CN1817956A - Smokeless and halogen-free expanding fire-retardant electric wire materials with thermoplastic elastomer and production thereof - Google Patents
Smokeless and halogen-free expanding fire-retardant electric wire materials with thermoplastic elastomer and production thereof Download PDFInfo
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- CN1817956A CN1817956A CN 200510121081 CN200510121081A CN1817956A CN 1817956 A CN1817956 A CN 1817956A CN 200510121081 CN200510121081 CN 200510121081 CN 200510121081 A CN200510121081 A CN 200510121081A CN 1817956 A CN1817956 A CN 1817956A
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Abstract
A low-smoke non-halogen and expansive flame-retardant electric wire material of thermoplastic elastomer and its production are disclosed. It consists of thermoplastic elastomer resin mixture 58~64 proportion, nitrogen-phosphorus composite fire retardant 30~35 proportion, disperser 3~6 proportion, lubricating agent 3~5 proportion and antioxidant 0.2~0.5 proportion. The thermoplastic elastomer resin mixture comprises PP/EPDM thermoplastic elastomer, PP, POE and EVA. The procedure is carried out by high-speed mixing, extruding into s trips by double-screw mixed extruder, cooling, dicing cutting and obtaining the final product. It has no harmful substances and gas, has better physical behaviors, quality and safety and costs low.
Description
Technical field
The present invention relates to a kind of production method of electric wire materials, particularly a kind of low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer and preparation method thereof.
Background technology
Existing electric wire materials mainly comprises the coated material and the Insulation Material of electric wire, by electric wire materials form by polyvinyl chloride resin and various softening agent, stablizer, lubricant, fire retardant, the raising along with temperature in the course of processing of this material can discharge vinyl chloride monomer, and it is a kind of toxic substance of serious harm HUMAN HEALTH; The electric wire materials that has is made up of polyurethane elastomer and halogen flame (as hexabromocyclododecane, decabromodiphynly oxide, tetrabromo-bisphenol etc.), dispersion agent, lubricant, this material can produce a large amount of black smokes in burning, can produce obnoxious flavour and materials such as a large amount of hydrogen halide simultaneously, environment around polluting, bring personal injury to people, costing an arm and a leg of polyurethane elastomer limited its use range simultaneously; Some auxiliary agents of adopting of these materials mostly contain objectionable impuritiess such as lead, cadmium, mercury, sexavalent chrome, poly-bromo biphenyl, poly-dibromodiphenyl ether in addition, and this is that states such as developed country such as European Union, Japan, the U.S. prohibite the material that uses in electrical equipment and material thereof.In order to overcome the shortcoming of above-mentioned materials, people have invented some halogen-free low-smoke flame retardant materials as CABLE MATERIALS, electric wire materials etc., it has different characteristics, provide " prescription and the producing and manufacturing technique of low smoke and zero halogen non-toxic, environmental friendly cable material " as number of patent application " CN200410013782.9 ", by 68 kilograms of ethene-vinyl acetates, wherein vinyl acetate content 28%, 52 kilograms of high density polyethylene(HDPE)s, 108 kilograms of hydrotalcites, activation treatment, particle diameter is less than 2 microns, 4 kilograms of high-purity smoke suppressors, particle diameter is less than 3 microns, 8.5 kilograms in red phosphorus, littleization processing, 1 kilogram of primary antioxidant, 1 kilogram of auxiliary anti-oxidant, 3 kilograms of silane coupling agents, 1 kilogram of polyethylene wax, 4 kilograms of processing of white oil are formulated.A kind of fireproofing cable material without halide that number of patent application " CN200510038048.2 " provides comprises methyl vinyl silicone rubber, ethylene/vinyl Butyl acrylate multipolymer, interfacial compatibilizer, aluminium hydroxide, magnesium hydroxide, carbon flame-retardant system and draws oxygen lubricated, its weight proportion methyl vinyl silicone rubber 15%, ethylene/vinyl Butyl acrylate multipolymer 25-30%, interfacial compatibilizer 5%, aluminium hydroxide 20-25%, magnesium hydroxide 10-15%, carbon flame-retardant system 13% and draw oxygen lubricated 5%.Number of patent application " CN02111063.8 " relates to a kind of low smoke halogen-free fire retardant polyolefin cable material and preparation method thereof, the raw material of this CABLE MATERIALS comprises following component and content (weight part): ethene-Methane Carboxylic Acid multipolymer 65～75, high density polyethylene(HDPE) 25～35, fire retardant A90～140, fire retardant B7～10, compatilizer 15～30, oxidation inhibitor A1～2.5, oxidation inhibitor B1～2.5, lubricant 1～1.5, linking agent 4～5; The preparation method of this CABLE MATERIALS comprises processing steps such as batching, mixing, granulation, drying; Be difficult for advantages such as drippage when compared with prior art, the present invention has machinery and good processability, temperature resistant grade height, burning.
Summary of the invention
The purpose of this invention is to provide a kind of new low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer and preparation method thereof, improve the security and the physicals of wire products, promote quality product, non-halogen hydrogen toxic gas pollutes.
Purpose of the present invention can realize by following technical measures: this low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer is made up of thermoplastic elastomer resin mixture and nitrogen phosphorus composite flame-retardant agent, dispersion agent, lubricant, oxidation inhibitor, through high-speed mixing, extrude, pelletizing is finished product.Electric wire materials feed composition and content (weight part) are as follows:
58～64 parts in thermoplastic elastomer resin mixture, 30～35 parts of nitrogen phosphorus composite flame-retardant agents, 3～6 parts of dispersion agents, 3～5 parts of lubricants, 0.2～0.5 part in oxidation inhibitor;
Described thermoplastic elastomer resin mixture is made up of homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer, homopolymer polypropylene (PP), ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA), and its weight proportion is homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer: homopolymer polypropylene (PP): ethylene-octene copolymer (POE): ethylene-vinyl acetate copolymer (EVA)=(9～12): (4.9～5.5): 1: 3.3;
Described nitrogen phosphorus composite flame-retardant agent is a modification nitrogen phosphorus composite flame-retardant agent, is the nitrogen phosphorus composite flame-retardant agent of crossing through coupling agent treatment.Nitrogen phosphorus composite flame-retardant agent is an ammonium polyphosphate, and molecular weight is greater than 100,000;
Described dispersion agent is made up of the maleic anhydride grafts of ethylene-vinyl acetate copolymer and the maleic anhydride grafts of homopolymer polypropylene, and its weight proportion is the maleic anhydride grafts of ethylene-vinyl acetate copolymer: the maleic anhydride grafts of homopolymer polypropylene=3～5: 1;
Described lubricant is silicone or amides;
Described oxidation inhibitor is formed by 1010 and 168, and its weight proportion is 1010: 168=3: 5.
The preparation method of electric wire materials of the present invention comprises the steps:
(1), nitrogen phosphorus composite flame-retardant agent is carried out drying, make its water content less than 0.2%, drying temperature is 80～100 ℃;
(2), the nitrogen phosphorus composite flame-retardant agent with step (1) gained drops in the high-speed mixer, add coupling agent KH570 and under normal pressure, carry out coupling processing, the consumption of coupling agent is 1～2% of a nitrogen phosphorus composite flame-retardant agent weight, 70～120 ℃ of coupling processing temperature, 10～15 minutes time;
(3), with step (2) gained in baking oven, dry by the fire 2～3 hours modification nitrogen phosphorus composite flame-retardant agent, 100～120 ℃ of oven temperatures;
(4), homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer, homopolymer polypropylene (PP), ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA) are carried out combination treatment, by said ratio the thermoplastic elastomer resin mixture.
(5) nitrogen phosphorus composite flame-retardant agent, dispersion agent, lubricant, the oxidation inhibitor of thermoplastic elastomer resin mixture, coupling processing being crossed by said ratio is put in the high-speed mixer in order, normal temperature high-speed mixing 5～10 minutes, and discharging is stand-by;
(6), the material of step (5) gained is added hot-extrudable strip in the twin screw compounding forcing machine, get through cooling and dicing.
Beneficial effect of the present invention: owing to objectionable impuritiess such as not halogen-containing and plumbous, cadmium, mercury, sexavalent chrome, poly-bromo biphenyl, poly-dibromodiphenyl ethers, in the course of processing, do not have poisonous, obnoxious flavour effusion, even in the incendiary process, can not produce deleterious hydrogen halide contaminate environment yet, improved the security of wire products, met the requirement of the Rosh instruction of European Union and Japanese Jis, U.S. UL standard appliance material.Material cost of the present invention only is about half of polyurethane elastomer electric wire materials cost, and not only cost is low to produce electric wire with it, and good physical performance, has promoted the quality of product well.
The used fire retardant of the present invention is a nitrogen phosphorus composite flame-retardant agent, and it can be in when burning foaming, expand, and forms a thin carbon layer at resin surface, has completely cut off effectively and the contacting of air, and has improved flame retardant properties greatly.
Embodiment
Polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer that embodiment adopts is 6075 of Nanjing Ao Pute company production; Homopolymer polypropylene (PP) is the T30S that Maoming ethene company produces; The DF805 that ethylene-octene copolymer (POE) is produced for Mitsui company; Ethylene-vinyl acetate copolymer (EVA) is 0328 of the production of EXXON company; The maleic anhydride grafts of the ethylene-vinyl acetate copolymer of dispersion agent is the MC328 that the light company of Ningbo energy produces, and the maleic anhydride grafts of homopolymer polypropylene is the self-control product; Nitrogen phosphorus composite flame-retardant agent is selected the Hangzhou victory for use and the PNP1 of think of company production; The lubricant silicone compound is the Lysl-100 that Chongqing produces with power company, and amides is the TAS-2A that Suzhou state light company produces; 1010,168 compositions that oxidation inhibitor is produced for vapour Bagong department.
Embodiment one:
(1), nitrogen phosphorus composite flame-retardant agent PNP1 being put into loft drier is heated to 85 ℃ and carries out drying, make its water content less than 0.2%, it is dropped in the high-speed mixer, the coupling agent KH570 that adds PNP1 weight 1% carried out coupling processing 15 minutes for 75 ℃ in normal pressure, temperature, and baking got modification nitrogen phosphorus composite flame-retardant agent in 3 hours in 100 ℃ of baking ovens of temperature again;
(2), homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer by weight ratio: homopolymer polypropylene (PP): ethylene-octene copolymer (POE): ethylene-vinyl acetate copolymer (EVA)=10: 5: 1: 3.3 become the thermoplastic elastomer resin mixture with mixing of materials;
(3), by the maleic anhydride grafts of ethylene-vinyl acetate copolymer: the maleic anhydride grafts of homopolymer polypropylene=3: 1 is mixed with dispersion agent;
(4), be 1010 by weight ratio: 168=3: 5 are mixed with oxidation inhibitor;
(5), 6.1 kilograms in thermoplastic elastomer resin mixture, 3.4 kilograms of modification nitrogen phosphorus composite flame-retardant agents, 0.4 kilogram of dispersion agent, 0.15 kilogram of Lysl-100 lubricant, oxidation inhibitor are put in the high-speed mixer for 0.04 kilogram in order, the discharging in 6 minutes of normal temperature high-speed mixing is stand-by;
(6), the heating trade mark be the twin screw compounding forcing machine of TE60, each the district Heating temperature be respectively: 150～160 ℃ in I district, 190～200 ℃ in II district, 190～195 ℃ in III district, 190～195 ℃ in IV district, 185～190 ℃ in V district, 180～185 ℃ in VI district, 180～185 ℃ in VII district, 175～180 ℃ in VIII district.To treat that materials drop in the forcing machine, and at screw speed 80r/min, be extruded into strip under the rate of feeding 8r/min, through cooling, pelletizing is a finished product.Material property sees the following form:
| Melt flow rate (MFR) g/10min | Density g/cm 3 | Hardness Shao A | Tensile break strength MPa | Tension fracture elongation rate % | Combustionproperty UL94 standard |
| 0.5 | 1.12 | 90 | 10.75 | Greater than 200 | V-0 |
Embodiment two:
(1), nitrogen phosphorus composite flame-retardant agent PNP1 being put into loft drier is heated to 95 ℃ and is dried to water content less than 0.2%, drop into high-speed mixer, the coupling agent KH570 that adds PNP1 weight 1.5% carried out coupling processing 13 minutes for 95 ℃ in normal pressure, temperature, and baking got modification nitrogen phosphorus composite flame-retardant agent in 2.5 hours in 110 ℃ of baking ovens of temperature again;
(2), homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer by weight ratio: homopolymer polypropylene (PP): ethylene-octene copolymer (POE): ethylene-vinyl acetate copolymer (EVA)=10.5: 5.2: 1: 3.3 become the thermoplastic elastomer resin mixture with mixing of materials;
(3), by the maleic anhydride grafts of ethylene-vinyl acetate copolymer: the maleic anhydride grafts of homopolymer polypropylene=4: 1 is mixed with dispersion agent;
(4), be 1010 by weight ratio: 168=3: 5 are mixed with oxidation inhibitor;
(5), 5.9 kilograms in thermoplastic elastomer resin mixture, 3.5 kilograms of modification nitrogen phosphorus composite flame-retardant agents, 0.6 kilogram of dispersion agent, 0.25 kilogram of TAS-2A lubricant, oxidation inhibitor are put in the high-speed mixer for 0.04 kilogram in order, the discharging in 8 minutes of normal temperature high-speed mixing is stand-by;
(6), the heating trade mark be the twin screw compounding forcing machine of TE60, each the district Heating temperature be respectively: 150～160 ℃ in I district, 190～200 ℃ in II district, 190～195 ℃ in III district, 190～195 ℃ in IV district, 185～190 ℃ in V district, 180～185 ℃ in VI district, 180～185 ℃ in VII district, 175～180 ℃ in VIII district.To treat that materials drop in the forcing machine, and at screw speed 100r/min, be extruded into strip under the rate of feeding 11r/min, through cooling, pelletizing is a finished product.Material property sees the following form:
| Melt flow rate (MFR) g/10min | Density g/cm 3 | Hardness Shao A | Tensile break strength MPa | Tension fracture elongation rate % | Combustionproperty UL94 standard |
| 0.4 | 1.05 | 92 | 11.2 | Greater than 200 | V-0 |
Embodiment three:
(1), PNP1 is dried to water content less than 0.2% at 105 ℃, the KH570 that drops into high-speed mixer and its weight 2% carried out coupling processing 10 minutes for 120 ℃ in normal pressure, temperature, must modification nitrogen phosphorus composite flame-retardant agent 120 ℃ of bakings of temperature 2 hours;
(2), homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer by weight ratio: homopolymer polypropylene (PP): ethylene-octene copolymer (POE): ethylene-vinyl acetate copolymer (EVA)=12: 5.5: 1: 3.3 become the thermoplastic elastomer resin mixture with mixing of materials;
(3), by the maleic anhydride grafts of ethylene-vinyl acetate copolymer: the maleic anhydride grafts of homopolymer polypropylene=5: 1 is mixed with dispersion agent;
(4), be 1010 by weight ratio: 168=3: 5 are mixed with oxidation inhibitor;
(5), 6.2 kilograms in thermoplastic elastomer resin mixture, 3.3 kilograms of modification nitrogen phosphorus composite flame-retardant agents, 0.5 kilogram of dispersion agent, 0.22 kilogram of TAS-2A lubricant, oxidation inhibitor are put in the high-speed mixer for 0.04 kilogram in order, the discharging in 10 minutes of normal temperature high-speed mixing is stand-by;
(6), add the twin screw compounding forcing machine, the Heating temperature in each district is respectively: 150～160 ℃ in I district, 190～200 ℃ in II district, 190～195 ℃ in III district, 185～190 ℃ in IV district, 185～190 ℃ in V district, 180～185 ℃ in VI district, 175～180 ℃ in VII district, 175～180 ℃ in VIII district.To treat that materials drop in the forcing machine, and at screw speed 110r/min, be extruded into strip under the rate of feeding 14r/min, through cooling, pelletizing is a finished product.Material property sees the following form:
。
| Melt flow rate (MFR) g/10min | Density g/cm 3 | Hardness Shao A | Tensile break strength MPa | Tension fracture elongation rate % | Combustionproperty UL94 standard |
| 0.6 | 1.10 | 91 | 11.52 | Greater than 200 | V-0 |
Claims (4)
1, a kind of low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer is characterized in that electric wire materials feed composition and content (weight part) are as follows:
58～64 parts in thermoplastic elastomer resin mixture, 30～35 parts of nitrogen phosphorus composite flame-retardant agents, 3～6 parts of dispersion agents, 3～5 parts of lubricants, 0.2～0.5 part in oxidation inhibitor;
Wherein the thermoplastic elastomer resin mixture is made up of homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer, homopolymer polypropylene (PP), ethylene-octene copolymer (POE), ethylene-vinyl acetate copolymer (EVA), and its weight proportion is homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer: homopolymer polypropylene (PP): ethylene-octene copolymer (POE): ethylene-vinyl acetate copolymer (EVA)=(9～12): (4.9～5.5): 1: 3.3.
2, a kind of low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer according to claim 1, it is characterized in that dispersion agent is made up of the maleic anhydride grafts of ethylene-vinyl acetate copolymer and the maleic anhydride grafts of homopolymer polypropylene, its weight proportion is the maleic anhydride grafts of ethylene-vinyl acetate copolymer: the maleic anhydride grafts of homopolymer polypropylene=3～5: 1.
3, a kind of low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer according to claim 1 is characterized in that oxidation inhibitor forms by 1010 and 168, and its weight proportion is 1010: 168=3: 5.
4, the preparation method of the described a kind of low-smoke halogen-free expansion flame-retarded electric wire materials with thermoplastic elastomer of claim 1 is characterized in that comprising the steps:
(1), nitrogen phosphorus composite flame-retardant agent is carried out drying, make its water content less than 0.2%, drying temperature is 80～100 ℃;
(2), the nitrogen phosphorus composite flame-retardant agent with step (1) gained drops in the high-speed mixer, add coupling agent KH570 and under normal pressure, carry out coupling processing, the consumption of coupling agent is 1～2% of a nitrogen phosphorus composite flame-retardant agent weight, 70～120 ℃ of coupling processing temperature, 10～15 minutes time;
(3), with step (2) gained in baking oven, dry by the fire 2～3 hours modification nitrogen phosphorus composite flame-retardant agent, 100～120 ℃ of oven temperatures;
(4), by weight ratio for homopolymer polypropylene (PP)/terpolymer EP rubber (EPDM) thermoplastic elastomer: homopolymer polypropylene (PP): ethylene-octene copolymer (POE): ethylene-vinyl acetate copolymer (EVA)=(9～12): (4.9～5.5): feed intake at 1: 3.3 and to carry out combination treatment, the thermoplastic elastomer resin mixture;
(5) 0.2～0.5 part in 58～64 parts in thermoplastic elastomer resin mixture, 30～35 parts of nitrogen phosphorus composite flame-retardant agents, 3～6 parts of dispersion agents, 3～5 parts of lubricants, oxidation inhibitor are put in the high-speed mixer by proportioning, order, normal temperature high-speed mixing 5～10 minutes, discharging is stand-by;
(6), the material of step (5) gained is added hot-extrudable strip in the twin screw compounding forcing machine, get through cooling and dicing.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101210811A CN100374497C (en) | 2005-12-21 | 2005-12-21 | Smokeless and halogen-free expanding fire-retardant electric wire materials with thermoplastic elastomer and production thereof |
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| CN100374497C CN100374497C (en) | 2008-03-12 |
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| CN101792557A (en) * | 2010-02-24 | 2010-08-04 | 沈阳军航电源科技有限公司 | Application of thermoplastic elastomer on soft power cable for wind power generation |
| CN101845174A (en) * | 2010-05-31 | 2010-09-29 | 江苏凯诺电缆集团有限公司 | Sheath material of solar photovoltaic cable and cable |
| WO2011079457A1 (en) * | 2009-12-31 | 2011-07-07 | Dow Global Technologies Inc. | Halogen-free, flame retardant thermoplastic compositions for wire and cable applications |
| CN101161775B (en) * | 2006-10-09 | 2012-06-13 | 浙江省化工研究院有限公司 | Novel halogen-free environment-friendly type flame-proof polypropylene material |
| CN102746573A (en) * | 2012-06-07 | 2012-10-24 | 安徽胜华电缆集团有限公司 | Methyl vinyl silicone rubber insulating heat-resistant control cable material and preparation method thereof |
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| CN103554657A (en) * | 2013-10-18 | 2014-02-05 | 浙江工业大学之江学院工业研究院 | Halogen-free flame-retardant polypropylene composite cable material and preparation method thereof |
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| US7378463B2 (en) * | 2004-02-04 | 2008-05-27 | Enerdel, Inc. | Halogen-free fire retardant system for low heat release polymers |
| CN1133692C (en) * | 2000-07-22 | 2004-01-07 | 中国科学技术大学 | Prepn of fireproofing cable material without halide |
| CN1331931C (en) * | 2003-04-30 | 2007-08-15 | 刘信东 | Halogen-free low-smoke electric wire and cable sheathing material containing phosphorus, nitrogen, layered silicate and compound polythene and method for preparing the same |
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| WO2011079457A1 (en) * | 2009-12-31 | 2011-07-07 | Dow Global Technologies Inc. | Halogen-free, flame retardant thermoplastic compositions for wire and cable applications |
| US9321912B2 (en) | 2009-12-31 | 2016-04-26 | Dow Global Technologies Llc | Halogen-free flame retardant thermoplastic compositions for wire and cable applications |
| CN101792557B (en) * | 2010-02-24 | 2011-05-04 | 沈阳军航电源科技有限公司 | Application of thermoplastic elastomer on soft power cable for wind power generation |
| CN101792557A (en) * | 2010-02-24 | 2010-08-04 | 沈阳军航电源科技有限公司 | Application of thermoplastic elastomer on soft power cable for wind power generation |
| CN101845174B (en) * | 2010-05-31 | 2013-02-27 | 江苏凯诺电缆集团有限公司 | Sheath material of solar photovoltaic cable and cable |
| CN101845174A (en) * | 2010-05-31 | 2010-09-29 | 江苏凯诺电缆集团有限公司 | Sheath material of solar photovoltaic cable and cable |
| CN102746573B (en) * | 2012-06-07 | 2016-01-20 | 安徽胜华电缆集团有限公司 | A kind of methyl vinyl silicone rubber insulate heat-resisting control cables material and preparation method thereof |
| CN102746573A (en) * | 2012-06-07 | 2012-10-24 | 安徽胜华电缆集团有限公司 | Methyl vinyl silicone rubber insulating heat-resistant control cable material and preparation method thereof |
| CN102838803B (en) * | 2012-08-28 | 2015-11-04 | 安徽双荣电器电缆有限公司 | Heat-resisting control cables material of a kind of silicon rubber insulation and preparation method thereof |
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| CN103554657A (en) * | 2013-10-18 | 2014-02-05 | 浙江工业大学之江学院工业研究院 | Halogen-free flame-retardant polypropylene composite cable material and preparation method thereof |
| CN107652556A (en) * | 2017-09-27 | 2018-02-02 | 东莞市领亚环保材料有限公司 | A kind of high-speed cable high fire-retardance low dielectric constant insulating material and preparation method thereof |
| CN112662055A (en) * | 2020-12-10 | 2021-04-16 | 南京大学 | Modified polypropylene material for composite insulator |
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