CN104194139B - High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof - Google Patents
High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof Download PDFInfo
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- CN104194139B CN104194139B CN201410423907.9A CN201410423907A CN104194139B CN 104194139 B CN104194139 B CN 104194139B CN 201410423907 A CN201410423907 A CN 201410423907A CN 104194139 B CN104194139 B CN 104194139B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 33
- 238000005299 abrasion Methods 0.000 title claims abstract description 30
- 238000004132 cross linking Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 22
- 238000011049 filling Methods 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 230000003078 antioxidant Effects 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- VOLSCWDWGMWXGO-UHFFFAOYSA-N cyclobuten-1-yl acetate Chemical compound CC(=O)OC1=CCC1 VOLSCWDWGMWXGO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 17
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 32
- UAUDZVJPLUQNMU-KTKRTIGZSA-N (Z)-docos-13-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 16
- 210000003135 Vibrissae Anatomy 0.000 claims description 16
- 159000000003 magnesium salts Chemical class 0.000 claims description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims description 13
- -1 pentaerythritol ester Chemical class 0.000 claims description 11
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-tris(prop-2-enoxy)-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- HGZNRFJUXYMRGZ-UHFFFAOYSA-N 4-nonyl-2-(1-phenylethyl)phenol Chemical compound CCCCCCCCCC1=CC=C(O)C(C(C)C=2C=CC=CC=2)=C1 HGZNRFJUXYMRGZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QXUAMGWCVYZOLV-UHFFFAOYSA-N boride(3-) Chemical compound [B-3] QXUAMGWCVYZOLV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002588 toxic Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
The invention relates to a high-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for an automobile thin-wall wire and a preparation method thereof. The high wear-resistant irradiation crosslinking halogen-free flame retardant polyolefin material is prepared by mixing raw materials such as linear low-density polyethylene resin, ethylene vinyl acetate resin, modified resin, a halogen-free flame retardant, silicon dioxide, a filling modifier, an antioxidant, a crosslinking agent, a compound slip agent and the like through a mixing machine, mixing and extruding through an extruder. The automobile thin-wall electric wire manufactured by adopting the high-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material not only has the performances of halogen-free flame retardance, environmental protection, high temperature resistance and low temperature resistance; the halogen-free flame-retardant and high-temperature-resistant automobile thin-wall wire insulating layer has good scratch and abrasion resistance, high extrusion speed and good processability, can meet the requirement of an automobile thin-wall wire with the temperature resistance level of 125 ℃, and can be used as a raw material for manufacturing the halogen-free flame-retardant and high-temperature-resistant (125 ℃) automobile thin-wall wire insulating layer.
Description
Technical field
The present invention relates to a kind of plastic pellet and preparation method thereof.Specifically, making raw material------high abrasion irradiation crosslinking halogen-free fire retardant polyolefin particle of halogen-free flameproof car thin-wall electric wire insulation layer with relatively high-temperature resistant grade (125 degrees Celsius) and preparation method thereof it is used to.
Background technology
Along with the fast development of auto industry, the safety of automobile, operability, economy, the feature of environmental protection are also developed rapidly with its electronization.Along with increase, the temperature of engine power raise and the requirement of automotive light weight technology, more and more higher to the requirement of the insulating coating of electric wire on automobile, both required relatively thin thickness, required again that it had higher high and low temperature resistance, anti-wear performance, ageing resistace and halogen-free flameproof performance.
At present, the raw material being used for making car thin-wall electric wire insulation layer is all particulate polyvinyl chloride or some Halogen fire retardant polyolefin material.Polrvinyl chloride has that price is relatively low, be easy to the advantages such as processing, but polrvinyl chloride exists the shortcomings such as decomposition temperature is low, resistance to elevated temperatures is poor, not only constrains its development, and use occasion is restricted.Polrvinyl chloride and Halogen fire retardant polyolefin material, can discharge the toxic and harmfuls such as a large amount of hydrogen halides during burning, be unfavorable for personnel escape and cause secondary to endanger instrument and equipment etc., to environment.For solving problem above, the most mostly substitute polrvinyl chloride and Halogen fire retardant polyolefin with halogen-free material.Although using halogen-free material to substitute polrvinyl chloride and Halogen polyolefin can being avoided discharging toxic and harmful during burning, air will not be polluted, and with similar on market can the car thin-wall electric wire insulation layer made of irradiation crosslinking halogen-free fire retardant polyolefin particle, all there is the defect that resistance to scraped finish is poor, extruded velocity is slow, processing characteristics is bad, it is difficult to meet the requirement of the car thin-wall electric wire that temperature resistant grade is 125 degrees Celsius.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material.The car thin-wall electric wire using this high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material to make, not only has halogen-free flameproof, environmental protection, high temperature resistant, resistance to low temperature；And scrape abrasion resistance can be good, extruded velocity is fast, and good processability can meet the requirement of the car thin-wall electric wire that temperature resistant grade is 125 degrees Celsius.
Another problem that the invention solves the problems that is to provide a kind of method preparing car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material.
For solving the problems referred to above, take techniques below scheme:
The feature of the car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material of the present invention is made up of the raw material of following parts by weight:
Linear low density polyethylene resin 16 ~ 22 weight portion；Ethylene vinyl acetate resin 60 ~ 71 weight portion；Modified resin 13 ~ 18 weight portion；Halogen-free flame retardants 90 ~ 110 weight portion；Silicon dioxide 20 ~ 30 weight portion；Filling modifying agent 30 ~ 40 weight portion；Antioxidant 0.4 ~ 1 weight portion；Cross-linking agent 0.8 ~ 1.5 weight portion；Compounding slipping agent 2 ~ 3 weight portion；Described silicon dioxide is made up after aminosilane-treated of nano silicon.
Wherein, the melt index of described linear low density polyethylene resin is 1.0 ~ 2.0g/10min.In described ethylene vinyl acetate resin, the weight content of vinyl acetate is 28%, melt index≤6g/10min.Described modified resin is the polar monomer graft thing of ethylene-vinyl acetate copolymer, and it is carried out graft reaction by maleic anhydride monomer and makes, and in this polar monomer graft thing, the content of maleic anhydride grafted monomers is 1.5%.Described halogen-free flame retardants is with magnesium hydroxide and aluminium hydroxide, and according to magnesium hydroxide: the part by weight of aluminium hydroxide=2:3 and make.Described filling modifying agent is with barium sulfate, magnesium salt whisker and carborundum, and according to barium sulfate: magnesium salt whisker: the part by weight of carborundum=5:5:2 and make.Described antioxidant be four [3-(3 ', 5 ' di-t-butyl 4 ' hydroxy phenyls) propanoic acid] pentaerythritol ester or 2,6 two (1-phenyl) ethyl 4 nonyl phenol.Described cross-linking agent is by cumyl peroxide and triallyl cyanurate, according to cumyl peroxide: the part by weight of triallyl cyanurate=1:5 and make.Described compounding slipping agent is with erucyl amide, siloxanes and Tissuemat E, and according to erucyl amide: siloxanes: the part by weight of Tissuemat E=2:2:1 and make.
The feature of the preparation method of the car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material of the present invention is to comprise the following steps successively:
First, nano silicon is put in the homogenizer of 1350 ~ 1450 revs/min, and under stirring, in 2 minutes, use spray method to spray into amino silicane coupling agent；Afterwards, with the rotating speed of 600 ~ 700 revs/min, continue stirring 1 ~ 2 minute, obtain the silicon dioxide handled well；
Then, linear low density polyethylene resin, ethylene vinyl acetate resin, modified resin, halogen-free flame retardants, silicon dioxide, filling modifying agent, antioxidant, cross-linking agent, compounding slipping agent are added together in the mixing roll that temperature is 150 ~ 160 degrees Celsius mixing 12 ~ 15 minutes, make dough material；
Finally, with the double screw extruder with six temperature sections, described dough material extruded and made graininess, obtaining high abrasion irradiation crosslinking halogen-free fire retardant polyolefin particle, i.e. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material；The temperature of six temperature sections of described double screw extruder is respectively 135 degrees Celsius, 150 degrees Celsius, 160 degrees Celsius, 165 degrees Celsius, 165 degrees Celsius, 160 degrees Celsius.
Use such scheme, have the advantage that
As can be seen from the above scheme, owing to the raw material of the present invention have employed nano silicon through aminosilane-treated technology, nano silicon can be preferably distributed in material, and more firm with resin-bonded power, it is ensured that the wearability of product is improved.
Simultaneously, have employed the filling modifying agent that barium sulfate, magnesium salt whisker and carborundum are compounding in the raw material of the present invention, this filling modifying agent system substantially increases product rheology, anti-flammability and wearability so that material is in the course of processing, extruded velocity is fast, good processability.
The raw material of the present invention uses erucyl amide, siloxanes and the compounding slipping agent of Tissuemat E, solves product surface formation wax layer and decrease coefficient of friction to improve wearability and to prevent the contradiction between product surface bloom.It addition, the erucyl amide in treated nano silicon and compounding slipping agent has synergism so that the erucyl amide of higher amount is exposed on surface, improve the wearability of product further.
The raw materials such as linear low density polyethylene resin, ethylene vinyl acetate resin, modified resin, halogen-free flame retardants, silicon dioxide, filling modifying agent, antioxidant, cross-linking agent, compounding slipping agent are contained due to the present invention.Make with during this production car thin-wall electric wire, extrusion molding speed fast (the fastest up to more than 330m/min), the car thin-wall electric wire made has a temperature resistant grade high (long-term 125 DEG C) simultaneously, the characteristic such as excellent halogen-free flameproof, environmental protection, oil resistant, resistance to ozone, low temperature resistant, stress crack resistant, resistance to crushing, solvent resistant, the welding of resistance to molten iron, short circuit temperature draw point high, resistance to scraped finish excellent performance.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment one
First, nano silicon is put in the homogenizer of 1350 revs/min, and under stirring, in 2 minutes, use spray method to spray into amino silicane coupling agent；Afterwards, with the rotating speed of 600 revs/min, continue stirring 2 minutes, obtain the silicon dioxide handled well.
Then, the linear low density polyethylene resin of 16 weight portions, the ethylene vinyl acetate resin of 71 weight portions, the modified resin of 13 weight portions, the halogen-free flame retardants of 90 weight portions, the silicon dioxide of 20 weight portions, the filling modifying agent of 30 weight portions, the antioxidant of 0.4 weight portion, the cross-linking agent of 0.8 weight portion, the compounding slipping agent of 2 weight portions are chosen.
Afterwards, linear low density polyethylene resin, ethylene vinyl acetate resin, modified resin, halogen-free flame retardants, silicon dioxide, filling modifying agent, antioxidant, cross-linking agent, compounding slipping agent are added together in the mixing roll that temperature is 150 degrees Celsius mixing 12 minutes, make dough material.
Finally, with the double screw extruder with six temperature sections, described dough material extruded and made graininess, obtaining high abrasion irradiation crosslinking halogen-free fire retardant polyolefin particle, i.e. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material；The temperature of six temperature sections of described double screw extruder is respectively 135 degrees Celsius, 150 degrees Celsius, 160 degrees Celsius, 165 degrees Celsius, 165 degrees Celsius, 160 degrees Celsius.
In the present embodiment:
The melt index of described linear low density polyethylene resin is 1.0 ~ 2.0g/10min.
In described ethylene vinyl acetate resin, the weight content of vinyl acetate is 28%, melt index≤6g/10min.
Described modified resin is the polar monomer graft thing of ethylene-vinyl acetate copolymer, and it is carried out graft reaction by maleic anhydride monomer and makes, and in this polar monomer graft thing, the content of maleic anhydride grafted monomers is 1.5%.Described modified resin is the S-of the liters macromolecular material company limited production of Shanghai day26Type modification resin.
Described halogen-free flame retardants is to use magnesium hydroxide and aluminium hydroxide, and according to magnesium hydroxide: the part by weight of aluminium hydroxide=2:3 is made.
Described nano silicon is the product that Shenyang Chemical Co., Ltd. produces.
Described filling modifying agent is to use barium sulfate, magnesium salt whisker and carborundum, and according to barium sulfate: magnesium salt whisker: the part by weight of carborundum=5:5:2 is made.Barium sulfate is that Shanghai jumps the product that river titanium dioxide maker produces, and magnesium salt whisker is the product that Wei Sike branch company of Yingkou Kangru Chemicals Co., Ltd. produces, and carborundum is the product of rich triumphant share nitrogen boride plant produced of ringing.
Described antioxidant be four [3-(3 ', 5 ' di-t-butyl 4 ' hydroxy phenyls) propanoic acid] pentaerythritol ester or 2,6 two (1-phenyl) ethyl 4 nonyl phenol, is the product produced by Ciba of Switzerland.
Described cross-linking agent is by cumyl peroxide and triallyl cyanurate, according to cumyl peroxide: the part by weight of triallyl cyanurate=1:5 and make, be the product produced by Chemical Co., Ltd. of Qingdao Cigna/Shanghai Ci Tai Yilong Industry Co., Ltd..
Described compounding slipping agent is with erucyl amide, siloxanes and Tissuemat E, and according to erucyl amide: siloxanes: the part by weight of Tissuemat E=2:2:1 and make.Erucyl amide is the product that Nanjing Tian Xin Chemical Co., Ltd. produces, and siloxanes is the product that Dow corning company produces, trade mark MB50-002, and Tissuemat E is the product that Shanghai Gaoqiao petro-chemical corporation produces.
Embodiment two
First, nano silicon is put in the homogenizer of 1400 revs/min, and under stirring, in 1.5 minutes, use spray method to spray into amino silicane coupling agent；Afterwards, with the rotating speed of 650 revs/min, continue stirring 1.5 minutes, obtain the silicon dioxide handled well.
Then, the linear low density polyethylene resin of 19 weight portions, the ethylene vinyl acetate resin of 66 weight portions, the modified resin of 15 weight portions, the halogen-free flame retardants of 100 weight portions, the silicon dioxide of 25 weight portions, the filling modifying agent of 35 weight portions, the antioxidant of 0.7 weight portion, the cross-linking agent of 1.2 weight portions, the compounding slipping agent of 2.5 weight portions are chosen.
Afterwards, linear low density polyethylene resin, ethylene vinyl acetate resin, modified resin, halogen-free flame retardants, silicon dioxide, filling modifying agent, antioxidant, cross-linking agent, compounding slipping agent are added together in the mixing roll that temperature is 155 degrees Celsius mixing 13 minutes, make dough material.
Finally, with having the double screw extruder staying a temperature section, described dough material extruded and made graininess, obtaining high abrasion irradiation crosslinking halogen-free fire retardant polyolefin particle, i.e. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material；The temperature of six temperature sections of described double screw extruder is respectively 135 degrees Celsius, 150 degrees Celsius, 160 degrees Celsius, 165 degrees Celsius, 165 degrees Celsius, 160 degrees Celsius.
In the present embodiment:
The melt index of described linear low density polyethylene resin is 1.0 ~ 2.0g/10min.
In described ethylene vinyl acetate resin, the weight content of vinyl acetate is 28%, melt index≤6g/10min.
Described modified resin is the polar monomer graft thing of ethylene-vinyl acetate copolymer, and it is carried out graft reaction by maleic anhydride monomer and makes, and in this polar monomer graft thing, the content of maleic anhydride grafted monomers is 1.5%.Described modified resin is the S-of the liters macromolecular material company limited production of Shanghai day26Type modification resin.
Described halogen-free flame retardants is to use magnesium hydroxide and aluminium hydroxide, and according to magnesium hydroxide: the part by weight of aluminium hydroxide=2:3 is made.
Described nano silicon is the product that Shenyang Chemical Co., Ltd. produces.
Described filling modifying agent is to use barium sulfate, magnesium salt whisker and carborundum, and according to barium sulfate: magnesium salt whisker: the part by weight of carborundum=5:5:2 is made.Barium sulfate is that Shanghai jumps the product that river titanium dioxide maker produces, and magnesium salt whisker is the product that Wei Sike branch company of Yingkou Kangru Chemicals Co., Ltd. produces, and carborundum is the product of rich triumphant share nitrogen boride plant produced of ringing.
Described antioxidant be four [3-(3 ', 5 ' di-t-butyl 4 ' hydroxy phenyls) propanoic acid] pentaerythritol ester or 2,6 two (1-phenyl) ethyl 4 nonyl phenol, is the product produced by Ciba of Switzerland.
Described cross-linking agent is by cumyl peroxide and triallyl cyanurate, according to cumyl peroxide: the part by weight of triallyl cyanurate=1:5 and make, be the product produced by Chemical Co., Ltd. of Qingdao Cigna/Shanghai Ci Tai Yilong Industry Co., Ltd..
Described compounding slipping agent is with erucyl amide, siloxanes and Tissuemat E, and according to erucyl amide: siloxanes: the part by weight of Tissuemat E=2:2:1 and make.Erucyl amide is the product that Nanjing Tian Xin Chemical Co., Ltd. produces, and siloxanes is the product that Dow corning company produces, trade mark MB50-002, and Tissuemat E is the product that Shanghai Gaoqiao petro-chemical corporation produces.
Embodiment three
First, nano silicon is put in the homogenizer of 1450 revs/min, and under stirring, in 1 minutes, use spray method to spray into amino silicane coupling agent；Afterwards, with the rotating speed of 700 revs/min, continue stirring 1 minute, obtain the silicon dioxide handled well.
Then, the linear low density polyethylene resin of 22 weight portions, the ethylene vinyl acetate resin of 60 weight portions, the modified resin of 18 weight portions, the halogen-free flame retardants of 110 weight portions, the silicon dioxide of 30 weight portions, the filling modifying agent of 40 weight portions, the antioxidant of 1 weight portion, the cross-linking agent of 1.5 weight portions, the compounding slipping agent of 3 weight portions are chosen.
Afterwards, linear low density polyethylene resin, ethylene vinyl acetate resin, modified resin, halogen-free flame retardants, silicon dioxide, filling modifying agent, antioxidant, cross-linking agent, compounding slipping agent are added together in the mixing roll that temperature is 160 degrees Celsius mixing 15 minutes, make dough material；
Finally, with double screw extruder, described dough material extruded and made graininess, obtaining car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material；The temperature of six temperature sections of described double screw extruder is respectively 135 degrees Celsius, 150 degrees Celsius, 160 degrees Celsius, 165 degrees Celsius, 165 degrees Celsius, 160 degrees Celsius.
In the present embodiment:
The melt index of described linear low density polyethylene resin is 1.0 ~ 2.0g/10min.
In described ethylene vinyl acetate resin, the weight content of vinyl acetate is 28%, melt index≤6g/10min.
Described modified resin is the polar monomer graft thing of ethylene-vinyl acetate copolymer, and it is carried out graft reaction by maleic anhydride monomer and makes, and in this polar monomer graft thing, the content of maleic anhydride grafted monomers is 1.5%.Described modified resin is the S-of the liters macromolecular material company limited production of Shanghai day26Type modification resin.
Described halogen-free flame retardants is to use magnesium hydroxide and aluminium hydroxide, and according to magnesium hydroxide: the part by weight of aluminium hydroxide=2:3 is made.
Described nano silicon is the product that Shenyang Chemical Co., Ltd. produces.
Described filling modifying agent is to use barium sulfate, magnesium salt whisker and carborundum, and according to barium sulfate: magnesium salt whisker: the part by weight of carborundum=5:5:2 is made.Barium sulfate is that Shanghai jumps the product that river titanium dioxide maker produces, and magnesium salt whisker is the product that Wei Sike branch company of Yingkou Kangru Chemicals Co., Ltd. produces, and carborundum is the product of rich triumphant share nitrogen boride plant produced of ringing.
Described antioxidant be four [3-(3 ', 5 ' di-t-butyl 4 ' hydroxy phenyls) propanoic acid] pentaerythritol ester or 2,6 two (1-phenyl) ethyl 4 nonyl phenol, is the product produced by Ciba of Switzerland.
Described cross-linking agent is by cumyl peroxide and triallyl cyanurate, according to cumyl peroxide: the part by weight of triallyl cyanurate=1:5 and make, be the product produced by Chemical Co., Ltd. of Qingdao Cigna/Shanghai Ci Tai Yilong Industry Co., Ltd..
Described compounding slipping agent is with erucyl amide, siloxanes and Tissuemat E, and according to erucyl amide: siloxanes: the part by weight of Tissuemat E=2:2:1 and make.Erucyl amide is the product that Nanjing Tian Xin Chemical Co., Ltd. produces, and siloxanes is the product that Dow corning company produces, trade mark MB50-002, and Tissuemat E is the product that Shanghai Gaoqiao petro-chemical corporation produces.
Above three embodiment gained car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material, see table according to relative national standards test gained performance parameter:
Claims (7)
1. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material, it is characterised in that be made up of the raw material of following parts by weight:
Linear low density polyethylene resin 16 ~ 22 weight portion；
Ethylene vinyl acetate resin 60 ~ 71 weight portion；
Modified resin 13 ~ 18 weight portion；
Halogen-free flame retardants 90 ~ 110 weight portion；
Silicon dioxide 20 ~ 30 weight portion；
Filling modifying agent 30 ~ 40 weight portion；
Antioxidant 0.4 ~ 1 weight portion；
Cross-linking agent 0.8 ~ 1.5 weight portion；
Compounding slipping agent 2 ~ 3 weight portion；
Described modified resin is the polar monomer graft thing of ethylene-vinyl acetate copolymer, and it is carried out graft reaction by maleic anhydride monomer and makes, and in this polar monomer graft thing, the content of maleic anhydride grafted monomers is 1.5%；
Described silicon dioxide is made up after aminosilane-treated of nano silicon；
Described filling modifying agent is with barium sulfate, magnesium salt whisker and carborundum, and according to barium sulfate: magnesium salt whisker: the part by weight of carborundum=5:5:2 and make；
Described compounding slipping agent is with erucyl amide, siloxanes and Tissuemat E, and according to erucyl amide: siloxanes: the part by weight of Tissuemat E=2:2:1 and make.
2. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material as claimed in claim 1, it is characterised in that the melt index of described linear low density polyethylene resin is 1.0 ~ 2.0g/10min.
3. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material as claimed in claim 1, it is characterised in that in described ethylene vinyl acetate resin, the weight content of vinyl acetate is 28%, melt index≤6g/10min.
4. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material as claimed in claim 1, it is characterised in that described halogen-free flame retardants is with magnesium hydroxide and aluminium hydroxide, and according to magnesium hydroxide: the part by weight of aluminium hydroxide=2:3 and make.
5. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material as claimed in claim 1, it is characterized in that described antioxidant be four [3-(3 ', 5 ' di-t-butyl 4 ' hydroxy phenyls) propanoic acid] pentaerythritol ester or 2,6 two (1-phenyl) ethyl 4 nonyl phenol.
6. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material as claimed in claim 1, it is characterized in that described cross-linking agent is by cumyl peroxide and triallyl cyanurate, according to cumyl peroxide: the part by weight of triallyl cyanurate=1:5 and make.
7. the car thin-wall electric wire method of high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material described in preparation claim 1, it is characterised in that comprise the following steps successively:
First, nano silicon is put in the homogenizer of 1350 ~ 1450 revs/min, and under stirring, in 2 minutes, use spray method to spray into amino silicane coupling agent；Afterwards, with the rotating speed of 600 ~ 700 revs/min, continue stirring 1 ~ 2 minute, obtain the silicon dioxide handled well；
Then, linear low density polyethylene resin, ethylene vinyl acetate resin, modified resin, halogen-free flame retardants, silicon dioxide, filling modifying agent, antioxidant, cross-linking agent, compounding slipping agent are added together in the mixing roll that temperature is 150 ~ 160 degrees Celsius mixing 12 ~ 15 minutes, make dough material；Wherein, described filling modifying agent is with barium sulfate, magnesium salt whisker and carborundum, and according to barium sulfate: magnesium salt whisker: the part by weight of carborundum=5:5:2 and make；
Finally, with the double screw extruder with six temperature sections, described dough material extruded and made graininess, obtaining high abrasion irradiation crosslinking halogen-free fire retardant polyolefin particle, i.e. car thin-wall electric wire high abrasion irradiation crosslinking halogen-free fire retardant polyolefin material；The temperature of six temperature sections of described double screw extruder is respectively 135 degrees Celsius, 150 degrees Celsius, 160 degrees Celsius, 165 degrees Celsius, 165 degrees Celsius, 160 degrees Celsius.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410423907.9A CN104194139B (en) | 2014-08-26 | High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410423907.9A CN104194139B (en) | 2014-08-26 | High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104194139A CN104194139A (en) | 2014-12-10 |
| CN104194139B true CN104194139B (en) | 2017-01-04 |
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| CP03 | Change of name, title or address |
Address after: No.39, Yanqiao Road, Yanqiao supporting area, Huishan Economic Development Zone, Wuxi City, Jiangsu Province, 214000 Patentee after: Wuxi Jieke New Material Co.,Ltd. Address before: 214174 No. 39, Yanqiao Road, Yanqiao supporting area, Huishan District, Wuxi City, Jiangsu Province Patentee before: WUXI JAKE PLASTIC Co.,Ltd. |