patents
150 ℃ irradiation crosslinking low-smoke halogen-free cable material for UL3266 electronic wire and preparation method thereof Download PDFInfo
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- CN111690200A CN111690200A CN202010656699.2A CN202010656699A CN111690200A CN 111690200 A CN111690200 A CN 111690200A CN 202010656699 A CN202010656699 A CN 202010656699A CN 111690200 A CN111690200 A CN 111690200A
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000000779 smoke Substances 0.000 title claims abstract description 26
- 238000004132 cross linking Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title description 5
- 239000003063 flame retardant Substances 0.000 claims abstract description 57
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 55
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 49
- 239000000314 lubricant Substances 0.000 claims abstract description 17
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 16
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 230000002195 synergetic effect Effects 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 21
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 14
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 9
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 7
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 5
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 5
- 229910017059 organic montmorillonite Inorganic materials 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229920013638 modified polyphenyl ether Polymers 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 3
- -1 pentaerythritol ester Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920013683 Celanese Polymers 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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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
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
A150 ℃ irradiation crosslinking low-smoke halogen-free cable material for a UL3266 electronic wire is characterized by being prepared from the following raw materials in parts by weight: 50-65 parts of ethylene-vinyl acetate copolymer, 20-25 parts of ethylene-octene copolymer, 10-15 parts of metallocene catalyzed linear low-density polyethylene, 10-15 parts of compatilizer, 20-40 parts of phosphorus flame retardant, 0-40 parts of nitrogen flame retardant, 3-6 parts of synergistic flame retardant, 3 parts of cross-linking agent, 2-4 parts of high-performance lubricant and 4-6 parts of composite antioxidant. The 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for the UL3266 electronic wire provided by the invention has the advantages that the tensile strength of the UL3266 electronic wire manufactured by using the cable material after irradiation is not less than 13.8MPa, the elongation at break is not less than 300%, the flame retardant rating is VW-1, and other properties completely meet the standard requirements of the UL3266 electronic wire.
Description
Technical Field
The invention belongs to the technical field of cable materials, and particularly relates to a 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for a UL3266 electronic wire and a preparation method thereof.
Background
The electronic wire is used for weak current engineering, such as internal connection of electronic and electrical equipment. As the connecting wire inside the electrical equipment, the quality of the connecting wire directly relates to the use performance of the electrical equipment, because the current transmission and the signal transmission inside the electrical equipment are all realized by means of the electronic wire, if the quality of the electronic wire is poor, the phenomena of unstable current and unstable signal can be generated, and the faults can be caused in the use process of the electrical equipment directly.
The mainstream electronic lines in the domestic market are divided into two types: 3C electronic cable and American Standard (UL) electronic cable. The 3C electronic wire adopts national standard or IEC standard, the technology is relatively mature, and the product covers various temperature resistant grades such as 105 ℃, 125 ℃, 150 ℃ and the like. The UL electronic line is a general name of an electronic line passing UL certification and needs to meet the environmental protection requirement of European Union ROHS. The UL electrical wires can be classified into various models according to different uses and performances.
The UL3266 electronic wire is widely applied to connecting wires of household cables, lighting lamps, electronic equipment, instruments and meters, security equipment and the like. Because two standards of UL1581 and UL758 are mostly adopted in UL electronic wires, the main technical indexes of not less than 13.8MPa of tensile strength, not less than 300% of elongation at break, not less than 80% of retention rate of the tensile strength and the elongation at break after 180 ℃ for 168h of aging, flame resistance VW-1 and the like are required to be met.
Originally, low smoke and low halogen materials were mostly used for UL3266 electronic wire insulation. With the development of production technology and the improvement of environmental awareness of people, people begin to research and develop and prepare polyolefin low-smoke halogen-free cable materials, and materials such as hydroxide, red phosphorus, zinc borate and the like are adopted as flame retardants, however, the flame retardant efficiency of the flame retardants is low, and a certain flame retardant effect can be achieved only by the sufficient filling amount; the increase of the filling amount of the flame retardant inevitably causes the reduction of the mechanical properties such as tensile strength, elongation at break and the like of the cable material; on the other hand, the low-smoke halogen-free polyolefin has poor high-temperature resistance, and the performance of the prepared cable material cannot meet the market requirement.
In view of this, the subject of the present invention is how to design a high temperature aging resistant low smoke halogen-free cable material for UL3266 electronic wire meeting the standard.
Disclosure of Invention
The invention provides a 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for a UL3266 electronic wire and a preparation method thereof, aiming at solving the problem that the high temperature resistance, the mechanical property and the like of the existing UL3266 electronic wire can not meet the market requirements.
A150 ℃ irradiation crosslinking low-smoke halogen-free cable material for a UL3266 electronic wire is characterized by being mainly prepared from the following raw materials in parts by weight:
wherein the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer with the weight content of vinyl acetate greater than or equal to 26% and the melt flow rate of 3-8 g/10 min;
the phosphorus flame retardant is inorganic aluminum hypophosphite, diethyl aluminum hypophosphite or halogen-free phosphorus-nitrogen intumescent flame retardant;
the synergistic flame retardant is one of modified polyphenyl ether, nano organic montmorillonite and sepiolite;
the composite antioxidant is a blend of five antioxidants, namely 1010 antioxidant, DLTP antioxidant, 412S antioxidant, 626 antioxidant and 1024, wherein the weight ratio of the five antioxidants is 1010: antioxidant DLTP: antioxidant 412S: antioxidant 626: antioxidant 1024 is 1-1.5: 1-1.5: 0.5-1.5: 0.5-1.5: 0.5 to 1.
The following explains the related contents of the first and second technical solutions:
1. in the scheme, the halogen-free phosphorus-nitrogen intumescent flame retardant is Exolit IFR-10 series flame retardant or ExolitAP series flame retardant.
2. In the scheme, the nitrogen flame retardant is melamine cyanurate salt with melamine cyanurate content of more than or equal to 99.5wt%, medium particle size of less than or equal to 2 microns and decomposition temperature of more than or equal to 350 ℃.
3. In the scheme, the melt flow rate of the ethylene-octene copolymer is 2.5-8 g/10 min.
4. In the scheme, the melt flow rate of the metallocene-catalyzed linear low density polyethylene (mLLDPE) is 2.5-8 g/10 min.
5. In the above scheme, the compatibilizer is maleic anhydride grafted metallocene catalyzed linear low density polyethylene and/or maleic anhydride grafted ethylene-octene copolymer.
6. In the above scheme, the crosslinking agent is one of trimethylolpropane trimethacrylate (TMPTMA) or triallyl isocyanurate (TAIC).
7. In the scheme, the phosphorus content in the phosphorus flame retardant is more than or equal to 19wt% and the medium particle size is less than or equal to 10 microns.
8. In the scheme, the high-performance lubricant is a compound of polyester wax and polyamide wax with a dropping point of 62-67 ℃, or a blend of the compound of polyester wax and polyamide wax with a dropping point of 62-67 ℃ and silicone master batch with the number average molecular weight of siloxane exceeding 100 ten thousand.
9. In the scheme, the antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; the antioxidant DLTP is dilauryl thiodipropionate; the antioxidant 412S is pentaerythritol tetrakis (3-lauryl thiopropionate); the antioxidant 626 is bis (2, 4-di-tert-butylphenyl) propanoic acid ] pentaerythritol diphosphite; the antioxidant 1024 is N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
10. The cable material is mainly used for UL3266 electronic wires, but can also be used for other UL electronic wires.
In order to achieve the purpose, the preparation method of the irradiation crosslinking low-smoke halogen-free cable material at 150 ℃ for the UL3266 electronic wire is characterized by sequentially comprising the following steps of:
adding ethylene-vinyl acetate copolymer, metallocene catalyzed linear low-density polyethylene, ethylene-octene copolymer, compatilizer, phosphorus-nitrogen flame retardant, synergistic flame retardant, crosslinking agent, high-performance lubricant and composite antioxidant into an internal mixer at 80-90 ℃ in proportion, internally mixing for 10-13 minutes, discharging into a double-screw/single-screw double-stage mixing unit at 130-150 ℃ for plasticizing extrusion, cold air grinding, cutting, air cooling and screening by a vibrating screen to obtain the 150 ℃ irradiation crosslinking halogen-free low-smoke cable material for the UL3266 electronic wire.
The invention has the design characteristics and beneficial effects that:
1. the 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for the UL3266 electronic wire adopts the compounding of the normal-temperature antioxidant (namely, the antioxidant 1010 and the antioxidant DLTP) and the high-temperature antioxidant (namely, the antioxidant 412s and the antioxidant 626), can effectively inhibit the fracture and recombination of polyolefin molecular chains in a high-temperature and high-oxygen environment, and ensures that the retention rate of the tensile strength and the elongation at break of the material is still kept above 80 percent after the material is aged in a UL aging oven with the ventilation frequency of up to 200 times/h for 7 days; in addition, the added antioxidant 1024 has the functions of oxidation resistance and metal deactivation, and can inhibit the catalytic action of the copper conductor on the wire aging.
2. The invention selects five different antioxidants and limits the amount of the five antioxidants in proportion to achieve a synergistic effect, so that the application effect is greater than the sum of the effects of each antioxidant when used alone, the aging of the polyolefin is effectively inhibited, the stability of the polyolefin is also effectively enhanced, the high temperature resistance of the low-smoke halogen-free polyolefin is greatly improved, and the service life of the low-smoke halogen-free polyolefin is prolonged, namely the effect of 1+1 is greater than 2.
3. The UL3266 electronic wire uses the 150 ℃ irradiation crosslinking low-smoke halogen-free cable material, adopts the high-efficiency flame-retardant phosphorus flame retardant and nitrogen flame retardant as the main flame retardant, and has good flame-retardant effect with the synergistic flame retardant, so that the UL3266 electronic wire which is always low-smoke and low-halogen is non-halogenated. The high-performance lubricant adopted in the scheme can reduce the viscosity of the polyolefin and improve the compatibility of the flame retardant and the polyolefin and the aging performance of the material.
4. According to the invention, metallocene linear low-density polyethylene, ethylene-octene copolymer and ethylene-vinyl acetate copolymer are matched according to a reasonable proportion, and the cable material is free from poor mechanical properties caused by adding excessive flame retardant due to the reasonable compound proportion of the phosphorus nitrogen flame retardant and the synergistic flame retardant, so that the tensile property and the processing property of the cable material are greatly improved.
In a word, the UL3266 electronic wire prepared from the 150 ℃ irradiation crosslinking low-smoke halogen-free cable material has the tensile strength of not less than 13.8MPa after irradiation, the elongation at break of not less than 300 percent, the flame retardant rating of VW-1, and other properties completely meeting the UL3266 electronic wire standard requirements (UL1581 and UL 758).
Detailed Description
The invention is further described below with reference to the following examples:
in order to more clearly and concisely describe the following embodiments, some of the materials referred to in the embodiments have been given their english reference numerals.
The related English code has the Chinese meanings as follows: EVA is ethylene-vinyl acetate copolymer, LLDPE is linear low density polyethylene, mLLDPE is metallocene catalyzed linear low density polyethylene, POE is ethylene-octene copolymer, TMPTMA is trimethylolpropane trimethacrylate, TAIC is triallyl isocyanurate, mPO is modified polyphenyl ether, OMMT is nano organic montmorillonite, and MCA is melamine cyanurate.
Example (b): 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for UL3266 electronic wire
A150 ℃ irradiation crosslinking low-smoke halogen-free cable material for UL3266 electronic wires comprises the following raw materials (unit: weight portion) as shown in Table 1:
table 1A 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for UL3266 electronic wire
In example 1, EVA is manufactured by akoma corporation under the designation 2803; the ethylene-octene copolymer is a blend of two POEs, and is produced by Dow chemistry, wherein the number of Engage8200 is 12 parts, and the number of Engage8480 is 8 parts; mLLDPE is available from Exxon Mobil corporation under the designation 3518 CB; the compatilizer is maleic anhydride grafted mLLDPE, which is produced by Jiangsu plasticizing company and is of the brand number M506-4C; the phosphorus-nitrogen flame retardant is a blend of inorganic aluminum hypophosphite and MCA; the synergistic flame retardant is mPO, produced by Saebick company; the cross-linking agent is TMPTMA, produced by Dahua corporation of full sentence capacity; the high-performance lubricant is silicone master batch (brand GT-300) produced by Jiahua corporation and lubricant (brand TR451) produced by Struktol corporation, 1.5 parts each; the composite antioxidant is a blend of 1.5 parts of antioxidant 1010, 1 part of antioxidant DLTP, 0.5 part of antioxidant 412S, 1.5 parts of antioxidant 626 and 0.5 part of antioxidant 1024.
In example 2, EVA is produced by LG corporation under the brand number EC 28005; the ethylene-octene copolymer is a blend of two POEs, 15 parts of LC670 produced by LG chemical company and 10 parts of Engage8480 produced by Dow chemical company; mLLDPE is available from Exxon Mobil corporation under the designation 3518 CB; the compatilizer is maleic anhydride grafted POE, produced by Darland plastics industry of Town, and is of the brand TRD-200 PM; the phosphorus-nitrogen flame retardant is a blend of diethyl aluminum hypophosphite and MCA; the synergistic flame retardant is OMMT, produced by Nanocor company; the cross-linking agent is TAIC, produced by Tawatsu Dahua corporation; the high-performance lubricant is 1.5 parts of silicone master batch (the mark is GT-300) produced by Jiahua company and 2.5 parts of lubricant (the mark is TR451) produced by Struktol company; the composite antioxidant is a blend of 1.5 parts of 1010, 1.5 parts of antioxidant DLTP, 1 part of antioxidant 412S, 1 part of antioxidant 626 and 0.8 part of antioxidant 1024.
In example 3, EVA is manufactured by Exxon Mobil corporation under the designation UL 00328; the ethylene-octene copolymer is a blend of two POEs, both produced by LG chemical company, wherein 10 parts of LC100 and 10 parts of LC 670; mLLDPE is produced by Dondall corporation under the brand number FB 2230; the compatilizer is a blend of 10 parts of maleic anhydride grafted mLLDPE, produced by Jiangsu plasticizing company under the brand number of M506-4C, 5 parts of maleic anhydride grafted POE, produced by Darland plastics industry under the brand number of TRD-200 PM; the phosphorus-nitrogen flame retardant is a blend of diethyl aluminum hypophosphite and MCA; the synergistic flame retardant is sepiolite; the cross-linking agent is TMPTMA, produced by Dahua corporation of full sentence capacity; the high performance lubricant is a lubricant manufactured by Struktol corporation, and is provided with the brand number TR 451; the composite antioxidant is a blend of 1 part of antioxidant 1010, 1 part of antioxidant DLTP, 1.5 parts of antioxidant 412S, 0.5 part of antioxidant 626 and 1 part of antioxidant 1024.
In example 4, EVA is manufactured by Exxon Mobil corporation under the designation UL 00328; the ethylene-octene copolymer is a blend of two POEs, 15 parts of LC670 produced by LG chemical company and 10 parts of Engage8480 produced by Dow chemical company; mLLDPE is available from Exxon Mobil corporation under the designation 3518 CB; the compatilizer is a blend of 10 parts of maleic anhydride grafted mLLDPE, produced by Jiangsu plasticizing company, of which the mark is M506-4C, 5 parts of maleic anhydride grafted POE, produced by Daiseda plastics industry of Ching, of which the mark is TRD-200 PM; the phosphorus-nitrogen flame retardant is a halogen-free phosphorus-nitrogen intumescent flame retardant which is produced by Hoechst Celanese company and is sold under the trademark of Exolit IFR-10; the synergistic flame retardant is mPPO produced by Sabbick company; the cross-linking agent is TMPTMA, produced by Dahua corporation of full sentence capacity; the high performance lubricant is a lubricant manufactured by Struktol corporation, and is provided with the brand number TR 451; the compound antioxidant is a blend of 1 part of antioxidant 1010, 1 part of antioxidant DLTP, 1 part of antioxidant 412S, 1 part of antioxidant 626 and 0.8 part of antioxidant 1024.
In example 5, EVA is manufactured by arkema corporation under the designation 2803; the ethylene-octene copolymer is a blend of two POEs, and is produced by Dow chemistry, wherein the number of Engage8200 is 15 parts, and the number of Engage8480 is 10 parts; mLLDPE is available from Exxon Mobil corporation under the designation 3518 CB; the compatilizer is maleic anhydride grafted mLLDPE, produced by Jiangsu plastication department and is of a brand number M506-4C; the phosphorus-nitrogen flame retardant is a blend of halogen-free phosphorus-nitrogen intumescent flame retardant and MCA, the halogen-free phosphorus-nitrogen intumescent flame retardant is produced by Hoechst Celanese company and is sold as Exolit IFR-AP; the synergistic flame retardant is mPPO produced by Saibek company; the cross-linking agent is TAIC, produced by Tawatsu Dahua corporation; the high-performance lubricant is silicone master batch (brand GT-300) produced by Jiahua corporation and lubricant (brand TR451) produced by Struktol corporation, 1.5 parts each; the composite antioxidant is a blend of 1.5 parts of antioxidant 1010, 1 part of antioxidant DLTP, 0.5 part of antioxidant 412S, 1.5 parts of antioxidant 626 and 0.5 part of antioxidant 1024.
The production method of all examples is as follows:
EVA, mLLDPE, ethylene-octene copolymer, compatilizer, phosphorus flame retardant, nitrogen flame retardant, synergistic flame retardant, crosslinking agent, high-performance lubricant and composite antioxidant are added into an internal mixer at 80-90 ℃ in proportion, after internal mixing is carried out for 10-13 minutes, the mixture is discharged into a double-screw/single-screw double-stage mixing mill set at 130-150 ℃ for plasticizing extrusion, cold air milling and surface cutting, and then air cooling and vibrating screen separation are carried out, so that the 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for the UL3266 electronic wire can be prepared.
The properties of the UL3266 electronic wire prepared by the embodiments and the 150 ℃ irradiation crosslinking low-smoke halogen-free cable material are shown in Table 2:
TABLE 2 Properties of 150 ℃ irradiation crosslinked LSOH cable material for UL3266 electronic wire
Wherein, in the technical scheme of the invention, mildew preventive, ultraviolet light absorber, brightener and the like can be added according to the condition, which is known and understood by those skilled in the art.
Examples 1 to 5: the above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A150 ℃ irradiation crosslinking low-smoke halogen-free cable material for a UL3266 electronic wire is characterized by being mainly prepared from the following raw materials in parts by weight:
wherein the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer with the weight content of vinyl acetate greater than or equal to 26% and the melt flow rate of 3-8 g/10 min;
the phosphorus flame retardant is inorganic aluminum hypophosphite, diethyl aluminum hypophosphite or halogen-free phosphorus-nitrogen intumescent flame retardant;
the synergistic flame retardant is one of modified polyphenyl ether, nano organic montmorillonite and sepiolite;
the composite antioxidant is a blend of five antioxidants, namely 1010 antioxidant, DLTP antioxidant, 412S antioxidant, 626 antioxidant and 1024, wherein the weight ratio of the five antioxidants is 1010: antioxidant DLTP: antioxidant 412S: antioxidant 626: antioxidant 1024= 1-1.5: 1-1.5: 0.5-1.5: 0.5-1.5: 0.5 to 1.
2. The cable material according to claim 1, wherein: the halogen-free phosphorus-nitrogen intumescent flame retardant is ExolitIFR-10 series flame retardant or Exolit AP series flame retardant.
3. The cable material according to claim 1, wherein: the nitrogen flame retardant is melamine cyanurate salt with melamine cyanurate content of more than or equal to 99.5wt%, medium particle size of less than or equal to 2 microns and decomposition temperature of more than or equal to 350 ℃.
4. The cable material according to claim 1, wherein: the melt flow rate of the ethylene-octene copolymer is 2.5-8 g/10 min.
5. The cable material according to claim 1, wherein: the melt flow rate of the metallocene-catalyzed linear low-density polyethylene is 2.5-8 g/10 min.
6. The cable material according to claim 1, wherein: the compatilizer is maleic anhydride grafted metallocene catalyzed linear low density polyethylene and/or maleic anhydride grafted ethylene-octene copolymer.
7. The cable material according to claim 1, wherein: the cross-linking agent is one of trimethylolpropane trimethacrylate or triallyl isocyanurate.
8. The cable material according to claim 1, wherein: the phosphorus content in the phosphorus flame retardant is greater than or equal to 19wt% and the medium particle size is less than or equal to 10 micrometers.
9. The cable material according to claim 1, wherein: the high-performance lubricant is a compound of polyester wax and polyamide wax with a dropping point of 62-67 ℃, or a blend of the compound of polyester wax and polyamide wax with a dropping point of 62-67 ℃ and silicone master batch with the number average molecular weight of siloxane exceeding 100 ten thousand.
10. A method for preparing a cable material according to any one of claims 1 to 9, comprising the following steps in sequence: adding ethylene-vinyl acetate copolymer, metallocene-catalyzed linear low-density polyethylene, ethylene-octene copolymer, compatilizer, phosphorus flame retardant, nitrogen flame retardant, synergistic flame retardant, crosslinking agent, high-performance lubricant and composite antioxidant into an internal mixer at 80-90 ℃ in proportion, internally mixing for 10-13 minutes, discharging into a double-screw/single-screw double-stage mixing unit at 130-150 ℃ for plasticizing extrusion, cold air grinding, cutting, air cooling and screening by a vibrating screen to obtain the 150 ℃ irradiation crosslinking low-smoke halogen-free cable material for the UL3266 electronic wire.
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