CN103450552A - Irradiation crosslinked LSOH (low smoke halogen-free) high-flame-retardant polyolefin cable material and preparation method thereof - Google Patents
Irradiation crosslinked LSOH (low smoke halogen-free) high-flame-retardant polyolefin cable material and preparation method thereof Download PDFInfo
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- CN103450552A CN103450552A CN2013104162528A CN201310416252A CN103450552A CN 103450552 A CN103450552 A CN 103450552A CN 2013104162528 A CN2013104162528 A CN 2013104162528A CN 201310416252 A CN201310416252 A CN 201310416252A CN 103450552 A CN103450552 A CN 103450552A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention relates to an irradiation crosslinked LSOH (low smoke halogen-free) high-flame-retardant polyolefin cable material and a preparation method thereof. The preparation method is characterized in that the irradiation crosslinked LSOH high-flame-retardant polyolefin cable material is prepared from linear low-density polyethylene resin, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, aluminum hydroxide, magnesium hydroxide, 3.5 hydrated zinc borate, a high-viscosity organic silicon mixture, magnesium stearate, a phosphorus-containing halogen-free flame retardant, polyethylene wax, an antioxidant, a crosslinking agent, and the like through the steps of mixing the raw materials by using a closed mixing machine and then carrying out extrusion by using a six-temperature-period twin-screw extruder. An electric wire and a cable prepared by taking the irradiation crosslinked LSOH high-flame-retardant polyolefin cable material as an insulating layer not only have the advantages of good flame retardance, high light transmittance, good electrical insulation, good water resistance and the like, but also have the characteristics of high-temperature resistance level (can be used for a long time in a 105 DEG C environment), good mechanical and physical properties of insulating layers, and the like. The irradiation crosslinked LSOH high-flame-retardant polyolefin cable material can be used as a raw material of LSOH high-flame-retardant insulating layers of electric wires.
Description
Technical field
The present invention relates to a kind of plastic pellet and preparation method thereof.Specifically, be raw material for making the low-smoke bittern-free highly fire-proof electric wire insulation layer and preparation method thereof.
Background technology
Fast development along with industries such as China's metallurgy, electric power, electronics, automatization and informatization and networks, make the consumption of supporting with it flame-retardant electric wire and cable and power cable, control cables, signal cable, instrument cable, computer cable isoelectric line cable sharply increase.
Traditional flame retardant cable mostly adopts polyvinyl chloride as insulation or sheath.Although polyvinyl chloride has fire-retardant good, inexpensive, the characteristics such as expressing technique is good, because it contains halogen, while running into the fire burning, can discharge a large amount of hydrogen halides and dense smoke, cause " the secondary harm " of fire, thus the loss that has strengthened fire.Through scientific research, confirm, the harm that halogenide causes HUMAN HEALTH and environment is more and more serious, and people are attaching importance to environmental protection more and more, and European Union etc. have all proposed the regulations to polyvinyl chloride restriction use.At home, Beijing Power Supply Bureau sends the documents and provide against the polyvinyl chloride electric wire and use in this office system in March, 1998, and " the covil construction electric wire fire protection design rules " that East China Municipal Architecture Design and Research Institute in 2002 is released have clearly proposed to use the requirement of low smoke no-halogen wire cable.Above these, make low-smoke halogen-free flame-retardant electric wire and cable be used widely and present very large development potentiality, particularly in densely populated occasions such as subway, Highrise buildings, various venue buildings, all require to use low-smoke halogen-free flame-retardant electric wire and cable.But there are the defects such as flame retardant resistance is not high, electrical insulation properties is poor, water tolerance is bad in low smoke halogen-free fire retardant polyolefin cable material in the market, are difficult to meet the fire-retardant requirement of category-B and the requirement of the low-smoke non-halogen flame-retardant building cotton covered wire that moister occasion used is arranged.
Summary of the invention
The problem that the present invention will solve is to provide a kind of irradiated crosslinking low-smoke and halogen-free polyolefine high flame-retardant cable material.The electric wire that adopts the present invention to make as insulation layer, not only there is the advantages such as good flame resistance (can by single vertical fire-retardant and the category-B bunchy is fire-retardant), transmittance high (>=80%), electric insulating quality are good, water-tolerant (can be used for the moist occasions such as vault), and there are the characteristics such as temperature resistant grade high (can under 105 ℃ of environment life-time service), insulation layer mechanical and physical performance are good.
Another problem that the present invention will solve is to provide a kind of method for preparing irradiated crosslinking low-smoke and halogen-free polyolefine high flame-retardant cable material.
For addressing the above problem, take following technical scheme:
Irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin characteristics of the present invention are the raw materials that comprise following parts by weight:
Type low density polyethylene resin 20 ~ 25 weight parts;
Ethylene vinyl acetate 35 ~ 45 weight parts;
Ethylene ethyl acrylate copolymer 45 ~ 30 weight parts;
Aluminium hydroxide 80 ~ 90 weight parts;
Magnesium hydroxide 70 ~ 60 weight parts;
3.5 hydrate zinc borate 10 ~ 20 weight parts;
Highly viscous organosilicon mixture 15 ~ 20 weight parts;
Magnesium Stearate 5 ~ 8 weight parts;
Phosphor-containing halogen-free fire retardant 15 ~ 20 weight parts;
Polyethylene wax 0.5 ~ 1.0 weight part;
Oxidation inhibitor 0.8 ~ 1.2 weight part;
Linking agent 0.7 ~ 1.0 weight part.
Wherein:
The melting index of described type low density polyethylene resin is 1.0 ~ 2.0g/10min;
In described ethylene vinyl acetate, the weight content of vinyl acetate between to for plastic is 28%, and melting index is 4 ~ 6 g/10min;
In described ethylene ethyl acrylate copolymer, the weight content of ethyl propenoate is 15 ~ 19%, and melting index is 0.5 ~ 5dg/min;
Described highly viscous organosilicon mixture is the SFR 100 type highly viscous organosilicon mixtures that organosilicon company limited of GE Toshiba produces;
Described phosphor-containing halogen-free fire retardant is the OP 935 type efficient halogen-free anti-inflaming agent that German Clariant company produces, and its phosphorus content is about 23 ~ 24 % by weight;
Described oxidation inhibitor is 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] or four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described linking agent is triallyl cyanurate.
The method characteristic for preparing described irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin is to comprise the following steps successively:
First type low density polyethylene resin, ethylene vinyl acetate, ethylene ethyl acrylate copolymer, aluminium hydroxide, magnesium hydroxide, 3.5 hydrate zinc borates, Magnesium Stearate, phosphor-containing halogen-free fire retardant, polyethylene wax, oxidation inhibitor are dropped in the closed mixing machine that temperature is 135 ~ 145 ℃ together with linking agent, mixing 8 ~ 10 minutes, obtain the bulk material;
Then, highly viscous organosilicon mixture is joined in the closed mixing machine that said temperature is 135 ~ 145 ℃, continue together with described bulk material mixing 4 ~ 6 minutes, obtain material base;
Finally, described material base is dropped in six temperature section twin screw extruders, extrude into particle, obtain irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin; Wherein, six temperature section temperature of described Liu's temperature section twin screw extruder are respectively 135 ℃, 145 ℃, 155 ℃, 160 ℃, 160 ℃, 155 ℃.
Adopt such scheme, there is following advantage:
Owing to containing ethylene ethyl acrylate copolymer and ethylene vinyl acetate in raw material of the present invention, by the cooperation of ethylene ethyl acrylate copolymer and ethylene vinyl acetate, all can fill a large amount of halogen-free flame retardantss.Wherein, the former has higher thermostability, makes the adaptable processing window of the present invention wider, and for anti-drippage, obvious contribution is arranged when running into the fire burning.In addition, the former electrical insulating property is good, makes the present invention have electrical insulation properties preferably.The latter has flowing property preferably, contributes to improve to extrude the mobility that adds man-hour.
Owing to containing highly viscous organosilicon mixture and Magnesium Stearate in raw material of the present invention, after the two coordinated, contribute to aluminium hydroxide/splendid carbon-coating of magnesium hydroxide flame retardant System forming again, greatly improved flame retardant properties of the present invention.
The phosphor-containing halogen-free fire retardant resistant to hydrolysis performance adopted due to the present invention is outstanding, the self-extinguishing energy in the time of significantly improving the present invention and meet the fire burning as efficient phosphorus active element.And adding of highly viscous organosilicon mixture can make the thermostability of phosphor-containing halogen-free fire retardant be improved, contribute to improve system flame retardant effect of the present invention.
In addition, adding of highly viscous organosilicon mixture, also improved water tolerance of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment mono-
First choose the type low density polyethylene resin of 20 weight parts, the ethylene vinyl acetate of 35 weight parts, the ethylene ethyl acrylate copolymer of 45 weight parts, the aluminium hydroxide of 80 weight parts, the magnesium hydroxide of 70 weight parts, 3.5 hydrate zinc borates of 10 weight parts, the highly viscous organosilicon mixture of 15 weight parts, the Magnesium Stearate of 5 weight parts, the phosphor-containing halogen-free fire retardant of 15 weight parts, 0.5 the polyethylene wax of weight part, 0.8 the oxidation inhibitor of weight part, 0.7 the linking agent of weight part.
Then, type low density polyethylene resin, ethylene vinyl acetate, ethylene ethyl acrylate copolymer, aluminium hydroxide, magnesium hydroxide, 3.5 hydrate zinc borates, Magnesium Stearate, phosphor-containing halogen-free fire retardant, polyethylene wax, oxidation inhibitor are dropped in the closed mixing machine that temperature is 135 ℃ together with linking agent, mixing 8 minutes, obtain the bulk material.
Afterwards, highly viscous organosilicon mixture is joined in the closed mixing machine that said temperature is 135 ℃, continue together with described bulk material mixing 4 minutes, obtain material base.
Finally, described material base is dropped in six temperature section twin screw extruders, extrude into particle, obtain irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin.Wherein, six temperature section temperature of described Liu's temperature section twin screw extruder are respectively 135 ℃, 145 ℃, 155 ℃, 160 ℃, 160 ℃, 155 ℃.
In the present embodiment:
The melting index of described type low density polyethylene resin is 1.0 ~ 2.0g/10min;
In described ethylene vinyl acetate, the weight content of vinyl acetate between to for plastic is 28%, and melting index is 4 ~ 6 g/10min;
In described ethylene ethyl acrylate copolymer, the weight content of ethyl propenoate is 15 ~ 19%, and melting index is 0.5 ~ 5dg/min;
Described highly viscous organosilicon mixture is the SFR 100 type highly viscous organosilicon mixtures that organosilicon company limited of GE Toshiba produces;
Described phosphor-containing halogen-free fire retardant is the OP 935 type efficient halogen-free anti-inflaming agent that German Clariant company produces, and its phosphorus content is about 23 ~ 24 % by weight;
Described oxidation inhibitor is 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate];
Described linking agent is triallyl cyanurate.
Embodiment bis-
First choose the type low density polyethylene resin of 22 weight parts, the ethylene vinyl acetate of 40 weight parts, the ethylene ethyl acrylate copolymer of 38 weight parts, the aluminium hydroxide of 85 weight parts, the magnesium hydroxide of 65 weight parts, 3.5 hydrate zinc borates of 15 weight parts, the highly viscous organosilicon mixture of 17 weight parts, the Magnesium Stearate of 7 weight parts, the phosphor-containing halogen-free fire retardant of 18 weight parts, the polyethylene wax of 0.7 weight part, the oxidation inhibitor of 1.0 weight parts, the linking agent of 0.8 weight part.
Then, type low density polyethylene resin, ethylene vinyl acetate, ethylene ethyl acrylate copolymer, aluminium hydroxide, magnesium hydroxide, 3.5 hydrate zinc borates, Magnesium Stearate, phosphor-containing halogen-free fire retardant, polyethylene wax, oxidation inhibitor are dropped in the closed mixing machine that temperature is 140 ℃ together with linking agent, mixing 9 minutes, obtain the bulk material.
Afterwards, highly viscous organosilicon mixture is joined in the closed mixing machine that said temperature is 140 ℃, continue together with described bulk material mixing 5 minutes, obtain material base.
Finally, described material base is dropped in six temperature section twin screw extruders, extrude into particle, obtain irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin.Wherein, six temperature section temperature of described Liu's temperature section twin screw extruder are respectively 135 ℃, 145 ℃, 155 ℃, 160 ℃, 160 ℃, 155 ℃.
In the present embodiment:
The melting index of described type low density polyethylene resin is 1.0 ~ 2.0g/10min;
In described ethylene vinyl acetate, the weight content of vinyl acetate between to for plastic is 28%, and melting index is 4 ~ 6 g/10min;
In described ethylene ethyl acrylate copolymer, the weight content of ethyl propenoate is 15 ~ 19%, and melting index is 0.5 ~ 5dg/min;
Described highly viscous organosilicon mixture is the SFR 100 type highly viscous organosilicon mixtures that organosilicon company limited of GE Toshiba produces;
Described phosphor-containing halogen-free fire retardant is the OP 935 type efficient halogen-free anti-inflaming agent that German Clariant company produces, and its phosphorus content is about 23 ~ 24 % by weight;
Described oxidation inhibitor is four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described linking agent is triallyl cyanurate.
Embodiment tri-
First choose the type low density polyethylene resin of 25 weight parts, the ethylene vinyl acetate of 45 weight parts, the ethylene ethyl acrylate copolymer of 30 weight parts, the aluminium hydroxide of 90 weight parts, the magnesium hydroxide of 60 weight parts, 3.5 hydrate zinc borates of 20 weight parts, the highly viscous organosilicon mixture of 20 weight parts, the Magnesium Stearate of 8 weight parts, the phosphor-containing halogen-free fire retardant of 20 weight parts, the polyethylene wax of 1.0 weight parts, the oxidation inhibitor of 1.2 weight parts, the linking agent of 1.0 weight parts.
Then, type low density polyethylene resin, ethylene vinyl acetate, ethylene ethyl acrylate copolymer, aluminium hydroxide, magnesium hydroxide, 3.5 hydrate zinc borates, Magnesium Stearate, phosphor-containing halogen-free fire retardant, polyethylene wax, oxidation inhibitor are dropped in the closed mixing machine that temperature is 145 ℃ together with linking agent, mixing 10 minutes, obtain the bulk material.
Afterwards, highly viscous organosilicon mixture is joined in the closed mixing machine that said temperature is 145 ℃, continue together with described bulk material mixing 6 minutes, obtain material base.
Finally, described material base is dropped in six temperature section twin screw extruders, extrude into particle, obtain irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin.Wherein, six temperature section temperature of described Liu's temperature section twin screw extruder are respectively 135 ℃, 145 ℃, 155 ℃, 160 ℃, 160 ℃, 155 ℃.
In the present embodiment:
The melting index of described type low density polyethylene resin is 1.0 ~ 2.0g/10min;
In described ethylene vinyl acetate, the weight content of vinyl acetate between to for plastic is 28%, and melting index is 4 ~ 6 g/10min;
In described ethylene ethyl acrylate copolymer, the weight content of ethyl propenoate is 15 ~ 19%, and melting index is 0.5 ~ 5dg/min;
Described highly viscous organosilicon mixture is the SFR 100 type highly viscous organosilicon mixtures that organosilicon company limited of GE Toshiba produces;
Described phosphor-containing halogen-free fire retardant is the OP 935 type efficient halogen-free anti-inflaming agent that German Clariant company produces, and its phosphorus content is about 23 ~ 24 % by weight;
Described oxidation inhibitor is four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described linking agent is triallyl cyanurate.
Claims (9)
1. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin is characterized in that comprising the raw material of following parts by weight:
Type low density polyethylene resin 20 ~ 25 weight parts;
Ethylene vinyl acetate 35 ~ 45 weight parts;
Ethylene ethyl acrylate copolymer 45 ~ 30 weight parts;
Aluminium hydroxide 80 ~ 90 weight parts;
Magnesium hydroxide 70 ~ 60 weight parts;
3.5 hydrate zinc borate 10 ~ 20 weight parts;
Highly viscous organosilicon mixture 15 ~ 20 weight parts;
Magnesium Stearate 5 ~ 8 weight parts;
Phosphor-containing halogen-free fire retardant 15 ~ 20 weight parts;
Polyethylene wax 0.5 ~ 1.0 weight part;
Oxidation inhibitor 0.8 ~ 1.2 weight part;
Linking agent 0.7 ~ 1.0 weight part.
2. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, the melting index that it is characterized in that described type low density polyethylene resin is 1.0 ~ 2.0g/10min.
3. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, is characterized in that in described ethylene vinyl acetate, and the weight content of vinyl acetate between to for plastic is 28%, and melting index is 4 ~ 6 g/10min.
4. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, is characterized in that in described ethylene ethyl acrylate copolymer, and the weight content of ethyl propenoate is 15 ~ 19%, and melting index is 0.5 ~ 5dg/min.
5. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, is characterized in that described highly viscous organosilicon mixture is the SFR 100 type highly viscous organosilicon mixtures that organosilicon company limited of GE Toshiba produces.
6. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, is characterized in that described phosphor-containing halogen-free fire retardant is the OP 935 type efficient halogen-free anti-inflaming agent that German Clariant company produces, and its phosphorus content is about 23 ~ 24 % by weight.
7. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, it is characterized in that described oxidation inhibitor is 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] or four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
8. irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin as claimed in claim 1, is characterized in that described linking agent is triallyl cyanurate.
9. prepare the method for the described irradiated crosslinking low-smoke and halogen-free high flame retardant of claim 1 cable material of polyolefin, it is characterized in that comprising the following steps successively:
First type low density polyethylene resin, ethylene vinyl acetate, ethylene ethyl acrylate copolymer, aluminium hydroxide, magnesium hydroxide, 3.5 hydrate zinc borates, Magnesium Stearate, phosphor-containing halogen-free fire retardant, polyethylene wax, oxidation inhibitor are dropped in the closed mixing machine that temperature is 135 ~ 145 ℃ together with linking agent, mixing 8 ~ 10 minutes, obtain the bulk material;
Then, highly viscous organosilicon mixture is joined in the closed mixing machine that said temperature is 135 ~ 145 ℃, continue together with described bulk material mixing 4 ~ 6 minutes, obtain material base;
Finally, described material base is dropped in six temperature section twin screw extruders, extrude into particle, obtain irradiated crosslinking low-smoke and halogen-free high flame retardant cable material of polyolefin; Wherein, six temperature section temperature of described Liu's temperature section twin screw extruder are respectively 135 ℃, 145 ℃, 155 ℃, 160 ℃, 160 ℃, 155 ℃.
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Cited By (6)
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| CN103871643A (en) * | 2014-02-27 | 2014-06-18 | 安徽江淮电缆集团有限公司 | Low-cost halogen-free low-smoke low-toxicity anti-flaming power cable for ships and insulating sizing material of power cable |
| CN104194139A (en) * | 2014-08-26 | 2014-12-10 | 无锡杰科塑业有限公司 | High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof |
| CN104448462A (en) * | 2014-03-26 | 2015-03-25 | 江苏荣宜电缆有限公司 | Polyethylene material for high-performance electric wire and cable |
| CN106928532A (en) * | 2015-12-29 | 2017-07-07 | 天津市普立泰高分子科技有限公司 | Thermoplastic low-smoke halide-free high fire-retardance polyolefin jacket material and preparation method thereof |
| CN108034121A (en) * | 2017-12-20 | 2018-05-15 | 苏州希普拉斯新材料有限公司 | Flame resistance irradiation is crosslinked low-smoke low-halogen polyolefine material |
| CN110396241A (en) * | 2019-01-29 | 2019-11-01 | 常州吉斯佰恩新材料科技有限公司 | A kind of irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALS |
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| CN106928532A (en) * | 2015-12-29 | 2017-07-07 | 天津市普立泰高分子科技有限公司 | Thermoplastic low-smoke halide-free high fire-retardance polyolefin jacket material and preparation method thereof |
| CN108034121A (en) * | 2017-12-20 | 2018-05-15 | 苏州希普拉斯新材料有限公司 | Flame resistance irradiation is crosslinked low-smoke low-halogen polyolefine material |
| CN110396241A (en) * | 2019-01-29 | 2019-11-01 | 常州吉斯佰恩新材料科技有限公司 | A kind of irradiated crosslinking low-smoke and halogen-free flame retardant CABLE MATERIALS |
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Application publication date: 20131218 |