CN111690199A - Ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof - Google Patents
Ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 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 title claims abstract description 52
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 238000004132 cross linking Methods 0.000 title claims abstract description 38
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 35
- 239000000779 smoke Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012965 benzophenone Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 14
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 14
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 14
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 14
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 13
- 230000002195 synergetic effect Effects 0.000 claims abstract description 7
- 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 15
- 239000002656 Distearyl thiodipropionate Substances 0.000 claims description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 11
- 235000019305 distearyl thiodipropionate Nutrition 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 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 8
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- -1 pentaerythritol ester Chemical class 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 230000007306 turnover Effects 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 3
- 150000002367 halogens Chemical class 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010008 shearing 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- 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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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
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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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- 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
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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
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- C08L2312/06—Crosslinking by radiation
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Abstract
The invention discloses an ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and a preparation method thereof, belonging to the technical field of crosslinking type cable materials. The flame retardant is composed of 15-25 parts of ethylene-vinyl acetate copolymer, 5-15 parts of ethylene octene copolymer, 5-10 parts of low density polyethylene, 30-60 parts of modified flame retardant, 5-8 parts of synergistic flame retardant, 1.5-2 parts of lubricant, 0.5-1 part of antioxidant, 0.5-1 part of auxiliary antioxidant, 0.8-2 parts of initiator, 1-3 parts of polyfunctional group cross-linking agent, 0.5-1 part of silane coupling agent, 5-8 parts of maleic anhydride grafted polyethylene material and 0.5-1 part of nano montmorillonite carbon forming agent. In the formula, benzophenone is used as an initiator and interacts with a polyfunctional group cross-linking agent, and an ultraviolet irradiation device is utilized, so that the high-speed production of a cable plant is realized, and the stable thermal extension is ensured; the prepared cable material has the paying-off speed of over 135m/min and the thermal elongation of 65-70%.
Description
Technical Field
The invention belongs to the technical field of irradiation cable materials, and particularly relates to an ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and a preparation method thereof.
Background
In recent years, the wire and cable industry has entered into leap-type mileage along with the rapid development of national economy, and special novel wires and cables and related matched low-smoke halogen-free cable materials have been developed and gradually applied to various industries and are spread throughout human life. Incomplete statistics is rejected, more than 40 percent of fire disasters occur in China due to wires and cables, and more than 25 percent of fire disasters are caused because the temperature resistance and the flame retardant grade of the wires cannot meet the requirements. Therefore, the life and property safety of people is protected to the maximum extent in fire accidents, and the proportion of the high-temperature-resistant and heat-resistant low-smoke halogen-free flame-retardant wire and cable products in the cable industry is increased year by year. Different irradiation processes are adopted to achieve the purpose of improving the temperature resistance and heat resistance level of the cable material. At present, the electron beam irradiation crosslinking technology is applied to the production of low-smoke halogen-free flame-retardant crosslinked polyolefin wires and cables, but the technology has the defects of high cost, complex production process, large equipment investment, poor crosslinking controllability and the like. The ultraviolet crosslinking technology is successfully applied to the production of electric wires and cables, but the traditional ultraviolet crosslinking equipment adopts a high-pressure mercury lamp, generates a large amount of heat during irradiation to cause insulating materials with colors to fade seriously, and has large power consumption of the whole machine and short service life of a lamp tube; and the prepared cable product has poor flame retardant property, and has great limitation on the use of the cable product.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material, which takes benzophenone as an initiator to interact with a polyfunctional group crosslinking agent, so that the production speed is high, and the stable thermal extension is ensured. The invention also provides a preparation method of the ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material, and the novel ultraviolet light LED crosslinking technology has the characteristics of low cost, simple and convenient process, low investment, long service life, more energy conservation, high efficiency, controllability and the like, and has great promotion significance for the development of the wire and cable industry.
In order to solve the problems, the invention adopts the following technical scheme:
an ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 15-25 parts of ethylene-vinyl acetate copolymer, 5-15 parts of ethylene octene copolymer, 5-10 parts of low density polyethylene, 30-60 parts of modified flame retardant, 5-8 parts of synergistic flame retardant, 1.5-2 parts of lubricant, 0.5-1 part of antioxidant, 0.5-1 part of auxiliary antioxidant, 0.8-2 parts of initiator, 1-3 parts of polyfunctional group cross-linking agent, 0.5-1 part of silane coupling agent, 5-8 parts of maleic anhydride grafted polyethylene material and 0.5-1 part of nano montmorillonite carbon forming agent.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 15-20 parts of ethylene-vinyl acetate copolymer, 8-12.5 parts of ethylene octene copolymer, 7-8 parts of low-density polyethylene, 55 parts of modified flame retardant, 5 parts of synergistic flame retardant, 1.5-2 parts of lubricant, 0.5 part of antioxidant, 0.5 part of auxiliary antioxidant, 0.8-1.2 parts of initiator, 1-1.25 parts of polyfunctional group cross-linking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted PE material and 0.5 part of nano montmorillonite carbon forming agent.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is characterized in that the modified flame retardant is one or a mixture of magnesium hydroxide and aluminum hydroxide, and the synergistic flame retardant is melamine cyanurate.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is characterized in that the lubricant is an organic silicon lubricant, and the initiator is benzophenone.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is characterized in that the antioxidant is pentaerythritol ester, and the auxiliary antioxidant is distearyl thiodipropionate.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is prepared by compounding any two of triallyl cyanurate, triallyl isocyanurate or trimethylolpropane tri (methyl) acrylate.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 20 parts of ethylene-vinyl acetate copolymer, 8 parts of ethylene octene copolymer, 8 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of melamine cyanurate, 1.5 parts of organic silicon lubricant, 0.5 part of pentaerythritol ester, 0.5 part of distearyl thiodipropionate, 0.8 part of benzophenone, 1 part of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the polyfunctional group cross-linking agent is prepared by mixing triallyl cyanurate and triallyl isocyanurate in a mass ratio of 1: 1.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 15 parts of ethylene-vinyl acetate copolymer, 12.5 parts of ethylene octene copolymer, 7 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of melamine cyanurate, 1.5 parts of organic silicon lubricant, 0.5 part of pentaerythritol ester, 0.5 part of distearyl thiodipropionate, 1 part of benzophenone, 1 part of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the multifunctional crosslinking agent is prepared by mixing triallyl cyanurate and trimethylolpropane tri (methyl) acrylate in a mass ratio of 1: 1.
The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 15 parts of ethylene-vinyl acetate copolymer, 12.5 parts of ethylene octene copolymer, 7 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of melamine cyanurate, 1.5 parts of organic silicon lubricant, 0.5 part of pentaerythritol ester, 0.5 part of distearyl thiodipropionate, 1.2 parts of benzophenone, 1.25 parts of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the polyfunctional group crosslinking agent is prepared by mixing triallyl isocyanurate and trimethylolpropane tri (methyl) acrylate according to the mass ratio of 1: 1.
The preparation method of the ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following steps:
(1) accurately weighing the raw materials for later use, and raising the temperature of an internal mixer to 160 ℃;
(2) adding the flame retardant into an internal mixer, sequentially adding the resin, the antioxidant and the initiator, turning over for 3-4min in a sealing pan, putting down a press hammer to start pressing and sealing, lifting the press hammer at 125 ℃, 135 ℃ and 145 ℃ to turn over materials, discharging at 155-160 ℃, and entering an extrusion molding process;
(3) the temperature zones of the extruding machine are set according to the temperature of 90 ℃, 95 ℃, 100 ℃ and 140 ℃, the materials are dispersed and sheared again by utilizing the double screws, so that the material particles are dispersed more uniformly and plasticized more thoroughly, and finally, granulation is carried out.
Has the advantages that: compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes the benzophenone as the initiator to interact with the polyfunctional group crosslinking agent, thereby realizing high production speed and simultaneously ensuring stable thermal extension; the prepared cable material has the paying-off speed of 135m/min and the thermal elongation of 65 percent.
(2) The invention adopts the novel ultraviolet light LED crosslinking technology, has the characteristics of low cost, simple and convenient process, low investment, long service life, more energy conservation, high efficiency, controllability and the like, and has great promotion significance for the development of the wire and cable industry.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
An ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 20 parts of ethylene-vinyl acetate copolymer, 8 parts of ethylene octene copolymer, 8 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of Melamine Cyanurate (MCA), 1.5 parts of organic silicon lubricant, 0.5 part of tetrapentaerythritol ester, 0.5 part of distearyl thiodipropionate, 0.8 part of benzophenone, 1 part of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein, the polyfunctional group cross-linking agent is prepared by mixing triallyl cyanurate and triallyl isocyanurate in a mass ratio of 1: 1.
The preparation method of the ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following steps:
(1) accurately weighing all the raw materials, accurately weighing for later use, and raising the temperature of an internal mixer to 160 ℃;
(2) firstly adding a modified flame retardant and MCA into an internal mixer, then adding resin, an antioxidant and an initiator into the internal mixer, after the mixture is subjected to hollow turning for 3-4min in the internal mixer, putting down a press hammer to start pressing and compacting, lifting the press hammer at the temperature of 125 ℃, 135 ℃ and 145 ℃ to turn over the material, discharging the material at the temperature of 155-160 ℃, and entering the extrusion molding process in the step (3);
(3) temperature zones of the extruding machine are set according to the temperature of 90 ℃, 95 ℃, 100 ℃ and 140 ℃, under the temperature condition, the double screws are used for dispersing and shearing the materials again, so that the materials are dispersed more uniformly and plasticized more thoroughly, finally, the first product is prepared by granulation, and the product performance of the first product is tested, and the results are shown in table 1.
Example 2
An ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 15 parts of ethylene-vinyl acetate copolymer, 12.5 parts of ethylene octene copolymer, 7 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of Melamine Cyanurate (MCA), 1.5 parts of organic silicon lubricant, 0.5 part of tetrapentaerythritol ester, 0.5 part of distearyl thiodipropionate, 1 part of benzophenone, 1 part of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the polyfunctional group crosslinking agent is prepared by mixing triallyl cyanurate and trimethylolpropane tri (methyl) acrylate according to the mass ratio of 1: 1.
The preparation process in example 1 was used to produce a second product, which was tested for product performance, and the results are shown in table 1.
Example 3
An ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material comprises the following components in parts by weight: 15 parts of ethylene-vinyl acetate copolymer, 12.5 parts of ethylene octene copolymer, 7 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of Melamine Cyanurate (MCA), 1.5 parts of organic silicon lubricant, 0.5 part of tetrapentaerythritol ester, 0.5 part of distearyl thiodipropionate, 1.2 parts of benzophenone, 1.25 parts of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the polyfunctional group crosslinking agent is prepared by mixing triallyl isocyanurate and trimethylolpropane tri (methyl) acrylate according to the mass ratio of 1: 1.
The preparation process in example 1 was used to produce a cable material, a third product was prepared, and the product performance of the third product was tested, with the results shown in table 1.
As can be seen from table 1, the preparation methods of examples 1 to 3 are simple, the product performance is excellent, and the simultaneous use and reasonable adjustment of the amount of the benzophenone and the polyfunctional group crosslinking agent in the formula enable the photoinitiator to absorb light energy with a specific wavelength more quickly and easily and convert the light energy into an excited state, so that hydrogen is abstracted from a polyolefin chain to generate radicals, a series of quick radical polymerization reactions are initiated, a cross-linked polyolefin structure with a three-dimensional network structure is generated from common polyolefin, and the stability of temperature resistance and heat resistance of the product is directly influenced by the degree of cross-linking. The proportion of a crosslinking system in the formula is adjusted, so that the production speed is high, and the stable thermal extension is ensured, the paying-off speed of the cable material in the embodiment of the invention can reach 135m/min, and the thermal extension is 65 percent, so that the standard requirement is met, and the high-efficiency industrial production of the low-smoke halogen-free flame-retardant polyolefin cable material can be realized.
Table 1 product Performance test results
Claims (10)
1. The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material is characterized by comprising the following components in parts by weight: 15-25 parts of ethylene-vinyl acetate copolymer, 5-15 parts of ethylene octene copolymer, 5-10 parts of low density polyethylene, 30-60 parts of modified flame retardant, 5-8 parts of synergistic flame retardant, 1.5-2 parts of lubricant, 0.5-1 part of antioxidant, 0.5-1 part of auxiliary antioxidant, 0.8-2 parts of initiator, 1-3 parts of polyfunctional group cross-linking agent, 0.5-1 part of silane coupling agent, 5-8 parts of maleic anhydride grafted polyethylene material and 0.5-1 part of nano montmorillonite carbon forming agent.
2. The ultraviolet light crosslinking low-smoke halogen-free flame retardant polyolefin cable material as claimed in claim 1, which is characterized by comprising the following components in parts by weight: 15-20 parts of ethylene-vinyl acetate copolymer, 8-12.5 parts of ethylene octene copolymer, 7-8 parts of low-density polyethylene, 55 parts of modified flame retardant, 5 parts of synergistic flame retardant, 1.5 parts of lubricant, 0.5 part of antioxidant, 0.5 part of auxiliary antioxidant, 0.8-1.2 parts of initiator, 1-1.25 parts of polyfunctional group cross-linking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent.
3. The ultraviolet light crosslinking low-smoke zero-halogen flame-retardant polyolefin cable material as claimed in claim 1 or 2, wherein the modified flame retardant is one or a mixture of magnesium hydroxide and aluminum hydroxide, and the synergistic flame retardant is melamine cyanurate.
4. The ultraviolet light crosslinking low smoke zero halogen flame retardant polyolefin cable material as claimed in claim 1 or 2, wherein the lubricant is an organosilicon lubricant and the initiator is benzophenone.
5. The ultraviolet light crosslinking low smoke zero halogen flame retardant polyolefin cable material as claimed in claim 1 or 2, characterized in that the antioxidant is pentaerythritol ester, and the auxiliary antioxidant is distearyl thiodipropionate.
6. The ultraviolet-crosslinked low-smoke halogen-free flame-retardant polyolefin cable material as claimed in claim 1 or 2, wherein the multifunctional crosslinking agent is prepared by compounding any two of triallyl cyanurate, triallyl isocyanurate or trimethylolpropane tri (meth) acrylate.
7. The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material as claimed in claim 1 or 2, which is characterized by comprising the following components in parts by weight: 20 parts of ethylene-vinyl acetate copolymer, 8 parts of ethylene octene copolymer, 8 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of melamine cyanurate, 1.5 parts of organic silicon lubricant, 0.5 part of pentaerythritol ester, 0.5 part of distearyl thiodipropionate, 0.8 part of benzophenone, 1 part of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the polyfunctional group cross-linking agent is prepared by mixing triallyl cyanurate and triallyl isocyanurate in a mass ratio of 1: 1.
8. The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material as claimed in claim 1 or 2, which is characterized by comprising the following components in parts by weight: 15 parts of ethylene-vinyl acetate copolymer, 12.5 parts of ethylene octene copolymer, 7 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of melamine cyanurate, 1.5 parts of organic silicon lubricant, 0.5 part of pentaerythritol ester, 0.5 part of distearyl thiodipropionate, 1 part of benzophenone, 1 part of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the multifunctional crosslinking agent is prepared by mixing triallyl cyanurate and trimethylolpropane tri (methyl) acrylate in a mass ratio of 1: 1.
9. The ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material as claimed in claim 1 or 2, which is characterized by comprising the following components in parts by weight: 15 parts of ethylene-vinyl acetate copolymer, 12.5 parts of ethylene octene copolymer, 7 parts of low-density polyethylene, 55 parts of aluminum hydroxide, 5 parts of melamine cyanurate, 1.5 parts of organic silicon lubricant, 0.5 part of pentaerythritol ester, 0.5 part of distearyl thiodipropionate, 1.2 parts of benzophenone, 1.25 parts of polyfunctional group crosslinking agent, 0.6 part of silane coupling agent, 5 parts of maleic anhydride grafted polyethylene material and 0.5 part of nano montmorillonite carbon forming agent; wherein the polyfunctional group crosslinking agent is prepared by mixing triallyl isocyanurate and trimethylolpropane tri (methyl) acrylate according to the mass ratio of 1: 1.
10. The preparation method of the ultraviolet crosslinking low-smoke halogen-free flame-retardant polyolefin cable material of claim 1 or 2, which is characterized by comprising the following steps:
(1) accurately weighing the reaction raw materials for later use, and raising the temperature of an internal mixer to 160 ℃;
(2) adding the flame retardant, sequentially adding the resin, the antioxidant and the initiator, turning over in a sealing pan for 3-4min, putting down a press hammer to start pressing and sealing, lifting the press hammer at 125 ℃, 135 ℃ and 145 ℃ to turn over, discharging at 155-160 ℃, and entering an extrusion molding process;
(3) the temperature zones of the extruding machine are set according to the temperature of 90 ℃, 95 ℃, 100 ℃ and 140 ℃, the materials are dispersed and sheared again by utilizing the double screws, so that the materials are dispersed more uniformly and plasticized more thoroughly, and finally, granulation is carried out.
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