CN108485124A - A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness and preparation method thereof - Google Patents
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness and preparation method thereof Download PDFInfo
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of fire-retardant high halogen-free environmental CABLE MATERIALSs of toughness and preparation method thereof, are related to CABLE MATERIALS field, including the raw material of following parts by weight meter：1.5 2.8 parts of 30 40 parts of polyvinyl chloride resin, 15 25 parts of phenolic resin, 8 16 parts of maleic anhydride inoculated polypropylene, 6 12 parts of diatomite, 5 10 parts of mica powder, 36 parts of saponite powder, 6 12 parts of polypropylene fibre, 47 parts of silicon carbide, 24 parts of carbon black, 35 parts of chitin, 46 parts of nano-titanium dioxide, 35 parts of antimony oxide, 0.8 1.5 parts of coupling agent, 1.2 2.5 parts of fire retardant and antioxidant；CABLE MATERIALS of the present invention has good anti-flammability and toughness, and stretch-resistance and fracture resistance are excellent, is free of any halogen species, environmentally protective, preparation method is simple, easy to produce.
Description
Technical field
The present invention relates to CABLE MATERIALS fields, and in particular to a kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness and its preparation side
Method.
Background technology
Line cable insulation and sheath are commonly called as CABLE MATERIALS with plastics, and which includes a variety of kinds such as rubber, plastics, nylon.
CABLE MATERIALS manufacturing enterprise is with cable manufacturing enterprise for user, there is the market of CABLE MATERIALS as long as live wire cabling requirements.Electric wire
In cable product insulating layer mouth is almost required in addition to the bare wires product such as steel-cored aluminium strand, electromagnetic wire.China's live wire electricity at present
Nearly 5000 of cable manufacturing enterprise, and have upgrading urban and rural power grids, development of the West Regions and communications facility large area upgrading to electric wire
The great demand of cable product, thus from the point of view of for a period of time, CABLE MATERIALS has extensive market development foreground in China.
As society is more and more closer to the concern of fire hazard, fireproofing of cable performance also requires higher.The prior art
In CABLE MATERIALS be mainly polyvinyl chloride cable material, the not high disadvantage of anti-flammability, and while burning discharge a large amount of pernicious gas,
Pollute environment.
Invention content
For problems of the prior art, the present invention provides a kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness and its
Preparation method, CABLE MATERIALS of the present invention have good anti-flammability and toughness, and stretch-resistance and fracture resistance are excellent, are free of any halogen
Plain substance, environmentally protective, preparation method is simple, easy to produce.
In order to achieve the above object, the present invention is achieved through the following technical solutions：
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, includes the raw material of following parts by weight meter：
30-40 parts of polyvinyl chloride resin, 15-25 parts of phenolic resin, 8-16 parts of maleic anhydride inoculated polypropylene, 6-12 parts of diatomite,
5-10 parts of mica powder, 3-6 parts of saponite powder, 6-12 parts of polypropylene fibre, 4-7 parts of silicon carbide, 2-4 parts of carbon black, 3-5 parts of chitin,
4-6 parts of nano-titanium dioxide, 3-5 parts of antimony oxide, 0.8-1.5 parts of coupling agent, 1.2-2.5 parts of fire retardant and antioxidant 1.5-
2.8 part.
Preferably, include the raw material of following parts by weight meter：33-37 parts of polyvinyl chloride resin, 18-22 parts of phenolic resin, maleic anhydride
12-14 parts of graft polypropylene, 8-10 parts of diatomite, 7-9 parts of mica powder, 4-5 parts of saponite powder, 8-10 parts of polypropylene fibre, carbonization
5-6 parts of silicon, 2.5-3.5 parts of carbon black, 3-4 parts of chitin, 4.5-5.5 parts of nano-titanium dioxide, 3.5-4.5 parts of antimony oxide,
2.1-2.4 parts of 1.2-1.4 parts of coupling agent, 1.8-2.2 parts of fire retardant and antioxidant.
Preferably, include the raw material of following parts by weight meter：35 parts of polyvinyl chloride resin, 20 parts of phenolic resin, maleic anhydride grafting are poly-
13 parts of propylene, 9 parts of diatomite, 8 parts of mica powder, 4.5 parts of saponite powder, 9 parts of polypropylene fibre, 5.5 parts of silicon carbide, 3 parts of carbon black, first
2.2 parts of 3.5 parts of shell element, 5 parts of nano-titanium dioxide, 4 parts of antimony oxide, 1.3 parts of coupling agent, 2 parts of fire retardant and antioxidant.
Preferably, the coupling agent is silane coupling agent or titanate coupling agent.
Preferably, it is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite that the fire retardant, which is the fire retardant,
According to mass ratio 1:1:1:3:2, which drift along or through, is combined into.
Preferably, the antioxidant is 2,6-di-tert-butyl p-cresol, 4,4- xenyls di 2 ethylhexyl phosphonic acid, four (2,4- di-t-butyls
Phenyl) one kind or several in ester, diphosphorous acid distearyl acid pentaerythritol ester and phosphorous acid three (2,4- di-tert-butyl-phenyls) ester
Kind combines.
A kind of preparation method of the above-mentioned fire-retardant high halogen-free environmental CABLE MATERIALS of toughness is also disclosed in the present invention, specifically, packet
Include following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide
It is put into high-speed mixer with antimony oxide, 80-100 degrees Celsius is warming up to, after mixing dehumidifies 10-15 minutes, successively to height
Fire retardant, antioxidant and coupling agent are added in fast mixing machine, after mixing 3-5 minutes, is cooled to 50-60 degrees Celsius, puts into PVC trees
Fat, phenolic resin and maleic anhydride inoculated polypropylene mix 5-10 minutes to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet is placed in 80-
It is 4-6 hours dry in 100 degrees Celsius of baking oven, it is cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
The present invention has following advantageous effect：
(1) CABLE MATERIALS of the present invention has good anti-flammability and toughness, and stretch-resistance and fracture resistance are excellent, without any
Halogen species, environmentally protective, preparation method is simple, easy to produce.
(2) maleic anhydride inoculated polypropylene is added in raw material of the present invention as primary raw material, maleic anhydride grafting poly- third
Alkene can become the bridge for promoting polar material and non-polar material cementability and compatibility, can be with inorganic material in reinforcing material
With the cohesive force of high molecular polymer, the stability of reinforcing material structure.
(3) polypropylene fibre is added in material of the present invention, polypropylene fibre has intensity height, good toughness, chemicals-resistant
Property and microbial resistance, to enhance the toughness, stretch-resistance and fold resistance of CABLE MATERIALS.
Specific implementation mode
The specific implementation mode of the present invention is further described with reference to embodiment, following embodiment is only used for more
Technical scheme of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, includes the raw material of following parts by weight meter：
30 parts of polyvinyl chloride resin, 15 parts of phenolic resin, 8 parts of maleic anhydride inoculated polypropylene, 6 parts of diatomite, 5 parts of mica powder, soap
3 parts of mountain flour, 6 parts of polypropylene fibre, 4 parts of silicon carbide, 2 parts of carbon black, 3 parts of chitin, 4 parts of nano-titanium dioxide, antimony oxide 3
Part, 0.8 part of coupling agent, 1.2 parts of fire retardant and 1.5 parts of antioxidant.
Coupling agent is silane coupling agent.
It is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite according to mass ratio 1 that fire retardant, which is the fire retardant,:
1:1:3:2, which drift along or through, is combined into.
Antioxidant is that DBPC 2,6 ditertiary butyl p cresol and 4,4- xenyls di 2 ethylhexyl phosphonic acid four (2,4- di-tert-butyl-phenyls) ester are pressed
According to mass ratio 1:1 mixing composition.
A kind of preparation method of the above-mentioned fire-retardant high halogen-free environmental CABLE MATERIALS of toughness is also disclosed in the present embodiment, specifically,
Include the following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide
It is put into high-speed mixer with antimony oxide, is warming up to 80 degrees Celsius, mixing dehumidifies after ten minutes, successively to high-speed mixer
Middle addition fire retardant, antioxidant and coupling agent are cooled to 50 degrees Celsius after mixing 3 minutes, input polyvinyl chloride resin, phenolic resin and
Maleic anhydride inoculated polypropylene mixes 5 minutes to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet, which is placed in 80, to be taken the photograph
It is 4 hours dry in the baking oven of family name's degree, it is cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
Embodiment 2
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, includes the raw material of following parts by weight meter：
40 parts of polyvinyl chloride resin, 25 parts of phenolic resin, 16 parts of maleic anhydride inoculated polypropylene, 12 parts of diatom, 10 parts of mica powder,
6 parts of saponite powder, 12 parts of polypropylene fibre, 7 parts of silicon carbide, 4 parts of carbon black, 5 parts of chitin, 6 parts of nano-titanium dioxide, three oxidations two
2.8 parts of 5 parts of antimony, 1.5 parts of coupling agent, 2.5 parts of fire retardant and antioxidant.
Coupling agent is titanate coupling agent.
It is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite according to mass ratio 1 that fire retardant, which is the fire retardant,:
1:1:3:2, which drift along or through, is combined into.
Antioxidant is diphosphorous acid distearyl acid pentaerythritol ester.
A kind of preparation method of the above-mentioned fire-retardant high halogen-free environmental CABLE MATERIALS of toughness is also disclosed in the present embodiment, specifically,
Include the following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide
It is put into high-speed mixer with antimony oxide, 100 degrees Celsius is warming up to, after mixing dehumidifies 15 minutes, successively to mixed at high speed
Fire retardant, antioxidant and coupling agent are added in machine, mixing after five minutes, is cooled to 60 degrees Celsius, input polyvinyl chloride resin, phenolic resin
And maleic anhydride inoculated polypropylene, 10 minutes are mixed to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet is placed in 100
Degree Celsius baking oven in, dry 6 hours, be cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
Embodiment 3
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, includes the raw material of following parts by weight meter：
33 parts of polyvinyl chloride resin, 18 parts of phenolic resin, 12 parts of maleic anhydride inoculated polypropylene, 8 parts of diatomite, 7 parts of mica powder,
4 parts of saponite powder, 8 parts of polypropylene fibre, 5 parts of silicon carbide, 2.5 parts of carbon black, 3 parts of chitin, 4.5 parts of nano-titanium dioxide, three oxygen
Change 2.1 parts of 3.5 parts of two antimony, 1.2 parts of coupling agent, 1.8 parts of fire retardant and antioxidant.
Coupling agent is silane coupling agent.
It is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite according to mass ratio 1 that fire retardant, which is the fire retardant,:
1:1:3:2, which drift along or through, is combined into.
Antioxidant is 4,4- xenyls di 2 ethylhexyl phosphonic acid four (2,4- di-tert-butyl-phenyls) ester.
A kind of preparation method of the above-mentioned fire-retardant high halogen-free environmental CABLE MATERIALS of toughness is also disclosed in the present embodiment, specifically,
Include the following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide
It is put into high-speed mixer with antimony oxide, 85 degrees Celsius is warming up to, after mixing dehumidifies 12 minutes, successively to high-speed mixer
Middle addition fire retardant, antioxidant and coupling agent are cooled to 55 degrees Celsius after mixing 4 minutes, input polyvinyl chloride resin, phenolic resin and
Maleic anhydride inoculated polypropylene mixes 8 minutes to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet, which is placed in 90, to be taken the photograph
It is 5 hours dry in the baking oven of family name's degree, it is cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
Embodiment 4
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, includes the raw material of following parts by weight meter：
37 parts of polyvinyl chloride resin, 22 parts of phenolic resin, 14 parts of maleic anhydride inoculated polypropylene, 10 parts of diatomite, 9 parts of mica powder,
5 parts of saponite powder, 10 parts of polypropylene fibre, 6 parts of silicon carbide, 3.5 parts of carbon black, 4 parts of chitin, 5.5 parts of nano-titanium dioxide, three oxygen
Change 2.4 parts of 4.5 parts of two antimony, 1.4 parts of coupling agent, 2.2 parts of fire retardant and antioxidant.
Coupling agent is titanate coupling agent.
It is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite according to mass ratio 1 that fire retardant, which is the fire retardant,:
1:1:3:2, which drift along or through, is combined into.
Antioxidant is diphosphorous acid distearyl acid pentaerythritol ester.
A kind of preparation method of the above-mentioned fire-retardant high halogen-free environmental CABLE MATERIALS of toughness is also disclosed in the present embodiment, specifically,
Include the following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide
It is put into high-speed mixer with antimony oxide, 90 degrees Celsius is warming up to, after mixing dehumidifies 13 minutes, successively to high-speed mixer
Middle addition fire retardant, antioxidant and coupling agent are cooled to 56 degrees Celsius after mixing 4 minutes, input polyvinyl chloride resin, phenolic resin and
Maleic anhydride inoculated polypropylene mixes 8 minutes to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet, which is placed in 90, to be taken the photograph
It is 5.5 hours dry in the baking oven of family name's degree, it is cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
Embodiment 5
A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, includes the raw material of following parts by weight meter：
35 parts of polyvinyl chloride resin, 20 parts of phenolic resin, 13 parts of maleic anhydride inoculated polypropylene, 9 parts of diatomite, 8 parts of mica powder,
4.5 parts of saponite powder, 9 parts of polypropylene fibre, 5.5 parts of silicon carbide, 3 parts of carbon black, 3.5 parts of chitin, 5 parts of nano-titanium dioxide, three
Aoxidize 2.2 parts of 4 parts of two antimony, 1.3 parts of coupling agent, 2 parts of fire retardant and antioxidant.
Coupling agent is titanate coupling agent.
It is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite according to mass ratio 1 that fire retardant, which is the fire retardant,:
1:1:3:2, which drift along or through, is combined into.
Antioxidant is phosphorous acid three (2,4- di-tert-butyl-phenyls) ester.
A kind of preparation method of the above-mentioned fire-retardant high halogen-free environmental CABLE MATERIALS of toughness is also disclosed in the present embodiment, specifically,
Include the following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide
It is put into high-speed mixer with antimony oxide, 95 degrees Celsius is warming up to, after mixing dehumidifies 13 minutes, successively to high-speed mixer
Middle addition fire retardant, antioxidant and coupling agent are cooled to 56 degrees Celsius after mixing 4 minutes, input polyvinyl chloride resin, phenolic resin and
Maleic anhydride inoculated polypropylene mixes 8 minutes to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet, which is placed in 95, to be taken the photograph
It is 5 hours dry in the baking oven of family name's degree, it is cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (7)
1. a kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness, which is characterized in that include the raw material of following parts by weight meter：Polyvinyl chloride resin
30-40 parts, 15-25 parts of phenolic resin, 8-16 parts of maleic anhydride inoculated polypropylene, 6-12 parts of diatomite, 5-10 parts of mica powder, soap
3-6 parts of mountain flour, 6-12 parts of polypropylene fibre, 4-7 parts of silicon carbide, 2-4 parts of carbon black, 3-5 parts of chitin, nano-titanium dioxide 4-6
Part, 3-5 parts of antimony oxide, 0.8-1.5 parts of coupling agent, 1.2-2.5 parts of fire retardant and 1.5-2.8 parts of antioxidant.
2. the high halogen-free environmental CABLE MATERIALS of fire-retardant toughness according to claim 1, which is characterized in that including following parts by weight meter
Raw material：33-37 parts of polyvinyl chloride resin, 18-22 parts of phenolic resin, 12-14 parts of maleic anhydride inoculated polypropylene, 8-10 parts of diatomite,
7-9 parts of mica powder, 4-5 parts of saponite powder, 8-10 parts of polypropylene fibre, 5-6 parts of silicon carbide, 2.5-3.5 parts of carbon black, chitin 3-4
Part, 4.5-5.5 parts of nano-titanium dioxide, 3.5-4.5 parts of antimony oxide, 1.2-1.4 parts of coupling agent, 1.8-2.2 parts of fire retardant
With 2.1-2.4 parts of antioxidant.
3. the high halogen-free environmental CABLE MATERIALS of fire-retardant toughness according to claim 1, which is characterized in that including following parts by weight meter
Raw material：35 parts of polyvinyl chloride resin, 20 parts of phenolic resin, 13 parts of maleic anhydride inoculated polypropylene, 9 parts of diatomite, 8 parts of mica powder, soap
4.5 parts of mountain flour, 9 parts of polypropylene fibre, 5.5 parts of silicon carbide, 3 parts of carbon black, 3.5 parts of chitin, 5 parts of nano-titanium dioxide, three oxygen
Change 2.2 parts of 4 parts of two antimony, 1.3 parts of coupling agent, 2 parts of fire retardant and antioxidant.
4. the high halogen-free environmental CABLE MATERIALS of fire-retardant toughness according to claim 1, which is characterized in that the coupling agent is silane
Coupling agent or titanate coupling agent.
5. the high halogen-free environmental CABLE MATERIALS of fire-retardant toughness according to claim 1, which is characterized in that the fire retardant is described
Fire retardant is aluminium oxide, zinc borate, zinc oxide, phosphate and phosphite according to mass ratio 1:1:1:3:2, which drift along or through, is combined into.
6. the high halogen-free environmental CABLE MATERIALS of fire-retardant toughness according to claim 1, which is characterized in that the antioxidant is 2,6-
Di-tert-butyl p-cresol, 4,4- xenyls di 2 ethylhexyl phosphonic acid four (2,4- di-tert-butyl-phenyls) ester, diphosphorous acid distearyl acid Ji Wusi
One or more of alcohol ester and phosphorous acid three (2,4- di-tert-butyl-phenyls) ester combine.
7. a kind of preparation method of the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness as claimed in any one of claims 1 to 6, feature
It is, includes the following steps：
(1) each component is weighed according to the raw material weight number of the high halogen-free environmental CABLE MATERIALS of fire retardant toughness；
(2) by diatomite, mica powder, saponite powder, polypropylene fibre, silicon carbide, carbon black, chitin, nano-titanium dioxide and three
It aoxidizes in two antimony input high-speed mixer, is warming up to 80-100 degrees Celsius, after mixing dehumidifies 10-15 minutes, is mixed successively to high speed
Be added fire retardant, antioxidant and coupling agent in conjunction machine, after mixing 3-5 minute, be cooled to 50-60 degrees Celsius, put into polyvinyl chloride resin,
Phenolic resin and maleic anhydride inoculated polypropylene mix 5-10 minutes to get mixed material；
(3) step (2) is made in mixed material addition Bitruder and carries out extruding pelletization, pellet, which is placed in 80-100, to be taken the photograph
It is 4-6 hours dry in the baking oven of family name's degree, it is cooled to room temperature to get the fire-retardant high halogen-free environmental CABLE MATERIALS of toughness.
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| CN201810351233.4A CN108485124A (en) | 2018-04-19 | 2018-04-19 | A kind of high halogen-free environmental CABLE MATERIALS of fire-retardant toughness and preparation method thereof |
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| CN110628148A (en) * | 2019-09-27 | 2019-12-31 | 安徽可尔海思塑业有限公司 | Novel PVC composite floor and production method thereof |
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