CN103509229A - Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material for photovoltaic cables - Google Patents

Irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material for photovoltaic cables Download PDF

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CN103509229A
CN103509229A CN201310473972.8A CN201310473972A CN103509229A CN 103509229 A CN103509229 A CN 103509229A CN 201310473972 A CN201310473972 A CN 201310473972A CN 103509229 A CN103509229 A CN 103509229A
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parts
powder
cable material
free flame
smoke halogen
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CN103509229B (en
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谢华
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Wenzhou Yuelai Electron Accelerator Application Co.,Ltd.
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Lvbao Cable Group Co Ltd
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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
    • C08L23/06—Polyethene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Abstract

The invention provides an irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin cable material for photovoltaic cables. The cable material is prepared from the following raw materials in parts by weight: 40-50 parts of polyethylene (PE), 30-40 parts of polyvinyl chloride resin, 20-30 parts of CSM2305, 10-12 parts of ethylene-acrylate copolymer, 10-15 parts of epichlorohydrin rubber T3100, 5-10 parts of epoxidized soybean oil, 2-3 parts of carbonyl iron powder, 10-12 parts of high abrasion carbon black N330, 5-10 parts of light calcium carbonate, 1-2 parts of zinc oxide, 5-10 parts of wollastonite powder, 4-5 parts of vermiculite, 1-2 parts of polytetrafluoroethylene micro powder, 1-2 parts of graphite, 1-2 parts of nano boron carbide, 2-3 parts of ferric oxide, 0.1-0.2 part of UV-O, 0.1-0.2 part of UV-53, 0.1-0.2 part of flame retardant TBC, 10-12 parts of aluminium hypophosphite, 5-8 parts of decabromodiphenyl ether, 8-10 parts of dioctyl terephthalate, 6-8 parts of trioctyl trimellitate, 8-10 parts of triethyl citrate, 1-2 parts of calcium stearate, 0.2-0.4 part of stearic acid, 0.1-0.2 part of oxidized polyethlene wax, 0.2-0.3 part of ethylene bis stearamide, 0.1-0.2 part of DCP, and 12-15 parts of modified filler. The cable material has the characteristics of high flame retardance, high ultraviolet resistance and high ageing resistance, and meanwhile, has a good mechanical property, and is environment-friendly.

Description

A kind of photovoltaic cable irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS
Technical field
The present invention relates to CABLE MATERIALS field, be specifically related to a kind of photovoltaic cable irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS.
Background technology
Electric wire has the effect of power transmission and information conveyance, in people's life with in producing, plays an important role.Design and prepare low cigarette, low toxicity, possessing again the CABLE MATERIALS of excellent fire-retardancy and insulating property simultaneously, becoming the focus of current fire-retardant research.Traditional magnesium hydroxide and aluminium hydroxide based flame retardant, although can give the flame retardant properties that material is good, but, because the matrix resin of most of CABLE MATERIALS is nonpolar polyolefins polymer,, the consistency of aluminium hydroxide is poor, tend to reduce mechanical property and the processing characteristics of material with the magnesium hydroxide of polarity.Work out and both there is good flame retardant properties, there is environmental-protecting performance simultaneously, the CABLE MATERIALS material of good machinability, good insulating property becomes the direction of CABLE MATERIALS development, the present invention is by adding modified filler, greatly improve the consistency of storeroom, when having improved the machining property of CABLE MATERIALS, also guaranteed the anti-flaming environment-friendly of CABLE MATERIALS.
Summary of the invention
The invention provides irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS and preparation method thereof for a kind of photovoltaic cable.The cable being processed into by CABLE MATERIALS of the present invention has good, the low cigarette of ultraviolet resistance, ageing-resistant, and flame retardant properties is good.
The technical solution used in the present invention is:
Use an irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, it is characterized in that, by the component raw material preparation of following weight part, obtained: polythene PE 40-50, polyvinyl chloride (PVC) RESINS 30-40, chlorosulfonated polyethylene rubber CSM2305 20-30, ethene and acrylate copolymer 10-12, chlorohydrin rubber T3100 10-15 epoxy soybean oil 5-10, carbonyl iron dust 2-3, high abrasion furnace carbon black N330 10-12, light calcium carbonate 5-10, zinc oxide 1-2, wollastonite powder 5-10, vermiculite 4-5, ptfe micropowder 1-2, graphite 1-2, nano boron carbide 1-2, ferric oxide 2-3, UV light absorber UV-O 0.1-0.2, ultraviolet absorbent UV-531 0.1-0.2, fire retardant TBC 0.1-0.2, hypo-aluminum orthophosphate 10-12, decabromodiphynly oxide 5-8, dioctyl terephthalate 8-10, trioctyl trimellitate 6-8, triethyl citrate 8-10, calcium stearate 1-2, stearic acid 0.2-0.4, oxidized polyethlene wax 0.1-0.2, ethylene bis stearamide 0.2-0.3, dicumyl peroxide DCP0.1-0.2, modified filler 12-15,
Described modified filler is to be prepared and obtained by following method: a. takes off the raw material of row weight part: kaolin 180-190, medical stone 30-34, nano-sized carbon 1-2, xitix 1-2, coix seed oil 1-2, aluminum nitride powder 1-2, Zinc Gluconate 2-3, jade powder 2-3, polyisobutene 2-3, aluminate coupling agent DL-411 1-2, stearic acid 2-3, antioxidant 1010 1-2;
B, kaolin, medical stone are calcined to 5-6h at 450-480 ℃, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, the hydrochloric acid soln that adds 12-15%, adjusting pH value is 4-5, ageing 10-15 hour, and it is neutral that repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH, filter, dry and obtain filler powder;
C, above-mentioned gained powder is mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, obtain.
Described photovoltaic cable irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, it is characterized in that, by the component raw material preparation of following weight part, obtained: polythene PE 45, polyvinyl chloride (PVC) RESINS 35, chlorosulfonated polyethylene rubber CSM2305 26, ethene and acrylate copolymer 11, chlorohydrin rubber T3100 13, epoxy soybean oil 7, carbonyl iron dust 3, high abrasion furnace carbon black N330 11, light calcium carbonate 8, zinc oxide 1, wollastonite powder 6, vermiculite 4, ptfe micropowder 1, graphite 1, nano boron carbide 1, ferric oxide 2, UV light absorber UV-O 0.1, ultraviolet absorbent UV-531 0.2, fire retardant TBC 0.1, hypo-aluminum orthophosphate 12, decabromodiphynly oxide 7, dioctyl terephthalate 9, trioctyl trimellitate 7, triethyl citrate 9, calcium stearate 2, stearic acid 0.3, oxidized polyethlene wax 0.1, ethylene bis stearamide 0.3, dicumyl peroxide DCP 0.1, modified filler 14,
Described modified filler is to be prepared and obtained by following method: a. takes off the raw material of row weight part: kaolin 185, medical stone 32, nano-sized carbon 1, xitix 1, coix seed oil 2, aluminum nitride powder 2, Zinc Gluconate 2, jade powder 3, polyisobutene 2, aluminate coupling agent DL-411 1, stearic acid 2, antioxidant 1010 1;
B, kaolin, medical stone are calcined to 5-6h at 450-480 ℃, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, the hydrochloric acid soln that adds 12-15%, adjusting pH value is 4-5, ageing 10-15 hour, and it is neutral that repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH, filter, dry and obtain filler powder;
C, above-mentioned gained powder is mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, obtain.
The preparation method of CABLE MATERIALS of the present invention:
By formula rate, take each constitutive material, constitutive material is dropped into homogenizer mixing 10-15miu, blowing, then the compound mixing is carried out to high-energy electron beam irradiation, irradiation energy is 180kGy, compound after irradiation is put in twin screw extruder, extruding pelletization, after entering again and being dried in hot air dryer, obtain photovoltaic cable irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, while extruding, twin screw extruder temperature setting is set to: 114 ℃ of feeding sections, 175 ℃ of melt zones, melt conveying zone 175-182 ℃, 190 ℃ of mixing sections, 185 ℃ of homogenizing zones, 185 ℃ of head metering zones.
Beneficial effect
The polyolefin resin compound system of the selected high-quality of the present invention and adopted adding of the composite synergistic system of fire retardant and modified filler, the consistency that material itself is had between extremely excellent flame retardant properties, anti-ultraviolet aging performance, while formula materials is fine, mechanical property is good, that the electric wire processing by this CABLE MATERIALS has is fire-retardant, uvioresistant, ageing-resistant characteristic, has good mechanical property, environmental protection simultaneously.
Embodiment
Use an irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, by the component raw material preparation of following weight (kg), obtained:
Polythene PE 45, polyvinyl chloride (PVC) RESINS 35, chlorosulfonated polyethylene rubber CSM2305 26, ethene and acrylate copolymer 11, chlorohydrin rubber T3100 13, epoxy soybean oil 7, carbonyl iron dust 3, high abrasion furnace carbon black N330 11, light calcium carbonate 8, zinc oxide 1, wollastonite powder 6, vermiculite 4, ptfe micropowder 1, graphite 1, nano boron carbide 1, ferric oxide 2, UV light absorber UV-O 0.1, ultraviolet absorbent UV-531 0.2, fire retardant TBC 0.1, hypo-aluminum orthophosphate 12, decabromodiphynly oxide 7, dioctyl terephthalate 9, trioctyl trimellitate 7, triethyl citrate 9, calcium stearate 2, stearic acid 0.3, oxidized polyethlene wax 0.1, ethylene bis stearamide 0.3, dicumyl peroxide DCP 0.1, modified filler 14,
Wherein, modified filler is to be prepared and obtained by following method:
Modified filler is to be prepared and obtained by following method: a. takes off the raw material of row weight part: kaolin 185, medical stone 32, nano-sized carbon 1, xitix 1, coix seed oil 2, aluminum nitride powder 2, Zinc Gluconate 2, jade powder 3, polyisobutene 2, aluminate coupling agent DL-411 1, stearic acid 2, antioxidant 1010 1;
B, kaolin, medical stone are calcined to 5-6h at 450-480 ℃, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, the hydrochloric acid soln that adds 12-15%, adjusting pH value is 4-5, ageing 10-15 hour, and it is neutral that repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH, filter, dry and obtain filler powder;
C, above-mentioned gained powder is mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, obtain.
The preparation method of irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS for photovoltaic cable:
By formula rate, take each constitutive material, constitutive material is dropped into homogenizer mixing 10-15miu, blowing, then the compound mixing is carried out to high-energy electron beam irradiation, irradiation energy is 180kGy, compound after irradiation is put in twin screw extruder, extruding pelletization, after entering again and being dried in hot air dryer, obtain photovoltaic cable irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, while extruding, twin screw extruder temperature setting is set to: 114 ℃ of feeding sections, 175 ℃ of melt zones, melt conveying zone 175-182 ℃, 190 ℃ of mixing sections, 185 ℃ of homogenizing zones, 185 ℃ of head metering zones.
The performance test results of the CABLE MATERIALS that the present embodiment makes is as following table:
Figure BDA0000394411330000041

Claims (2)

1. a photovoltaic cable irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, is characterized in that, is obtained: polythene PE 40-50 by the component raw material preparation of following weight part, polyvinyl chloride (PVC) RESINS 30-40, chlorosulfonated polyethylene rubber CSM2305 20-30, ethene and acrylate copolymer 10-12, chlorohydrin rubber T3100 10-15 epoxy soybean oil 5-10, carbonyl iron dust 2-3, high abrasion furnace carbon black N330 10-12, light calcium carbonate 5-10, zinc oxide 1-2, wollastonite powder 5-10, vermiculite 4-5, ptfe micropowder 1-2, graphite 1-2, nano boron carbide 1-2, ferric oxide 2-3, UV light absorber UV-O 0.1-0.2, ultraviolet absorbent UV-531 0.1-0.2, fire retardant TBC 0.1-0.2, hypo-aluminum orthophosphate 10-12, decabromodiphynly oxide 5-8, dioctyl terephthalate 8-10, trioctyl trimellitate 6-8, triethyl citrate 8-10, calcium stearate 1-2, stearic acid 0.2-0.4, oxidized polyethlene wax 0.1-0.2, ethylene bis stearamide 0.2-0.3, dicumyl peroxide DCP0.1-0.2, modified filler 12-15,
Described modified filler is to be prepared and obtained by following method: a. takes off the raw material of row weight part: kaolin 180-190, medical stone 30-34, nano-sized carbon 1-2, xitix 1-2, coix seed oil 1-2, aluminum nitride powder 1-2, Zinc Gluconate 2-3, jade powder 2-3, polyisobutene 2-3, aluminate coupling agent DL-411 1-2, stearic acid 2-3, antioxidant 1010 1-2;
B, kaolin, medical stone are calcined to 5-6h at 450-480 ℃, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, the hydrochloric acid soln that adds 12-15%, adjusting pH value is 4-5, ageing 10-15 hour, and it is neutral that repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH, filter, dry and obtain filler powder;
C, above-mentioned gained powder is mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, obtain.
2. photovoltaic cable according to claim 1 irradiation crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS, it is characterized in that, by the component raw material preparation of following weight part, obtained: polythene PE 45, polyvinyl chloride (PVC) RESINS 35, chlorosulfonated polyethylene rubber CSM2305 26, ethene and acrylate copolymer 11, chlorohydrin rubber T3100 13, epoxy soybean oil 7, carbonyl iron dust 3, high abrasion furnace carbon black N330 11, light calcium carbonate 8, zinc oxide 1, wollastonite powder 6, vermiculite 4, ptfe micropowder 1, graphite 1, nano boron carbide 1, ferric oxide 2, UV light absorber UV-O 0.1, ultraviolet absorbent UV-531 0.2, fire retardant TBC 0.1, hypo-aluminum orthophosphate 12, decabromodiphynly oxide 7, dioctyl terephthalate 9, trioctyl trimellitate 7, triethyl citrate 9, calcium stearate 2, stearic acid 0.3, oxidized polyethlene wax 0.1, ethylene bis stearamide 0.3, dicumyl peroxide DCP 0.1, modified filler 14,
Described modified filler is to be prepared and obtained by following method: a. takes off the raw material of row weight part: kaolin 185, medical stone 32, nano-sized carbon 1, xitix 1, coix seed oil 2, aluminum nitride powder 2, Zinc Gluconate 2, jade powder 3, polyisobutene 2, aluminate coupling agent DL-411 1, stearic acid 2, antioxidant 1010 1;
B, kaolin, medical stone are calcined to 5-6h at 450-480 ℃, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, the hydrochloric acid soln that adds 12-15%, adjusting pH value is 4-5, ageing 10-15 hour, and it is neutral that repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH, filter, dry and obtain filler powder;
C, above-mentioned gained powder is mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, obtain.
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