CN1629216A - Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby - Google Patents
Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby Download PDFInfo
- Publication number
- CN1629216A CN1629216A CN 200310104076 CN200310104076A CN1629216A CN 1629216 A CN1629216 A CN 1629216A CN 200310104076 CN200310104076 CN 200310104076 CN 200310104076 A CN200310104076 A CN 200310104076A CN 1629216 A CN1629216 A CN 1629216A
- Authority
- CN
- China
- Prior art keywords
- halogen
- free flame
- flame retardant
- heat shrinkable
- retardant heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims description 65
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 6
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 18
- 239000004945 silicone rubber Substances 0.000 claims abstract description 17
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 8
- 239000005060 rubber Substances 0.000 claims abstract description 8
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 7
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims abstract description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 31
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 235000019359 magnesium stearate Nutrition 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 claims description 8
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- -1 methyl phenyl vinyl Chemical group 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 6
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 4
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims 4
- 239000005042 ethylene-ethyl acrylate Substances 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 abstract description 7
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001684 low density polyethylene Polymers 0.000 abstract 2
- 239000004702 low-density polyethylene Substances 0.000 abstract 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 abstract 1
- 230000008602 contraction Effects 0.000 abstract 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RIANRUHKVPYCDS-UHFFFAOYSA-N C=Cc1ccccc1.C=CC(C=C)=Cc1ccccc1 Chemical compound C=Cc1ccccc1.C=CC(C=C)=Cc1ccccc1 RIANRUHKVPYCDS-UHFFFAOYSA-N 0.000 description 3
- MSAVICZWFPQFPO-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.C=C.CC(O)=O MSAVICZWFPQFPO-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical class C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- BNBQRQQYDMDJAH-UHFFFAOYSA-N benzodioxan Chemical compound C1=CC=C2OCCOC2=C1 BNBQRQQYDMDJAH-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention provides a bittern-free flame-proof thermal contraction sleeve which comprises (by weight ratio), (1) 100 parts of one or more selected from ethane-vinyl acetate copolymer (EVA), ethene-ethyl acrylate copolymer (EEA), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (2) 5-50 parts of one or more selected from ethylene-propylene terpolymerisate rubber (EPDM), ethylene propylene rubber (EPM), dimethyl silicone rubber (MQ), methylvinyl silicone rubber (VMQ), methylsilicone rubber with phenyl and vinyl Group (PVMQ), thermoplastic elastomer styrene - butadiene - styrene blocked copolymer (SBS), styrene-isoprene blocked copolymer (SIS), (3) 50-100 parts of bittern-free flame retardant, and (4) 0.5-6 parts of coupling agent.
Description
[technical field]
The present invention relates to the flame-retardant heat shrinkable sleeve field, especially a kind of halogen-free flame retardant heat shrinkable sheathing material reaches the halogen-free flame retardant heat shrinkable sheathing by this material preparation.
[background technology]
The flame-retardant heat shrinkable sleeve that provides in the market, basically all adopt the fire-retardant product of halogenide, wherein the overwhelming majority is to adopt organic bromide and the fire-retardant product of antimonous oxide, this series products environmental pollution, produce poisonous in a large number, mordant bromize hydrogen gas during burning, also might produce the Dioxins of severe toxicity, i.e. many bromos benzdioxan and bromo diphenylene-oxide, this is a kind of carcinogens.Antimonous oxide can produce dust pollution in process of production simultaneously, and this dust can damage personal respiratory system, can make personal skin produce the supersensitivity erythema, and the employing of antimonous oxide also can make the sleeve pipe heavy metal element exceed standard.
[summary of the invention]
The object of the present invention is to provide a kind of safe in utilization and have the halogen-free flame retardant heat shrinkable sheathing material of environment-friendly function and by the halogen-free flame retardant heat shrinkable sheathing of this material preparation.
The object of the present invention is achieved like this: this a kind of halogen-free flame retardant heat shrinkable sheathing material contains by weight: 1. the material of one or more in ethene-acetate ethylene copolymer (EVA), ethene-ethyl acrylate copolymer (EEA), new LDPE (film grade) (LDPE), the linear low density polyethylene (LLDPE) is 100 parts; 2. material 5-50 part of one or more in terpolymer EP rubber (EPDM), ethylene propylene rubber (EPM), dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ), thermoplastic elastomer vinylbenzene-divinyl-styrene block copolymer (SBS), the vinylbenzene-isoprene block copolymer (SIS); 3. halogen-free flame retardants 50-100 part; And 4. coupling agent 0.5-6 part.
Described halogen-free flame retardants is selected from following a kind of material or more than one material: aluminium hydroxide, magnesium hydroxide, red phosphorus powder, polyphosphoric acid ammonia, hydration zinc borate.
Described coupling agent is selected from following a kind of material or more than one materials: vinyl three (methoxyethoxy) silane (A-172), r-(methacryloxy) propyl trimethoxy silicane (A-174), vinyltriethoxysilane (A-151).
The material of this a kind of halogen-free flame retardant heat shrinkable sheathing contains by weight:
1. the material of one or more in ethene-acetate ethylene copolymer (EVA), ethene-ethyl acrylate copolymer (EEA), new LDPE (film grade) (LDPE), the linear low density polyethylene (LLDPE) is 100 parts;
2. material 5-50 part of one or more in terpolymer EP rubber (EPDM), ethylene propylene rubber (EPM), dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ), thermoplastic elastomer vinylbenzene-divinyl-styrene block copolymer (SBS), the vinylbenzene-isoprene block copolymer (SIS);
3. halogen-free flame retardants 50-100 part, it is selected from following a kind of material or more than one material: aluminium hydroxide, magnesium hydroxide, red phosphorus powder, polyphosphoric acid ammonia, hydration zinc borate;
4. coupling agent 0.5-6 part, it is a silicon additive;
5. lubricant 0.5-1 part, it is selected from following one or more material: Zinic stearas (ZnSt), Magnesium Stearate (MgSt), stearic acid (HSt), n-butyl stearate (BS);
6. tinting material colour batch 2-10 part, it is selected from following a kind of material or more than one materials: carbon black, iron oxide red powder, ultramarine, phthalocyanine blue B, phthalocyanine blue B X, Fast Yellow G, permanent yellow HSZG, the red B of plastics, fluorescent yellow YG-51; And
7. oxidation inhibitor 0.5-1 part.
Compared with prior art, the present invention has following advantage: the present invention is environmentally friendly, can toxigenicity gas during burning, do not contain harmful heavy metal in the material simultaneously, so have the effect of safety and environmental protection, and raw material is easy to obtain, and manufacture method adopts traditional manufacture method, is suitable for industrialization production.
[embodiment]
A kind of halogen-free flame retardant heat shrinkable sheathing material of the present invention, wherein by weight, contain:
1. the material of one or more in ethene-acetate ethylene copolymer (EVA), ethene-ethyl acrylate copolymer (EEA), new LDPE (film grade) (LDPE), the linear low density polyethylene (LLDPE) is 100 parts;
2. material 5-50 part of one or more in terpolymer EP rubber (EPDM), ethylene propylene rubber (EPM), dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ), thermoplastic elastomer vinylbenzene-divinyl-styrene block copolymer (SBS), the vinylbenzene-isoprene block copolymer (SIS);
3. halogen-free flame retardants 50-100 part, it is selected from following a kind of material or more than one material: fine aluminum hydroxide powder, magnesium hydroxide micro mist, microcapsule red phosphorus powder, micro encapsulation polyphosphoric acid ammonia, hydration zinc borate powder;
4. coupling agent 0.5-6 part, it can be silicon additive, can be selected from following a kind of material or more than one materials: vinyl three (methoxyethoxy) silane (A-172), r-(methacryloxy) propyl trimethoxy silicane (A-174), vinyltriethoxysilane (A-151);
This halogen-free flame retardant heat shrinkable sheathing material also can contain:
5. oxidation inhibitor 0.5-1 part, it is existing antioxidant, as is four [β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid] seasons to become tetrol esters (antioxidant 1010);
6. lubricant 0.5-1 part, it is selected from following one or more material: Zinic stearas (ZnSt), Magnesium Stearate (MgSt), stearic acid (HSt), n-butyl stearate (BS);
7. tinting material colour batch 2-10 part, it is selected from following a kind of material or more than one materials: mineral dye or pigment dyestuff that carbon black, iron oxide red powder, ultramarine, phthalocyanine blue B, phthalocyanine blue B X, Fast Yellow G, permanent yellow HSZG, the red B of plastics, fluorescent yellow YG-51 etc. be not halogen-containing, do not contain heavy metal.
The preparation method of halogen-free flame retardant heat shrinkable sheathing of the present invention is as follows: the composition of 1) etc. above-mentioned various materials adopts high-speed mixer to mix, adopt the method for mechanical blending to make it to become a kind of polymer alloy master batch of halogen-free flameproof then, the method for this mechanical blending refers to following any one method: 1. compressing tablet pelletizing after the blend of electrically heated twin-roll plastic mixing mill; 2. Banbury mixer blend, the pelletizing of twin-roll plastic mixing mill compressing tablet; 3. the parallel double-screw blend extrude, pelletizing; 2) with the Halogenless fire retarded polymer alloy master batch that obtains with common plastics list screw extrusion molding, obtain the Halogenless fire retarded polymer alloy pipe of any specification; 3) tubing that obtains is crosslinked by high-energy ray irradiation, make the degree of crosslinking of polymer alloy tubing reach 50-90%, energetic ray is meant the r ray that utilizes electron beam that high-energy electron accelerator obtains or cobalt 60 radioactive sources to emit; 4) tubing with certain degree of crosslinking that step 3) is obtained is heated to softening temperature, adopts mechanical means, pneumatic process or vacuum method or both bonded methods that it is carried out radial dilatation, and the quenching typing of expansion back promptly obtains halogen-free flame retardant heat shrinkable sheathing.
Zhi Bei halogen-free flame retardant heat shrinkable sheathing according to the method described above, the main physical mechanical performance index all meets the requirement of UL224 standard, and its key technical indexes is as follows: tensile strength 〉=10.4Mpa; Elongation at break 〉=200%; Under the condition of 158 ℃ and 168 hours, the tensile strength 〉=7.3Mpa after the hot air aging, aging back elongation at break 〉=100%, disruptive strength 〉=15kv/mm, volume resistivity 〉=1 * 10
14Ohmcm, the fire-retardant FV-1 level that meets; It is qualified that environmental-protecting performance detects by SGS, the concrete test result of the content of test halogens and eight big metals is as follows: not fluorine-containing (F), bromine (Ar), iodine (I), chlorine is 57.62PPM, lead＜2PPM, cadmium＜2PPM, antimony＜2PPM, barium＜2PPM, chromium＜2PPM, mercury＜2PPM, arsenic＜2PPM, tin＜2PPM.
Below put down in writing several embodiment of the present invention, unless otherwise indicated, all umbers all by weight:
Embodiment one: get 94 parts of ethylene vinyl acetates (EVA), 6 parts low linear density polyethylene (LLDPE), 10 parts of terpolymer EP rubbers (EPDM), 80 parts of fine aluminum hydroxide powders, 8 parts of red phosphorus powder, 1 part of ZnSt, 1 part of A-151,1 part of antioxidant 1010,4 parts of carbonarius master batches, above-mentioned substance is crosslinked through mixing, twin screw blend granulation, single screw extrusion molding, electron beam irradiation (radiation dosage is 8Mrad), obtain the black halogen-free flame-retardant heat shrinkable sleeve after adding thermal enlargement and cooling and shaping.
Embodiment two: get 94 parts of ethylene vinyl acetates (EVA), 6 parts of new LDPE (film grade)s (LDPE), 16 parts of SBS, 50 parts of fine aluminum hydroxide powders, 40 parts of magnesium hydroxide micro mists, 6 parts of red phosphorus powder, 7 parts of A-172,1 part of antioxidant 1010,1 part of ZnSt, 4 parts of carbonarius mothers, adopt the method identical with embodiment one, irradiation dose adopts 9Mrad, obtains the black halogen-free flame-retardant heat shrinkable sleeve.
Embodiment three: get 60 parts of ethylene vinyl acetates (EVA), 30 parts of ethylene acrylic acid co polymers (EEA), 10 parts of linear low density polyethylenes (LIDPE), 2 parts of methyl vinyl silicone rubbers (VMQ), 40 parts of fine aluminum hydroxide powders, 20 parts of hydration zinc borate powder, 40 parts of micro encapsulation polyphosphoric acid ammonia, 2 parts of A-174,1 part of antioxidant 1010,1 part of MgSt, 6 parts of red B Masterbatchs of plastics, adopt on the working method identical, obtain red halogen-free flame retardant heat shrinkable sheathing with embodiment one.
Halogen-free flame retardant heat shrinkable sheathing of the present invention is environmentally friendly, can toxigenicity gas during burning, do not contain harmful heavy metal in the sleeve pipe simultaneously, it is a kind of green product of safe environment protection type, and raw material is easy to obtain, manufacture method adopts traditional manufacture method, is suitable for industrialization production.
Claims (10)
1. halogen-free flame retardant heat shrinkable sheathing material is characterized in that: wherein by weight, contain:
1. the material of one or more in ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), new LDPE (film grade) (LDPE), the linear low density polyethylene (LLDPE) is 100 parts;
2. material 5-50 part of one or more in terpolymer EP rubber (EPDM), ethylene propylene rubber (EPM), dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ), thermoplastic elastomer styrene-butadiene-styrene block copolymer (SBS), the styrene-isoprene block copolymer (SIS);
3. halogen-free flame retardants 50-100 part; And
4. coupling agent 0.5-6 part.
2. a kind of halogen-free flame retardant heat shrinkable sheathing material as claimed in claim 1 is characterized in that: described halogen-free flame retardants is selected from following a kind of material or more than one material: aluminium hydroxide, magnesium hydroxide, red phosphorus powder, polyphosphoric acid ammonia, hydration zinc borate.
3. a kind of halogen-free flame retardant heat shrinkable sheathing material as claimed in claim 1 is characterized in that: described coupling agent is a silicon additive.
4. a kind of halogen-free flame retardant heat shrinkable sheathing material as claimed in claim 1 is characterized in that: described coupling agent is selected from following a kind of material or more than one materials: vinyl three (methoxyethoxy) silane (A-172), r-(methacryloxy) propyl trimethoxy silicane (A-174), vinyltriethoxysilane (A-151).
5. as any described a kind of halogen-free flame retardant heat shrinkable sheathing material of claim 1-4, it is characterized in that: also comprise 0.5-1 part oxidation inhibitor.
6. a kind of halogen-free flame retardant heat shrinkable sheathing material as claimed in claim 5 is characterized in that: described oxidation inhibitor is four [β-(3.5-di-tert-butyl-hydroxy phenyl) propionic acid] seasons to become the tetrol ester.
7. as any described a kind of halogen-free flame retardant heat shrinkable sheathing material of claim 1-4, it is characterized in that: also comprise lubricant 0.5-1 part, it is selected from following one or more material: Zinic stearas (ZnSt), Magnesium Stearate (MgSt), stearic acid (HSt), n-butyl stearate (BS).
8. as any described a kind of halogen-free flame retardant heat shrinkable sheathing material of claim 1-4, it is characterized in that: also comprise tinting material colour batch 2-10 part, it is selected from following a kind of material or more than one materials: carbon black, iron oxide red powder, ultramarine, phthalocyanine blue B, phthalocyanine blue B X, Fast Yellow G, permanent yellow HSZG, the red B of plastics, fluorescent yellow YG-51.
9. halogen-free flame retardant heat shrinkable sheathing, it is characterized in that: its material contains by weight:
1. the material of one or more in ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), new LDPE (film grade) (LDPE), the linear low density polyethylene (LLDPE) is 100 parts;
2. material 5-50 part of one or more in terpolymer EP rubber (EPDM), ethylene propylene rubber (EPM), dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ), thermoplastic elastomer styrene-butadiene-styrene block copolymer (SBS), the styrene-isoprene block copolymer (SIS);
3. halogen-free flame retardants 50-100 part, it is selected from following a kind of material or more than one material: aluminium hydroxide, magnesium hydroxide, red phosphorus powder, polyphosphoric acid ammonia, hydration zinc borate;
4. coupling agent 0.5-6 part, it is a silicon additive;
5. lubricant 0.5-1 part, it is selected from following one or more material: Zinic stearas (ZnSt), Magnesium Stearate (MgSt), stearic acid (HSt), n-butyl stearate (BS);
6. tinting material colour batch 2-10 part, it is selected from following a kind of material or more than one materials: carbon black, iron oxide red powder, ultramarine, phthalocyanine blue B, phthalocyanine blue B X, Fast Yellow G, permanent yellow HSZG, the red B of plastics, fluorescent yellow YG-51; And
7. oxidation inhibitor 0.5-1 part.
10. halogen-free flame retardant heat shrinkable sheathing as claimed in claim 9 is characterized in that: this coupling agent is selected from following one or more material: vinyl three (methoxyethoxy) silane (A-172), r-(methacryloxy) propyl trimethoxy silicane (A-174), vinyltriethoxysilane (A-151).
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|---|---|---|---|
| CN 200310104076 CN1286895C (en) | 2003-12-16 | 2003-12-16 | Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby |
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|---|---|---|---|
| CN 200310104076 CN1286895C (en) | 2003-12-16 | 2003-12-16 | Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby |
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| CN1629216A true CN1629216A (en) | 2005-06-22 |
| CN1286895C CN1286895C (en) | 2006-11-29 |
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Application publication date: 20050622 Assignee: HUIZHOU LTK ELECTRONIC CABLE Co.,Ltd. Assignor: Shenzhen Woer Heat-shrinkable Material Co.,Ltd. Contract record no.: 2013440020237 Denomination of invention: Halogen-free flame-retardant thermal-shrinkage sleeve materials and sleeve prepared thereby Granted publication date: 20061129 License type: Exclusive License Record date: 20130805 |
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