CN1793212A - Low smoke non-halogen fire retarding expansive polyolefins electronic wire material and preparation process thereof - Google Patents
Low smoke non-halogen fire retarding expansive polyolefins electronic wire material and preparation process thereof Download PDFInfo
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Abstract
The invention relates to a low smoke non-bittern expanding inflaming retarding polyolefin electric material and the manufacture method that contains polyolefine resin mixture 48-52 portions, nitrogen and phosphor compounding fire retardant 38-42 portions, dispersing agent 8-12 portions, fire retarding synergist 0.2-0.5 portions, lubricant 1.5-3.5 portions, and antioxidant 0.4-0.6 portions. Polyolefine resin mixture is compounded from polyethylene mixture and EVA. The polyethylene mixture is made up from LDPE, LLDPE, and HDPE. The invention has the advantages of no vinyl chloride monomer, no halogen hydride gas pollution, good fire resistance property, save, environment protection, smoothing appearance, middle rigidity, strong tensile strength, etc.
Description
Technical field
The present invention relates to a kind of electric wire materials, particularly a kind of low smoke non-halogen fire retarding expansive polyolefins electronic wire material and preparation method thereof.
Background technology
Existing electric wire materials is made up of 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.Also have some lubricants, stablizer and auxiliary agents such as softening agent, fire retardant, mostly contain objectionable impuritiess such as lead, cadmium, mercury, sexavalent chrome, poly-bromo biphenyl, poly-dibromodiphenyl ether, this is that countries such as European Union, Japan, the U.S. prohibite the material that uses in electrical equipment and material thereof.The PVC material for electrical plug can be emitted a large amount of dense smokes in the incendiary process, PVC decomposes, emit HCl gas and the compound that contains objectionable impuritiess such as lead, cadmium, mercury, sexavalent chrome, poly-bromo biphenyl, poly-dibromodiphenyl ether, serious environment pollution damages the healthy of people.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 that methyl vinyl silicone rubber, ethylene/vinyl acrylic acid fourth resin copolymer, interfacial compatibilizer, aluminium hydroxide, magnesium hydroxide, carbon flame-retardant system and epoxy are 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 non-halogen fire retarding expansive polyolefins electronic wire material and preparation method thereof, improve the security of electronics line products, satisfy the requirement of product physicals, promote quality product, non-halogen hydrogen toxic gas pollutes.
Purpose of the present invention can realize by following technical measures: this electronic wire material by polyolefin resin mixture and nitrogen phosphorus composite flame-retardant agent, dispersion agent, retardant synergist, lubricant, oxidation inhibitor high-speed mixing after, through the compounding forcing machine extrude, cooling, pelletizing form.Electronic wire material feed composition and content (weight part) are as follows:
48～52 parts in polyolefin resin mixture, 38～42 parts of nitrogen phosphorus composite flame-retardant agents, 8～12 parts of dispersion agents, 0.2～0.5 part of retardant synergist, 1.5～3.5 parts of lubricants, 0.4～0.6 part in oxidation inhibitor;
Described polyolefin resin mixture is made up of polyethylene mixture and ethylene-vinyl acetate copolymer (EVA), and its weight proportion is a polyethylene mixture: ethylene-vinyl acetate copolymer (EVA)=0.8～1.2: 1;
Described polyethylene mixture is made up of new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), and its weight proportion is new LDPE (film grade) (LDPE): linear low density polyethylene (LLDPE): high density polyethylene(HDPE) (HDPE)=1: 3: 1;
Described nitrogen phosphorus composite flame-retardant agent is through coupling processing modification nitrogen phosphorus composite flame-retardant agent;
Described 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 linear low density polyethylene, and its weight proportion is 1: 1;
Described retardant synergist is a tetrafluoroethylene;
Described lubricant is a silicone compound;
Described oxidation inhibitor is formed by 1010,168 and 1024, and its weight proportion is 1010: 168: 1024=3: 5: 4.
The preparation method of electronic wire material of the present invention comprises the steps:
(1), nitrogen phosphorus composite flame-retardant agent is dried to its water content less than 0.2% under 80～100 ℃ of temperature, in the input 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, gained was got modification nitrogen phosphorus composite flame-retardant agent in 2～3 hours 100～120 ℃ of temperature bakings;
(2), by said ratio new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) are carried out combination treatment and get polyethylene mixture;
(3), by said ratio with polyethylene mixture and ethylene-vinyl acetate copolymer (EVA) carry out normal temperature mix the polyolefin resin mixture;
(4), polyolefin resin mixture, nitrogen phosphorus composite flame-retardant agent, dispersion agent, retardant synergist, lubricant, oxidation inhibitor are put in the high-speed mixer in order by said ratio, normal temperature high-speed mixing 5～10 minutes, discharging is stand-by;
(5), the material of step (4) gained is added hot-extrudable strip in the twin screw compounding forcing machine, get finished product through cooling and dicing.
Beneficial effect of the present invention: because not halogen-containing and plumbous; cadmium; mercury; sexavalent chrome; poly-bromo biphenyl; objectionable impuritiess such as poly-dibromodiphenyl ether; from processing environment and the environment for use of having improved material at all; in the course of processing, can not discharge deleterious vinyl chloride monomer; even in the incendiary process, can not produce deleterious hydrogen halide yet; played the effect of protection environment; used fire retardant is a nitrogen phosphorus composite flame-retardant agent; it can foam when burning; expand; and form a thin carbon layer at resin surface; completely cut off effectively and the contacting of air, improved flame retardant properties greatly.Meet the requirement of the Rosh instruction of European Union and Japanese Jis, U.S. UL standard to appliance material.
With the electronics line that electronic wire material of the present invention is produced, smooth in appearance, hardness is moderate, and tensile strength height, tension fracture elongation rate are greater than 200%, and combustionproperty reaches U.S. UL1581 standard, i.e. VW-1 level.
Embodiment
The 100WB that new LDPE (film grade) (LDPE) adopts EXXON company to produce, linear low density polyethylene (LLDPE) is 2076 of Maoming ethene company production, the QHJ-01 that high density polyethylene(HDPE) (HDPE) is produced for Qilu Petrochemical company, ethylene-vinyl acetate copolymer (EVA) select that French atropic company produces for use 2805, nitrogen phosphorus composite flame-retardant agent is selected the Hangzhou victory for use and the PNP1 of think of company production, the MC328 that the maleic anhydride grafts of the ethylene-vinyl acetate copolymer of dispersion agent adopts the light company of Ningbo energy to produce, the maleic anhydride grafts of linear low density polyethylene adopts 9904 of Nanjing multiple star company production, the A-449 that retardant synergist adopts U.S. big lake company to produce, the Lys1-100 that lubricant selects for use Chongqing to produce with power company, oxidation inhibitor select 1010 of vapour Bagong department production for use, 168 and 1024 form.
The preparation of polyethylene mixture is to be new LDPE (film grade) (LDPE) by weight ratio: linear low density polyethylene (LLDPE): high density polyethylene(HDPE) (HDPE)=1: 3: 1 feeds intake and carries out combination treatment and get.
The preparation of modification nitrogen phosphorus composite flame-retardant agent is to put nitrogen phosphorus composite flame-retardant agent PNP1 into loft drier to be heated to 95 ℃ and to be 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, baking 2.5 hours and getting in 110 ℃ of baking ovens of temperature again.
Dispersion agent is the maleic anhydride grafts of ethylene-vinyl acetate copolymer by weight ratio: the maleic anhydride grafts of linear low density polyethylene is formed=1: 1 mixed preparing.
Oxidation inhibitor is 1010: 168 by weight ratio: 1024=3: 5: 4 mixed preparing.
Embodiment one:
(1), by weight ratio for polyethylene mixture: ethylene-vinyl acetate copolymer (EVA)=0.9: 1 feed intake carry out normal temperature mix the polyolefin resin mixture;
(2), put into the proportioning of 50 kilograms in polyolefin resin mixture, 40 kilograms of modification nitrogen phosphorus composite flame-retardant agents, 10 kilograms of dispersion agents, 0.4 kilogram of A-449 retardant synergist, 2.5 kilograms of Lys1-100 lubricants, 0.5 kilogram in oxidation inhibitor in the high-speed mixer in order, normal temperature high-speed mixing 8 minutes, discharging is stand-by;
(3), the twin screw compounding forcing machine that the material of step (2) gained is added heating, the Heating temperature in each district is respectively: 150～160 ℃ in I district, 180～190 ℃ in II district, 180～190 ℃ in III district, 180～185 ℃ in IV district, 180～185 ℃ in V district, 175～18 ℃ in VI district, 175～180 ℃ in VII district, 175～180 ℃ in VIII district, at screw speed 80r/min, be extruded into strip under the rate of feeding 9r/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 |
| 0.3 | 1.18 | 93 | 9.84 | Greater than 200 | VW-1 |
Embodiment two:
(1), by weight ratio for polyethylene mixture: ethylene-vinyl acetate copolymer (EVA)=0.9: 1 feed intake carry out normal temperature mix the polyolefin resin mixture;
(2), put into the proportioning of 48 kilograms in polyolefin resin mixture, 42 kilograms of modification nitrogen phosphorus composite flame-retardant agents, 9 kilograms of dispersion agents, 0.5 kilogram of A-449 retardant synergist, 3.5 kilograms of Lys1-100 lubricants, 0.6 kilogram in oxidation inhibitor in the high-speed mixer in order, normal temperature high-speed mixing 10 minutes, discharging is stand-by;
(3), the twin screw compounding forcing machine that the material of step (2) gained is added heating, the Heating temperature in each district is respectively: 150～160 ℃ in I district, 180～190 ℃ in II district, 180～190 ℃ in III district, 180～185 ℃ in IV district, 180～185 ℃ in V district, 175～180 ℃ in VI district, 175～180 ℃ in VII district, 175～180 ℃ in VIII district, at screw speed 100r/min, be extruded into strip under the rate of feeding 12r/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 | 1.09 | 92 | 9.70 | Greater than 200 | VW-1 |
Embodiment three:
(1), by weight ratio for polyethylene mixture: ethylene-vinyl acetate copolymer (EVA)=1.2: 1 feed intake carry out normal temperature mix the polyolefin resin mixture;
(2), put into the proportioning of 52 kilograms in polyolefin resin mixture, 38 kilograms of modification nitrogen phosphorus composite flame-retardant agents, 12 kilograms of dispersion agents, 0.2 kilogram of A-449 retardant synergist, 1.5 kilograms of Lys1-100 lubricants, 0.4 kilogram in oxidation inhibitor in the high-speed mixer in order, normal temperature high-speed mixing 5 minutes, discharging is stand-by;
(3), the twin screw compounding forcing machine that the material of step (2) gained is added heating, the Heating temperature in each district is respectively: 150～160 ℃ in I district, 180～190 ℃ in II district, 180～190 ℃ in III district, 180～185 ℃ in IV district, 180～185 ℃ in V district, 175～180 ℃ in VI district, 175～180 ℃ in VII district, 175～180 ℃ in VIII district, at screw speed 120r/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 |
| 0.4 | 1.09 | 92 | 9.8 | Greater than 200 | VW-1 |
Claims (3)
1, a kind of low smoke non-halogen fire retarding expansive polyolefins electronic wire material is characterized in that its feed composition and content (weight part) are as follows:
48～52 parts in polyolefin resin mixture, 38～42 parts of nitrogen phosphorus composite flame-retardant agents, 8～12 parts of dispersion agents, 0.2～0.5 part of retardant synergist, 1.5～3.5 parts of lubricants, 0.4～0.6 part in oxidation inhibitor;
Described polyolefin resin mixture is made up of polyethylene mixture and ethylene-vinyl acetate copolymer (EVA), and its weight proportion is a polyethylene mixture: ethylene-vinyl acetate copolymer (EVA)=0.8～1.2: 1;
Described polyethylene mixture is made up of new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE), and its weight proportion is new LDPE (film grade) (LDPE): linear low density polyethylene (LLDPE): high density polyethylene(HDPE) (HDPE)=1: 3: 1.
2, low smoke non-halogen fire retarding expansive polyolefins electronic wire material 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 linear low density polyethylene, its weight proportion is 1: 1.
3, the preparation method of the described low smoke non-halogen fire retarding expansive polyolefins electronic wire material of claim 1 is characterized in that comprising the steps:
(1), nitrogen phosphorus composite flame-retardant agent is dried to its water content less than 0.2% under 80～100 ℃ of temperature, in the input 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, gained was got modification nitrogen phosphorus composite flame-retardant agent in 2～3 hours 100～120 ℃ of temperature bakings;
(2), by weight ratio for new LDPE (film grade) (LDPE): linear low density polyethylene (LLDPE): high density polyethylene(HDPE) (HDPE)=1: 3: 1 feeds intake and carries out combination treatment and get polyethylene mixture;
(3), by weight ratio for polyethylene mixture: ethylene-vinyl acetate copolymer (EVA)=0.8～1.2: 1 feeds intake carry out normal temperature mix the polyolefin resin mixture;
(4), put in the high-speed mixer in order by the proportioning of 48～52 parts in polyolefin resin mixture, 38～42 parts of nitrogen phosphorus composite flame-retardant agents, 8～12 parts of dispersion agents, 0.2～0.5 part of retardant synergist, 1.5～3.5 parts of lubricants, 0.4～0.6 part in oxidation inhibitor, normal temperature high-speed mixing 5～10 minutes, discharging is stand-by;
(5), the material of step (4) gained is added hot-extrudable strip in the twin screw compounding forcing machine, get finished product through cooling and dicing.
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| CN101177508B (en) * | 2006-11-09 | 2011-08-24 | 上海派瑞特塑业有限公司 | Modified high-density polyethylene material and method for making same |
| CN102295798A (en) * | 2010-06-24 | 2011-12-28 | 上海凯波特种电缆料厂有限公司 | Zero-halogen low-smoke flame-retardant injection molding material for branch cable and preparation as well as application thereof |
| CN103232628A (en) * | 2013-04-15 | 2013-08-07 | 中国核电工程有限公司 | Halogen free flame retardation thermal contraction material and thermal contraction casing pipe manufacturing method |
| CN103351505A (en) * | 2012-04-13 | 2013-10-16 | 江苏华磊机电有限公司 | Halogen-free insulation wire and cable material |
| CN104927154A (en) * | 2015-06-13 | 2015-09-23 | 常州大学 | Low-smoke halogen-free polyethylene and polypropylene copolymer flame-retardant cable material |
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| CN109810397A (en) * | 2019-02-02 | 2019-05-28 | 上海国缆检测中心有限公司 | A kind of electric railway low-smoke halogen-free flame-retardant sheath 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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| CN101177508B (en) * | 2006-11-09 | 2011-08-24 | 上海派瑞特塑业有限公司 | Modified high-density polyethylene material and method for making same |
| CN102295798A (en) * | 2010-06-24 | 2011-12-28 | 上海凯波特种电缆料厂有限公司 | Zero-halogen low-smoke flame-retardant injection molding material for branch cable and preparation as well as application thereof |
| CN102295798B (en) * | 2010-06-24 | 2013-01-02 | 上海凯波特种电缆料厂有限公司 | Zero-halogen low-smoke flame-retardant injection molding material for branch cable and preparation as well as application thereof |
| CN102140196A (en) * | 2011-03-14 | 2011-08-03 | 镇国广 | Room temperature self-crosslinked polyethylene insulation material |
| CN103351505A (en) * | 2012-04-13 | 2013-10-16 | 江苏华磊机电有限公司 | Halogen-free insulation wire and cable material |
| CN103232628A (en) * | 2013-04-15 | 2013-08-07 | 中国核电工程有限公司 | Halogen free flame retardation thermal contraction material and thermal contraction casing pipe manufacturing method |
| CN103232628B (en) * | 2013-04-15 | 2015-11-04 | 中国核电工程有限公司 | The manufacture method of a kind of halogen-free flame-retardant thermal shrinkage material and thermal contraction casing tube |
| CN104927154A (en) * | 2015-06-13 | 2015-09-23 | 常州大学 | Low-smoke halogen-free polyethylene and polypropylene copolymer flame-retardant cable material |
| CN109021376A (en) * | 2018-07-18 | 2018-12-18 | 江苏理工学院 | A kind of halogen-free flameproof EVA foamed material and preparation method thereof |
| CN109810397A (en) * | 2019-02-02 | 2019-05-28 | 上海国缆检测中心有限公司 | A kind of electric railway low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| CN110204810A (en) * | 2019-05-15 | 2019-09-06 | 荆州亮诚科技股份有限公司 | A kind of production method of environmental-protection flame-retardant silicone pipes |
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Address after: 525000 Guangdong Province, Maoming city Guandu Road No. 49 North Lane Co-patentee after: Xiao Dequan Patentee after: Xiao Qihai Co-patentee after: Lead Ya Electronic Technology Co., Ltd. Address before: 525000 Guangdong Province, Maoming city Guandu Road No. 49 North Lane Co-patentee before: Xiao Dequan Patentee before: Xiao Qihai Co-patentee before: Guangdong Xinya Wire&Cable Co., Ltd. |
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Address after: 525000 Guangdong Province, Maoming city Guandu Road No. 49 North Lane Co-patentee after: Xiao Dequan Patentee after: Xiao Qihai Co-patentee after: Linoya Electronics Co., Ltd. Address before: 525000 Guangdong Province, Maoming city Guandu Road No. 49 North Lane Co-patentee before: Xiao Dequan Patentee before: Xiao Qihai Co-patentee before: Lead Ya Electronic Technology Co., Ltd. |
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Owner name: XIAO DEQUAN Free format text: FORMER OWNER: XIAO DEQUAN LINOYA ELECTRONICS TECHNOLOGY CO., LTD. Effective date: 20120928 |
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Effective date of registration: 20120928 Address after: 525000 Guangdong Province, Maoming city Guandu Road No. 49 North Lane Patentee after: Xiao Qihai Patentee after: Xiao Dequan Address before: 525000 Guangdong Province, Maoming city Guandu Road No. 49 North Lane Patentee before: Xiao Qihai Patentee before: Xiao Dequan Patentee before: Linoya Electronics Co., Ltd. |
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Granted publication date: 20080123 Termination date: 20121221 |