CN104403190A - Ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof - Google Patents
Ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses an ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and a preparation method thereof, and relates to a flame retardant polyolefin cable material and a preparation method thereof, for solving the problems that a conventional flame retardant polyolefin cable material is complex in process, high in cost of cross-linking equipment and poor in oil resistance. The ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material is prepared from a base material, a halogen-free flame retardant, a cation initiator, a free radical initiator, a multi-functional cross-linking agent, a flame retardant synergist, an antismoke agent, a composite antioxidant and a lubricant in parts by weight. The preparation method comprises the following steps: feeding the raw materials into an internal mixer according to the parts by weight, uniformly mixing, feeding the mixture into a double-screw extruder, further mixing and plastifying uniformly, and feeding into a single-screw extruder for extrusion pelleting, thereby obtaining the ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material. The invention aims at preparing the ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material.
Description
Technical field
The present invention relates to a kind of flame-proof polyolefine cable material and preparation method thereof.
Background technology
In recent years, along with country is to the attention of Environment protection and safety, not only all require low-smoke halogen-free cable in some heavy construction or public places etc., and also have higher requirement to rolling stock electric wire used, requirement must have excellent Flame-Retardant and Oil-Resistant performance on the one hand, when ignition, the discharge of the amount of being fuming and corrosive gases is low, carrys out secondary disaster to prevent smoke zone.Require that it has the features such as thermotolerance, stress crack resistant, long service life on the other hand, therefore developing cross-linking type oil-resistant low-smoke halogen-free flame-retardant material has become a kind of trend.
It is main peroxide crosslinking low smoke and zero halogen material that US Patent No. 6227908B1 discloses with ethylene-vinyl acetate copolymer (EVA), magnesium hydroxide, compatible polymer, carbon black, linking agent, be issued to higher flame retardant resistance at relatively less fire retardant, improve mechanical property simultaneously; Chinese Patent Application No. 200910047568.8 discloses ethylene-vinyl acetate copolymer/paracril, aluminium hydroxide/magnesium hydroxide, red phosphorus, oxidation inhibitor, linking agent are that main grease-proof low-smoke halogen-free flame-proof cable material product line after high-energy electron beam irradiation is fire-retardant by bunchy burning C class, the mineral oil of resistance to IRM902 retention rate reaches more than 75%, and the oil fuel of resistance to IRM903 retention rate reaches more than 80%; Chinese Patent Application No. 201410016866 discloses prepares heatproof oil-resistant low-smoke halogen-free flame-retardant polyolefine material based on the co-mixing system high-energy electron beam irradiation cross-linking method of polyolefine, hyperbranched triazine char-forming agent microencapsulation inorganic flaming-resistant agent, more function group linking agent, goods oxygen index is greater than 38, excellent in mechanical performance, have passed oil resistant test.The halogen-free phosphorus-free inflaming retarding polyolefine material oxygen index that Chinese Patent Application No. 00112600.8 discloses with prepared by the silane cross-linking methods such as polyethylene, ethylene-vinyl acetate, magnesium hydroxide, vinylsiloxane, catalyzer reaches 32.5%, and tensile strength and elongation at break reach 12.8MPa and 426% respectively.But it is complicated that traditional peroxide crosslinking shortcoming is technical process, and investment is large, energy utilization rate is low, production efficiency is low, be not suitable for less wire diameter and produce; Son bundle cross-linking radiation due to facility investment large, maintenance of the equipment is more complicated, and protection is harsh, and the production cycle is long, and process characteristic is only suitable for producing thinner electric wire, and the electric wire uniformity of radiation of wall thickness is bad; And crosslinked with silicane relates to hydrolysis reaction, poor stability, pressure high-temp resistant grade is low, is not suitable for doing low-smoke halogen-free inflaming-retarding cable.
In recent years, UV irradiation cross-linking progressed into the sight line of people, and Chinese invention patent publication number CN1218963 and CN1919571, has dropped into the production of cross-linked wire and cable.Needed for this technology, cross-linking apparatus investment is low, and technique is simple, and production efficiency is high, and the cost of material is low, and quality is good, is applicable to the manufacture of electric wire.Disclose in the invention of China Patent Publication No. CN102153802B with polyolefine is base material, with radical initiator and radical cation initiator for mixed initiating system, add the auxiliary agents such as fire retardant, fire retarding synergist and linking agent and prepare excellent ultraviolet deep-crosslinked Halogen-free flame-retardant cable material, oxygen index reaches 43%, tensile strength 15.6MPa, elongation at break 220%, volume specific resistance 3.2 × 1013 Ω m, and have passed 145 DEG C of thermal ageings, but its oil resistance is low, the requirement of rolling stock electric wire used can not be met.
Summary of the invention
The present invention will solve the high and problem that oil resistance is low of existing flame-proof polyolefine cable material complex process, cross-linking apparatus cost.And a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin and preparation method thereof is provided.
A kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant of the present invention cable material of polyolefin is made up of 100 parts of base-materials, 120 ~ 130 parts of halogen-free flame retardantss, 1 ~ 3 part of cationic initiator, 1 ~ 3 part of radical initiator, 2 ~ 5 parts of multi-group crosslink agents, 5 ~ 10 parts of fire retarding synergists, 1 ~ 5 part of smoke suppressor, 0.1 ~ 0.5 part of composite antioxidant and 0.5 ~ 1.2 part of lubricant by weight;
Described base-material is for being ethylene, propylene methacrylate copolymers, ethylene-acrylate-carbonyl terpolymer, ethylene methyl acrylate copolymer, ethylene butyl acrylate multipolymer, Low Density Polyethylene, linear low density polyethylene, ethylene-alpha-octylene polymkeric substance, terpolymer EP rubber, styrene series thermoplastic elastomer, glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride graft vinyl acetate copolymer, a kind of or wherein several mixture in maleic anhydride grafted ethene-α-octene polymer and maleic anhydride grafted polyethylene, in wherein said ethylene-vinyl acetate copolymer rubber, the content of VA is 40% ~ 70%, in described paracril, the content of vinyl cyanide is 31% ~ 35%,
Described halogen-free flame retardants is surface modification flame retardant of magnesium hydroxide, surface modified aluminium hydroxide flame retardant or surface modification hypo-aluminum orthophosphate combustion inhibitor;
Described cationic initiator is a kind of or wherein several mixture in diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ethers;
Described radical initiator is benzoin dimethylether, a kind of or wherein several mixture in 2-hydroxy-2-methyl-1-phenyl-acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2,4 dihydroxyl benzophenone;
Described multi-group crosslink agent is a kind of or wherein several mixture in trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, triallyl cyanurate and cyamelide triallyl;
Described composite antioxidant is phenolic antioxidant, phosphite ester kind antioxidant, phosphoric acid ester oxidation inhibitor and two kinds or wherein several mixtures containing in sulphur ester antioxidant, wherein said phenolic antioxidant is β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, described phosphite ester kind antioxidant is triphenyl phosphite, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, described phosphoric acid ester oxidation inhibitor is triphenylphosphate, described sulphur ester antioxidant is Tyox B or thiodipropionic acid dilauryl osmanthus octadecyl ester.
The preparation method of above-mentioned a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take 100 parts of base-materials by weight, 120 ~ 130 parts of halogen-free flame retardantss, 1 ~ 3 part of cationic initiator, 1 ~ 3 part of radical initiator, 2 ~ 5 parts of multi-group crosslink agents, 5 ~ 10 parts of fire retarding synergists, 1 ~ 5 part of smoke suppressor, 0.1 ~ 0.5 part of composite antioxidant and 0.5 ~ 1.2 part of lubricant, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtain thermal material, then it is 130 DEG C ~ 145 DEG C in twin screw temperature, screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtain ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin,
Described base-material is for being ethylene, propylene methacrylate copolymers, ethylene-acrylate-carbonyl terpolymer, ethylene methyl acrylate copolymer, ethylene butyl acrylate multipolymer, Low Density Polyethylene, linear low density polyethylene, ethylene-alpha-octylene polymkeric substance, terpolymer EP rubber, styrene series thermoplastic elastomer, glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride graft vinyl acetate copolymer, a kind of or wherein several mixture in maleic anhydride grafted ethene-α-octene polymer and maleic anhydride grafted polyethylene, in wherein said ethylene-vinyl acetate copolymer rubber, the content of VA is 40% ~ 70%, in described paracril, the content of vinyl cyanide is 31% ~ 35%,
Described halogen-free flame retardants is surface modification flame retardant of magnesium hydroxide, surface modified aluminium hydroxide flame retardant or surface modification hypo-aluminum orthophosphate combustion inhibitor;
Described cationic initiator is a kind of or wherein several mixture in diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ethers;
Described radical initiator is benzoin dimethylether, a kind of or wherein several mixture in 2-hydroxy-2-methyl-1-phenyl-acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2,4 dihydroxyl benzophenone;
Described multi-group crosslink agent is a kind of or wherein several mixture in trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, triallyl cyanurate and cyamelide triallyl;
Described composite antioxidant is phenolic antioxidant, phosphite ester kind antioxidant, phosphoric acid ester oxidation inhibitor and two kinds or wherein several mixtures containing in sulphur ester antioxidant, wherein said phenolic antioxidant is β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, described phosphite ester kind antioxidant is triphenyl phosphite, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, described phosphoric acid ester oxidation inhibitor is triphenylphosphate, described sulphur ester antioxidant is Tyox B or thiodipropionic acid dilauryl osmanthus octadecyl ester.
Beneficial effect of the present invention:
Adopt ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant CABLE MATERIALS of the present invention, compared with traditional crosslinking method, have that production efficiency is high, technique carries out being cross-linked simply, online, facility investment is little, easy to maintenance, suitability is wide, and after ultraviolet light cross-linking, product mechanical property, oil resistance etc. are improved.
Embodiment
Embodiment one: a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant of present embodiment cable material of polyolefin is made up of 100 parts of base-materials, 120 ~ 130 parts of halogen-free flame retardantss, 1 ~ 3 part of cationic initiator, 1 ~ 3 part of radical initiator, 2 ~ 5 parts of multi-group crosslink agents, 5 ~ 10 parts of fire retarding synergists, 1 ~ 5 part of smoke suppressor, 0.1 ~ 0.5 part of composite antioxidant and 0.5 ~ 1.2 part of lubricant by weight;
Described base-material is for being ethylene, propylene methacrylate copolymers, ethylene-acrylate-carbonyl terpolymer, ethylene methyl acrylate copolymer, ethylene butyl acrylate multipolymer, Low Density Polyethylene, linear low density polyethylene, ethylene-alpha-octylene polymkeric substance, terpolymer EP rubber, styrene series thermoplastic elastomer, glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride graft vinyl acetate copolymer, a kind of or wherein several mixture in maleic anhydride grafted ethene-α-octene polymer and maleic anhydride grafted polyethylene, be mixed by any ratio for during mixture, in wherein said ethylene-vinyl acetate copolymer rubber, the content of VA is 40% ~ 70%, in described paracril, the content of vinyl cyanide is 31% ~ 35%,
Described halogen-free flame retardants is surface modification flame retardant of magnesium hydroxide, surface modified aluminium hydroxide flame retardant or surface modification hypo-aluminum orthophosphate combustion inhibitor;
Described cationic initiator is a kind of or wherein several mixture in diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ethers, is mixed by any ratio for during mixture;
Described radical initiator is benzoin dimethylether, and a kind of or wherein several mixture in 2-hydroxy-2-methyl-1-phenyl-acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2,4 dihydroxyl benzophenone, is mixed by any ratio for during mixture;
Described multi-group crosslink agent is a kind of or wherein several mixture in trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, triallyl cyanurate and cyamelide triallyl, is mixed by any ratio for during mixture;
Described composite antioxidant is phenolic antioxidant, phosphite ester kind antioxidant, phosphoric acid ester oxidation inhibitor and two kinds or wherein several mixtures containing in sulphur ester antioxidant, be mixed by any ratio for during mixture, wherein said phenolic antioxidant is β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, described phosphite ester kind antioxidant is triphenyl phosphite, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, described phosphoric acid ester oxidation inhibitor is triphenylphosphate, described sulphur ester antioxidant is Tyox B or thiodipropionic acid dilauryl osmanthus octadecyl ester.
The flame retardant of magnesium hydroxide of surface modification described in present embodiment, surface modified aluminium hydroxide flame retardant and surface modification hypo-aluminum orthophosphate combustion inhibitor adopt the surface-modifying agent of Dow corning 11-100 to carry out modification, modified particle diameter≤2 μm.
The ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin of present embodiment and traditional high-energy electron beam irradiation are cross-linked, chemically crosslinked, low smoke halogen-free fire retardant polyolefin cable material prepared by crosslinked with silicane technology is compared, this ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin, with the ethylene vinyl acetate copolymer of high vinyl acetate between to for plastic (VA) content more than 40% for main material, add paracril, acrylic acid esters co-polymer improves its oil-proofness, add the initiator system that cationic initiator combines with radical initiator simultaneously, can match with launching more wide wavelength range lamp source, cation light initiator is made to absorb more UV energy, at utmost improve its light-initiated efficiency in halogen-free anti-flaming polyolefin material and degree of uniformity thereof, the obvious cross-linking density improving material, add consistency, mechanical property, flame retardant resistance, processing characteristics etc. that the technique means such as compatilizer, elastomerics, crosslinking coagent, fire retardant, fire retarding synergist, lubricant improves material, develop that the investment of a kind of cross-linking apparatus is low, technique simple (being cross-linked online), production efficiency are high, energy-conserving and environment-protective, ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant polyolefine material that suitability is wide.
Embodiment two: present embodiment and embodiment one unlike: described cationic initiator is two dodecylbenzene hexafluoro arsenic formic acid salt compounded of iodine, 4, a kind of or wherein several mixture in 4 '-dimethyl diphenyl iodine phosphoric acid salt, phosphofluoric acid triaryl sulphur father-in-law's salt and cationic photoinitiator, is mixed by any ratio for during mixture.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: described fire retarding synergist is a kind of or wherein several mixture in hydrotalcite, zinc borate, polynite, wollastonite and aluminum silicon powder, is mixed by any ratio for during mixture.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: described smoke suppressor is a kind of or wherein several mixture in molybdenum sesquioxide, Ammonium Heptamolybdate and ammonium octamolybdate, is mixed by any ratio for during mixture.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: described lubricant is a kind of or wherein several mixture in stearic acid, Zinic stearas, PE-wax and liquid siloxane polymer, is mixed by any ratio for during mixture.Other is identical with one of embodiment one to four.
Embodiment six: the preparation method of a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant of present embodiment cable material of polyolefin carries out according to the following steps:
Take 100 parts of base-materials by weight, 120 ~ 130 parts of halogen-free flame retardantss, 1 ~ 3 part of cationic initiator, 1 ~ 3 part of radical initiator, 2 ~ 5 parts of multi-group crosslink agents, 5 ~ 10 parts of fire retarding synergists, 1 ~ 5 part of smoke suppressor, 0.1 ~ 0.5 part of composite antioxidant and 0.5 ~ 1.2 part of lubricant, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtain thermal material, then it is 130 DEG C ~ 145 DEG C in twin screw temperature, screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtain ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin,
Described base-material is for being ethylene, propylene methacrylate copolymers, ethylene-acrylate-carbonyl terpolymer, ethylene methyl acrylate copolymer, ethylene butyl acrylate multipolymer, Low Density Polyethylene, linear low density polyethylene, ethylene-alpha-octylene polymkeric substance, terpolymer EP rubber, styrene series thermoplastic elastomer, glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride graft vinyl acetate copolymer, a kind of or wherein several mixture in maleic anhydride grafted ethene-α-octene polymer and maleic anhydride grafted polyethylene, be mixed by any ratio for during mixture, in wherein said ethylene-vinyl acetate copolymer rubber, the content of VA is 40% ~ 70%, in described paracril, the content of vinyl cyanide is 31% ~ 35%,
Described halogen-free flame retardants is surface modification flame retardant of magnesium hydroxide, surface modified aluminium hydroxide flame retardant or surface modification hypo-aluminum orthophosphate combustion inhibitor;
Described cationic initiator is a kind of or wherein several mixture in diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ethers, is mixed by any ratio for during mixture;
Described radical initiator is benzoin dimethylether, and a kind of or wherein several mixture in 2-hydroxy-2-methyl-1-phenyl-acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2,4 dihydroxyl benzophenone, is mixed by any ratio for during mixture;
Described multi-group crosslink agent is a kind of or wherein several mixture in trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, triallyl cyanurate and cyamelide triallyl, is mixed by any ratio for during mixture;
Described composite antioxidant is phenolic antioxidant, phosphite ester kind antioxidant, phosphoric acid ester oxidation inhibitor and two kinds or wherein several mixtures containing in sulphur ester antioxidant, be mixed by any ratio for during mixture, wherein said phenolic antioxidant is β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, described phosphite ester kind antioxidant is triphenyl phosphite, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, described phosphoric acid ester oxidation inhibitor is triphenylphosphate, described sulphur ester antioxidant is Tyox B or thiodipropionic acid dilauryl osmanthus octadecyl ester.
The flame retardant of magnesium hydroxide of surface modification described in present embodiment, surface modified aluminium hydroxide flame retardant and surface modification hypo-aluminum orthophosphate combustion inhibitor adopt the surface-modifying agent of Dow corning 11-100 to carry out modification, modified particle diameter≤2 μm.
The ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin of present embodiment and traditional high-energy electron beam irradiation are cross-linked, chemically crosslinked, low smoke halogen-free fire retardant polyolefin cable material prepared by crosslinked with silicane technology is compared, this ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin, with the ethylene vinyl acetate copolymer of high vinyl acetate between to for plastic (VA) content more than 40% for main material, add paracril, acrylic acid esters co-polymer improves its oil-proofness, add the initiator system that cationic initiator combines with radical initiator simultaneously, can match with launching more wide wavelength range lamp source, cation light initiator is made to absorb more UV energy, at utmost improve its light-initiated efficiency in halogen-free anti-flaming polyolefin material and degree of uniformity thereof, the obvious cross-linking density improving material, add consistency, mechanical property, flame retardant resistance, processing characteristics etc. that the technique means such as compatilizer, elastomerics, crosslinking coagent, fire retardant, fire retarding synergist, lubricant improves material, develop that the investment of a kind of cross-linking apparatus is low, technique simple (being cross-linked online), production efficiency are high, energy-conserving and environment-protective, ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant polyolefine material that suitability is wide.
Embodiment seven: present embodiment and embodiment six unlike: described cationic initiator is two dodecylbenzene hexafluoro arsenic formic acid salt compounded of iodine, 4, a kind of or wherein several mixture in 4 '-dimethyl diphenyl iodine phosphoric acid salt, phosphofluoric acid triaryl sulphur father-in-law's salt and cationic photoinitiator, is mixed by any ratio for during mixture.Other is identical with embodiment six.
Embodiment eight: present embodiment and embodiment six or seven unlike: described fire retarding synergist is a kind of or wherein several mixture in hydrotalcite, zinc borate, polynite, wollastonite and aluminum silicon powder, is mixed by any ratio for during mixture.Other is identical with embodiment six or seven.
Embodiment nine: one of present embodiment and embodiment six to eight unlike: described smoke suppressor is a kind of or wherein several mixture in molybdenum sesquioxide, Ammonium Heptamolybdate and ammonium octamolybdate, is mixed by any ratio for during mixture.Other is identical with one of embodiment six to eight.
Embodiment ten: one of present embodiment and embodiment six to nine unlike: described lubricant is a kind of or wherein several mixture in stearic acid, Zinic stearas, PE-wax and liquid siloxane polymer, is mixed by any ratio for during mixture.Other is identical with one of embodiment six to nine.
Effect of the present invention is verified by following examples:
Comparative example: a kind of preparation method of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take the ethylene-vinyl acetate copolymer rubber that 50 parts of VA content are 45% by weight, 15 parts of linear low density polyethylenes, 10 parts of glycidyl methacrylate graft polyethylene, 10 parts of maleic anhydride graft vinyl acetate copolymers, 10 parts of maleic anhydride grafted polyethylenes, 5 parts of terpolymer EP rubbers, 120 parts of surface modification flame retardant of magnesium hydroxide, 5 parts of hydrotalcites, 1 part of 2,4 dihydroxyl benzophenone, 2 part 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, 2 parts of trimethylolpropane tris (methyl) acrylate, 0.1 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, 0.3 part of three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, 0.5 part of PE-wax, 2 parts of molybdenum sesquioxides and 0.5 part of stearic acid, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtaining thermal material, is then 130 DEG C ~ 145 DEG C in twin screw temperature, and screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtains ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin.
Embodiment one: a kind of preparation method of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take the ethylene-vinyl acetate copolymer rubber that 50 parts of VA content are 45% by weight, 5 parts of paracrils, 15 parts of linear low density polyethylenes, 5 parts of glycidyl methacrylate graft polyethylene, 10 parts of maleic anhydride graft vinyl acetate copolymers, 10 parts of maleic anhydride grafted polyethylenes, 5 parts of terpolymer EP rubbers, 120 parts of surface modification flame retardant of magnesium hydroxide, 5 parts of hydrotalcites, 1 part of 2,4 dihydroxyl benzophenone, 2 part 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, 2 parts of trimethylolpropane tris (methyl) acrylate, 0.1 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, 0.3 part of three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, 0.5 part of PE-wax, 2 parts of molybdenum sesquioxides and 0.5 part of stearic acid, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtaining thermal material, is then 130 DEG C ~ 145 DEG C in twin screw temperature, and screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtains ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin.
Embodiment two: a kind of preparation method of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take the ethylene-vinyl acetate copolymer rubber that 45 parts of VA content are 45% by weight, 5 parts of paracrils, 10 parts of linear low density polyethylenes, 10 parts of ethylene ethyl acrylate copolymers, 8 parts of glycidyl methacrylate graft polyethylene, 15 parts of maleic anhydride graft vinyl acetate copolymers, 7 parts of maleic anhydride grafted polyethylenes, 125 parts of surface modification flame retardant of magnesium hydroxide, 5 parts of zinc borates, 1.5 parts of benzophenone, 2 portions of phosphofluoric acid triaryl sulphur father-in-law salt, 2 parts of trimethylolpropane tris (methyl) acrylate, 0.15 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, 0.4 portion of triphenyl phosphite, 0.5 part of PE-wax, 2 parts of molybdenum sesquioxides and 0.5 part of Zinic stearas, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtaining thermal material, is then 130 DEG C ~ 145 DEG C in twin screw temperature, and screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtains ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin.
Embodiment three: a kind of preparation method of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take the ethylene-vinyl acetate copolymer rubber that 40 parts of VA content are 45% by weight, 5 parts of paracrils, 10 parts of linear low density polyethylenes, 5 parts of ethylene-acrylate-carbonyl terpolymers, 15 parts of maleic anhydride graft vinyl acetate copolymers, 10 parts of maleic anhydride grafted polyethylenes, 5 parts of maleic anhydride grafted ethene-α-octene polymer, 10 parts of ethylene-alpha-octylene polymkeric substance, 130 parts of surface modification flame retardant of magnesium hydroxide, 5 parts of aluminum silicon powders, 1 part of 2,4 dihydroxyl benzophenone, 2 part 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, 2.5 parts of cyamelide triallyls, 0.1 part of β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, 0.3 part of Tyox B, 0.4 part of PE-wax, 2 parts of molybdenum sesquioxides and 0.8 part of Zinic stearas, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtaining thermal material, is then 130 DEG C ~ 145 DEG C in twin screw temperature, and screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtains ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin.
Embodiment four: a kind of preparation method of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take the ethylene-vinyl acetate copolymer rubber that 55 parts of VA content are 45% by weight, 20 parts of linear low density polyethylenes, 5 parts of ethylene methyl acrylate copolymers, 10 parts of maleic anhydride graft vinyl acetate copolymers, 5 parts of maleic anhydride grafted polyethylenes, 5 parts of ethylene-alpha-octylene polymkeric substance, 80 parts of surface modification flame retardant of magnesium hydroxide, 50 parts of surface modified aluminium hydroxide flame retardants, 5 parts of wollastonites, 2 parts of 2-hydroxy-2-methyl-1-phenyl-acetones, 2 parts of cationic photoinitiators, 1 part of triallyl cyanurate, 1.5 parts of triallyl cyanurate, 0.2 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, 0.3 part of Tyox B, 0.6 part of liquid siloxane polymer and 2 parts of molybdenum sesquioxides, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtain thermal material, then it is 130 DEG C ~ 145 DEG C in twin screw temperature, screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtains ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin.
The ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin that comparative example, embodiment one, embodiment two, embodiment three and embodiment four are obtained, melting extrudes on conductive cable cores, enter immediately in ultraviolet light irradiation cross-linking apparatus and carry out ultraviolet light irradiation cross-linking to the material under molten state, crosslinking time is 5 seconds.Then with reference to GB/T12528-2008 ac rated voltage 3kV and following cable for rail transit vehicles, detected result is carried out in table 1 to its over-all properties.
The physicals detected result that electric wire after table 1 is crosslinked obtains after testing:
As can be seen from Table 1, interpolation paracril and acrylic polymer can improve its oil resistance, and the obtained complete conformance with standard requirement of each performance index of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin.
Claims (10)
1. a ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin, is characterized in that ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin is made up of 100 parts of base-materials, 120 ~ 130 parts of halogen-free flame retardantss, 1 ~ 3 part of cationic initiator, 1 ~ 3 part of radical initiator, 2 ~ 5 parts of multi-group crosslink agents, 5 ~ 10 parts of fire retarding synergists, 1 ~ 5 part of smoke suppressor, 0.1 ~ 0.5 part of composite antioxidant and 0.5 ~ 1.2 part of lubricant by weight;
Described base-material is for being ethylene, propylene methacrylate copolymers, ethylene-acrylate-carbonyl terpolymer, ethylene methyl acrylate copolymer, ethylene butyl acrylate multipolymer, Low Density Polyethylene, linear low density polyethylene, ethylene-alpha-octylene polymkeric substance, terpolymer EP rubber, styrene series thermoplastic elastomer, glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride graft vinyl acetate copolymer, a kind of or wherein several mixture in maleic anhydride grafted ethene-α-octene polymer and maleic anhydride grafted polyethylene, in wherein said ethylene-vinyl acetate copolymer rubber, the content of VA is 40% ~ 70%, in described paracril, the content of vinyl cyanide is 31% ~ 35%,
Described halogen-free flame retardants is surface modification flame retardant of magnesium hydroxide, surface modified aluminium hydroxide flame retardant or surface modification hypo-aluminum orthophosphate combustion inhibitor;
Described cationic initiator is a kind of or wherein several mixture in diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ethers;
Described radical initiator is benzoin dimethylether, a kind of or wherein several mixture in 2-hydroxy-2-methyl-1-phenyl-acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2,4 dihydroxyl benzophenone;
Described multi-group crosslink agent is a kind of or wherein several mixture in trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, triallyl cyanurate and cyamelide triallyl;
Described composite antioxidant is phenolic antioxidant, phosphite ester kind antioxidant, phosphoric acid ester oxidation inhibitor and two kinds or wherein several mixtures containing in sulphur ester antioxidant, wherein said phenolic antioxidant is β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, described phosphite ester kind antioxidant is triphenyl phosphite, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, described phosphoric acid ester oxidation inhibitor is triphenylphosphate, described sulphur ester antioxidant is Tyox B or thiodipropionic acid dilauryl osmanthus octadecyl ester.
2. a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 1, it is characterized in that described cationic initiator is a kind of or wherein several mixture in two dodecylbenzene hexafluoro arsenic formic acid salt compounded of iodine, 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, phosphofluoric acid triaryl sulphur father-in-law's salt and cationic photoinitiator.
3. a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 1, is characterized in that described fire retarding synergist is a kind of or wherein several mixture in hydrotalcite, zinc borate, polynite, wollastonite and aluminum silicon powder.
4. a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 1, is characterized in that described smoke suppressor is a kind of or wherein several mixture in molybdenum sesquioxide, Ammonium Heptamolybdate and ammonium octamolybdate.
5. a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 1, is characterized in that described lubricant is a kind of or wherein several mixture in stearic acid, Zinic stearas, PE-wax and liquid siloxane polymer.
6. the preparation method of a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin as claimed in claim 1, is characterized in that the preparation method of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin carries out according to the following steps:
Take 100 parts of base-materials by weight, 120 ~ 130 parts of halogen-free flame retardantss, 1 ~ 3 part of cationic initiator, 1 ~ 3 part of radical initiator, 2 ~ 5 parts of multi-group crosslink agents, 5 ~ 10 parts of fire retarding synergists, 1 ~ 5 part of smoke suppressor, 0.1 ~ 0.5 part of composite antioxidant and 0.5 ~ 1.2 part of lubricant, then drop in mixing room, start kneader, until discharging after plasticizing evenly, obtain thermal material, then it is 130 DEG C ~ 145 DEG C in twin screw temperature, screw speed is under the condition of 280r/min ~ 300r/min, thermal material is sent into twin screw extruder again after mixing plasticizing evenly, again sending into temperature is extruding pelletization in the single screw extrusion machine of 135 DEG C ~ 155 DEG C, obtain ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin,
Described base-material is for being ethylene, propylene methacrylate copolymers, ethylene-acrylate-carbonyl terpolymer, ethylene methyl acrylate copolymer, ethylene butyl acrylate multipolymer, Low Density Polyethylene, linear low density polyethylene, ethylene-alpha-octylene polymkeric substance, terpolymer EP rubber, styrene series thermoplastic elastomer, glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride graft vinyl acetate copolymer, a kind of or wherein several mixture in maleic anhydride grafted ethene-α-octene polymer and maleic anhydride grafted polyethylene, in wherein said ethylene-vinyl acetate copolymer rubber, the content of VA is 40% ~ 70%, in described paracril, the content of vinyl cyanide is 31% ~ 35%,
Described halogen-free flame retardants is surface modification flame retardant of magnesium hydroxide, surface modified aluminium hydroxide flame retardant or surface modification hypo-aluminum orthophosphate combustion inhibitor;
Described cationic initiator is a kind of or wherein several mixture in diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ethers;
Described radical initiator is benzoin dimethylether, a kind of or wherein several mixture in 2-hydroxy-2-methyl-1-phenyl-acetone, alpha-hydroxyalkyl benzophenone, benzophenone and 2,4 dihydroxyl benzophenone;
Described multi-group crosslink agent is a kind of or wherein several mixture in trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, triallyl cyanurate and cyamelide triallyl;
Described composite antioxidant is phenolic antioxidant, phosphite ester kind antioxidant, phosphoric acid ester oxidation inhibitor and two kinds or wherein several mixtures containing in sulphur ester antioxidant, wherein said phenolic antioxidant is β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid or four [methyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, described phosphite ester kind antioxidant is triphenyl phosphite, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester, described phosphoric acid ester oxidation inhibitor is triphenylphosphate, described sulphur ester antioxidant is Tyox B or thiodipropionic acid dilauryl osmanthus octadecyl ester.
7. the preparation method of a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 6, it is characterized in that described cationic initiator is a kind of or wherein several mixture in two dodecylbenzene hexafluoro arsenic formic acid salt compounded of iodine, 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, phosphofluoric acid triaryl sulphur father-in-law's salt and cationic photoinitiator.
8. the preparation method of a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 6, is characterized in that described fire retarding synergist is a kind of or wherein several mixture in hydrotalcite, zinc borate, polynite, wollastonite and aluminum silicon powder.
9. the preparation method of a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 6, is characterized in that described smoke suppressor is a kind of or wherein several mixture in molybdenum sesquioxide, Ammonium Heptamolybdate and ammonium octamolybdate.
10. the preparation method of a kind of ultraviolet light cross-linking oil-resistant low-smoke halogen-free flame-retardant cable material of polyolefin according to claim 6, is characterized in that described lubricant is a kind of or wherein several mixture in stearic acid, Zinic stearas, PE-wax and liquid siloxane polymer.
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