CN103436005A - High-temperature-resistant halogen-free flame retardant thermoplastic polyurethane elastomer for cable and preparation method thereof - Google Patents
High-temperature-resistant halogen-free flame retardant thermoplastic polyurethane elastomer for cable and preparation method thereof Download PDFInfo
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- CN103436005A CN103436005A CN2013103511042A CN201310351104A CN103436005A CN 103436005 A CN103436005 A CN 103436005A CN 2013103511042 A CN2013103511042 A CN 2013103511042A CN 201310351104 A CN201310351104 A CN 201310351104A CN 103436005 A CN103436005 A CN 103436005A
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- free flame
- halogen
- cable
- temperature resistant
- high temperature
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 42
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 42
- 229920001971 elastomer Polymers 0.000 title claims abstract description 29
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 239000000806 elastomer Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 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 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 claims description 47
- 239000004814 polyurethane Substances 0.000 claims description 47
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 46
- 238000004132 cross linking Methods 0.000 claims description 33
- 230000003712 anti-aging effect Effects 0.000 claims description 25
- 239000003112 inhibitor Substances 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- -1 phosphinate compound Chemical class 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 18
- 150000001718 carbodiimides Chemical class 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229940059574 pentaerithrityl Drugs 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920001897 terpolymer Polymers 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 229920000800 acrylic rubber Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 4
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims description 4
- 239000004636 vulcanized rubber Substances 0.000 claims description 4
- OYUMYJKDVNCXAX-UHFFFAOYSA-N 2-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O OYUMYJKDVNCXAX-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 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 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052753 mercury Inorganic materials 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 239000003381 stabilizer Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- 239000002341 toxic gas Substances 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 230000005540 biological transmission Effects 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-temperature-resistant halogen-free flame retardant thermoplastic polyurethane elastomer for a cable. The high-temperature-resistant halogen-free flame retardant thermoplastic polyurethane elastomer comprises the following components by weight percent: 28.9-88.9% of thermoplastic polyurethane, 10-70% of a halogen-free flame retardant, 1-30% of a crosslinking agent, 0.025-0.5% of an antioxygen, 0.025-0.5% of an antiager, 0.025-0.5% of a stabilizer, and 0.025-0.5% of an anti-hydrolytic agent. Compared with the prior art, the multiple excellent performance of the thermoplastic polyurethane is used, and besides, appropriate amount of the halogen-free flame retardant and the crosslinking agent are added, so that the high-temperature-resistant halogen-free flame retardant thermoplastic polyurethane elastomer provided by the invention has excellent characteristics of fire resistance and high-temperature resistance. As the added flame retardant contains no halogen or heavy metal elements like lead, cadmium, mercury, chromium and the like, the environmental requirement of zero-halogen is met. In addition, the invention further discloses a preparation method of the elastomer.
Description
Technical field
The invention belongs to technical field of polymer materials, high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer and preparation method thereof for the cable that to relate in particular to a kind of temperature resistant grade be 105 ℃.
Background technology
At present, cable is widely used in the fields such as power system, information transmission and instrumental system, but, catching fire in use easily occurs in the covering material of cable made from traditional macromolecular material PVC, cause fire, due to the cl content in PVC, up to 60%, it can produce the smog of the toxic gases such as hydrogen halide and carbon monoxide in combustion processes.
Polyurethane elastomer refers to a class elastomer polymer that contains more carbamate groups functional group (NH-CO-O-) on macromolecular main chain, typical segmented copolymer, it has, and wear resistance is good, durometer level is wide, intensity is high, elongation is high, the load support capacity is large, good damping effect, resistance to low temperature is good and oil-resistant weather-resistant can excellence etc. plurality of advantages.According to the difference of working method, polyurethane elastomer generally can be divided into Polyurethane Thermoplastic Elastomer (TPU), casting type polyurethane elastomer and blending-type polyurethane elastomerics.Wherein, the characteristics such as Polyurethane Thermoplastic Elastomer (TPU) has good springiness, physical property is good and physical strength is good, therefore be widely used in ejaculation, extrusion, roll and be dissolved into the processing modes such as solution-type resin, be the plastic material that the plastic cement processer often uses, its characteristics also can be applicable in electric wire industry it.
But, general Polyurethane Thermoplastic Elastomer does not have flame retardant resistance, in order to reach fire-retardant purpose, people generally realize by the fire retardant that adds halogen-containing (as bromine), but as previously mentioned,, this product not only can be emitted a large amount of cigarettes when burning, and can give off poisonous gas, serious harm people's the security of the lives and property, nor meet the environmental protection instruction of European Union.In addition, the resistance to elevated temperatures of TPU is poor, once its working temperature surpasses 80 ℃, its many premium propertiess will be lost, and material is even destroyed, and this has limited its application greatly.Therefore, there is the cable that halogen-free flameproof, burning do not discharge toxic gas and have an excellent high-temperature stability and must become by Polyurethane Thermoplastic Elastomer the main flow direction that people competitively research and develop.
For this reason, necessary high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer and preparation method thereof for cable that a kind of environmental protection, safety, environmental sound is provided and there is excellent high-temperature stability, can not discharge toxic gas during this Polyurethane Thermoplastic Elastomer burning, and there is good flame retardant properties, mechanical property and resistance to elevated temperatures (temperature resistant grade is 105 ℃), can be used as good covering material of cable and use.
Summary of the invention
One of purpose of the present invention is: for the deficiencies in the prior art, and a kind of environmental protection, safety, environmental sound are provided and there is high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer and preparation method thereof for cable of excellent high-temperature stability, can not discharge toxic gas during this Polyurethane Thermoplastic Elastomer burning, and there is good flame retardant properties, mechanical property and resistance to elevated temperatures (temperature resistant grade is 105 ℃), can be used as good covering material of cable and use.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, by weight percentage, it comprises following component:
Thermoplastic polyurethane 28.9-88.9%;
Halogen-free flame retardants 10-70%;
Crosslinking component 1-30%;
Oxidation inhibitor 0.025-0.5%;
Anti-aging agent 0.025-0.5%;
Stablizer 0.025-0.5%;
Hydrolysis-resisting agent 0.025-0.5%.
Described halogen-free flame retardants is at least one in ammonium phosphate, ammonium polyphosphate, trimeric cyanamide and compound thereof, zinc borate, polynite, clay, metal hydroxides, organophosphorus compounds, organic phosphinate compound and polyvalent alcohol.
Described crosslinking component is cross-linking vulcanized rubber, or the mixture of the rubber of uncrosslinked sulfuration and at least one following material: isocyanic ester, superoxide, sulphur, sulfide and resol.Wherein, superoxide is dicumyl peroxide or benzoyl peroxide, and sulfide is tetramethyl-thiuram disulfide or dimorpholinyl disulfide.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, by weight percentage, it comprises following component:
Thermoplastic polyurethane 35-82%;
Halogen-free flame retardants 10-30%;
Crosslinking component 5-15%;
Oxidation inhibitor 0.075-0.2%;
Anti-aging agent 0.075-0.2%;
Stablizer 0.075-0.2%;
Hydrolysis-resisting agent 0.075-0.2%.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, by weight percentage, it comprises following component:
Thermoplastic polyurethane 70%;
Halogen-free flame retardants 20%;
Crosslinking component 9.6%;
Oxidation inhibitor 0.1%;
Anti-aging agent 0.1%;
Stablizer 0.1%;
Hydrolysis-resisting agent 0.1%.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, described metal oxide is ferric oxide and/or zinc oxide.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer; described oxidation inhibitor is four [methylene radical-3; 3 '; 5-(di-t-butyl-4-hydroxyl-phenyl) propionic ester] pentaerythritol ester, N; [[3-(3 for N '-bis-; 5)-di-t-butyl-4 hydroxy phenyl] propionyl] hexanediamine, three [2; the 4-di-tert-butyl-phenyl] at least one in the stearic alcohol ester of phosphorous acid ester, diphosphorous acid tetramethylolmethane and β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, described anti-aging agent is N-phenyl-α-aniline, N-Phenyl beta naphthylamine, N-phenyl-N`-cyclohexyl Ursol D and N, at least one in N`-phenylbenzene-Ursol D.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, described stablizer is at least one in Zinic stearas, calcium stearate, the hard esteramides of ethylene and silicone powder.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, described hydrolysis-resisting agent is at least one in carbodiimide, two carbodiimide and polycarbodiimide.
A kind of improvement as cable of the present invention by the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, the rubber of described uncrosslinked sulfuration is terpolymer EP rubber or acrylic elastomer; Described cross-linking vulcanized rubber is Thermoplastic Vulcanizate, crosslinked terpolymer EP rubber powder or cross linked acrylic rubber powder.
With respect to prior art, the present invention utilizes the many-sided excellent properties of thermoplastic polyurethane, simultaneously by adding suitable and appropriate halogen-free flame retardants and crosslinking component, make Polyurethane Thermoplastic Elastomer of the present invention there is good flame retardant resistance and high-temperature stability, experiment shows, the temperature resistant grade of Polyurethane Thermoplastic Elastomer of the present invention is 105 ℃.Due to not halogen-containing in the fire retardant added in the present invention, also the heavy metal element such as not leaded, cadmium, mercury and chromium, meet the halogen-free environmental requirement, is a kind of material of environmental protection.In addition, a small amount of oxidation inhibitor, anti-aging agent, stablizer and the hydrolysis-resisting agent added in the present invention can also prevent that the cable that adopts material of the present invention to prepare is oxidized, aging and be hydrolyzed, thereby can extend the work-ing life of cable.
Another object of the present invention is to provide a kind of cable high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer, comprises the following steps:
The first step, by weight ratio, be (28.9-88.9): (10-70): (1-30): (0.025-0.5): (0.025-0.5): (0.025-0.5): thermoplastic polyurethane (0.025-0.5), halogen-free flame retardants, crosslinking component, oxidation inhibitor, anti-aging agent, stablizer and hydrolysis-resisting agent mix in high-speed mixer, obtain compound.
Second step, by compound in the screw machine of 170-210 ℃, extrude, traction, granulation, the rotating speed of screw machine is 180-600 rev/min, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
With respect to prior art, the present invention is by selecting reasonably formula and suitable temperature and rotating speed, and by mixing, extrude, the operation such as traction and granulation makes the high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer of the cable with good flame-retardance energy and resistance to elevated temperatures, technique is simple, with low cost.
Embodiment
The invention provides a kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
Embodiment 1
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer that the present embodiment provides, by weight percentage, it comprises following component:
Polyester type thermoplastic polyurethane 82%;
Halogen-free flame retardants ammonium phosphate 10%;
Crosslinking component isocyanic ester 4.2%;
Crosslinking component terpolymer EP rubber 3%;
Oxidation inhibitor four [methylene radical-3,3 ', 5-(di-t-butyl-4-hydroxyl-phenyl) propionic ester] pentaerythritol ester 0.2%;
Anti-aging agent N-phenyl-α-aniline 0.2%;
Stablizer Zinic stearas 0.2%;
Hydrolysis-resisting agent carbodiimide 0.2%.
Wherein, the polyester type thermoplastic polyurethane is with polyester polyol, 4, and 4 '-diphenylmethanediisocyanate (MDI) and BDO are that raw material is prepared from.
A kind of cable that the present embodiment provides comprises the following steps with the high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer:
The first step, the polyester type thermoplastic polyurethane that is 82:10:7.2:0.2:0.2:0.2:0.2 by weight ratio, halogen-free flame retardants ammonium phosphate, crosslinking component isocyanic ester, crosslinking component terpolymer EP rubber, oxidation inhibitor four [methylene radical-3,3 ', 5-(di-t-butyl-4-hydroxyl-phenyl) propionic ester] pentaerythritol ester, anti-aging agent N-phenyl-α-aniline, stablizer Zinic stearas and hydrolysis-resisting agent carbodiimide mix in high-speed mixer, obtains compound.
Second step, by compound in the screw machine of 180-210 ℃, extrude, traction, granulation, the rotating speed of screw machine is 300 rev/mins, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
Embodiment 2
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer that the present embodiment provides, by weight percentage, it comprises following component:
Polyether-type thermoplastic polyurethane 70.5%;
Non-halogen Flame Retardant Melamine 23%;
Crosslinking component benzoyl peroxide 1.5%
Crosslinking component terpolymer EP rubber 4.6%;
Oxidation inhibitor N, N '-bis-[[3-(3,5)-di-t-butyl-4 hydroxy phenyl] propionyl] hexanediamine 0.1%;
Anti-aging agent N-Phenyl beta naphthylamine 0.1%;
Stablizer calcium stearate 0.1%;
The two carbodiimide 0.1% of hydrolysis-resisting agent.
Wherein, the polyether-type thermoplastic polyurethane is to take polytetrahydrofuran, tolylene diisocyanate (TDI) and BDO to be prepared from as raw material.
A kind of cable that the present embodiment provides comprises the following steps with the high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer:
The first step; the polyether-type thermoplastic polyurethane that is 70.5:23:1.5:4.6:0.1:0.1:0.1:0.1 by weight ratio, Non-halogen Flame Retardant Melamine, crosslinking component benzoyl peroxide, crosslinking component terpolymer EP rubber, oxidation inhibitor N; [[3-(3 for N '-bis-; 5)-di-t-butyl-4 hydroxy phenyl] propionyl] hexanediamine, anti-aging agent N-Phenyl beta naphthylamine, stablizer calcium stearate and the two carbodiimide of hydrolysis-resisting agent mix in high-speed mixer, obtain compound.
Second step, by compound in the screw machine of 170-200 ℃, extrude, traction, granulation, the rotating speed of screw machine is 500 rev/mins, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
Embodiment 3
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer that the present embodiment provides, by weight percentage, it comprises following component:
Polyester type thermoplastic polyurethane 41%;
Halogen-free flame retardants polynite 49.7%;
Crosslinking component tetramethyl-thiuram disulfide 1%;
Crosslinking component acrylic elastomer 8%;
Oxidation inhibitor three [2,4-di-tert-butyl-phenyl] phosphorous acid ester 0.075%;
Anti-aging agent N-phenyl-N`-cyclohexyl Ursol D 0.075%;
The hard esteramides 0.075% of stablizer ethylene;
Hydrolysis-resisting agent polycarbodiimide 0.075%.
Wherein, the polyester type thermoplastic polyurethane is with polyester polyol, 4, and 4 '-diphenylmethanediisocyanate (MDI) and BDO are that raw material is prepared from.
A kind of cable that the present embodiment provides comprises the following steps with the high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer:
The first step, the polyester type thermoplastic polyurethane that is 41:49.7:1:8:0.075:0.075:0.075:0.075 by weight ratio, halogen-free flame retardants polynite, crosslinking component tetramethyl-thiuram disulfide, crosslinking component acrylic elastomer, oxidation inhibitor three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester, anti-aging agent N-phenyl-N`-cyclohexyl Ursol D, the hard esteramides of stablizer ethylene and hydrolysis-resisting agent polycarbodiimide mix in high-speed mixer, obtains compound.
Second step, by compound in the screw machine of 170 ℃, extrude, traction, granulation, the rotating speed of screw machine is 600 rev/mins, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
Embodiment 4
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer that the present embodiment provides, by weight percentage, it comprises following component:
Polyester type thermoplastic polyurethane 57.9%;
Halogen-free flame retardants clay 40%;
Crosslinking component Thermoplastic Vulcanizate 2%;
The stearic alcohol ester 0.025% of oxidation inhibitor diphosphorous acid tetramethylolmethane;
Anti-aging agent N, N`-phenylbenzene-Ursol D 0.025%;
Stablizer silicone powder 0.025%;
Hydrolysis-resisting agent polycarbodiimide 0.025%.
Wherein, the polyester type thermoplastic polyurethane is with polyester polyol, 4, and 4 '-diphenylmethanediisocyanate (MDI) and BDO are that raw material is prepared from.
A kind of cable that the present embodiment provides comprises the following steps with the high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer:
The first step, the polyester type thermoplastic polyurethane that is 57.9:40:2:0.025:0.025:0.025:0.025 by weight ratio, halogen-free flame retardants clay, crosslinking component Thermoplastic Vulcanizate, the stearic alcohol ester of oxidation inhibitor diphosphorous acid tetramethylolmethane, anti-aging agent N, N`-phenylbenzene-Ursol D, stablizer silicone powder and hydrolysis-resisting agent polycarbodiimide mix in high-speed mixer, obtain compound.
Second step, by compound in the screw machine of 210 ℃, extrude, traction, granulation, the rotating speed of screw machine is 200 rev/mins, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
Embodiment 5
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer that the present embodiment provides, by weight percentage, it comprises following component:
Polyether-type thermoplastic polyurethane 41%;
Halogen-free flame retardants magnesium hydroxide 55%;
Crosslinked terpolymer EP rubber powder 2%;
Oxidation inhibitor β-positive octadecanol ester 0.5% of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
Anti-aging agent N-phenyl-N`-cyclohexyl Ursol D 0.5%;
The hard esteramides 0.5% of stablizer ethylene;
Hydrolysis-resisting agent carbodiimide 0.5%.
Wherein, the polyether-type thermoplastic polyurethane is to take polytetrahydrofuran, tolylene diisocyanate (TDI) and BDO to be prepared from as raw material.
A kind of cable that the present embodiment provides comprises the following steps with the high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer:
The first step, the polyether-type thermoplastic polyurethane that is 41:55:2:0.5:0.5:0.5:0.5 by weight ratio, halogen-free flame retardants magnesium hydroxide, crosslinked terpolymer EP rubber powder, the stearic alcohol ester of oxidation inhibitor diphosphorous acid tetramethylolmethane, anti-aging agent N-phenyl-N`-cyclohexyl Ursol D, the hard esteramides of stablizer ethylene and hydrolysis-resisting agent carbodiimide mix in high-speed mixer, obtain compound.
Second step, by compound in the screw machine of 170-200 ℃, extrude, traction, granulation, the rotating speed of screw machine is 180 rev/mins, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
Embodiment 6
A kind of cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer that the present embodiment provides, by weight percentage, it comprises following component:
Polyether-type thermoplastic polyurethane 50%;
Halogen-free flame retardants organophosphorus compounds 20.3%;
The organic phosphinate compound 23% of halogen-free flame retardants;
Crosslinking component acrylic elastomer 5%;
Crosslinking component sulphur 0.5%;
The stearic alcohol ester 0.15% of oxidation inhibitor diphosphorous acid tetramethylolmethane;
Oxidation inhibitor three [2,4-di-tert-butyl-phenyl] phosphorous acid ester 0.075%;
Anti-aging agent N-phenyl-N`-cyclohexyl Ursol D 0.15%;
Anti-aging agent N-Phenyl beta naphthylamine 0.15%
The hard esteramides 0.15% of stablizer ethylene;
Stablizer silicone powder 0.025%
Hydrolysis-resisting agent carbodiimide 0.5%.
Wherein, the polyether-type thermoplastic polyurethane is to take polytetrahydrofuran, tolylene diisocyanate (TDI) and BDO to be prepared from as raw material.
A kind of cable that the present embodiment provides comprises the following steps with the high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer:
The first step, the polyether-type thermoplastic polyurethane that is 50:20.3:23:5:0.5:0:15:0.075:0.15:0.15:0.15:0.025:0.5 by weight ratio, the halogen-free flame retardants organophosphorus compounds, the organic phosphinate compound of halogen-free flame retardants, the crosslinking component acrylic elastomer, crosslinking component sulphur, the stearic alcohol ester of oxidation inhibitor diphosphorous acid tetramethylolmethane, oxidation inhibitor three [2, the 4-di-tert-butyl-phenyl] phosphorous acid ester, anti-aging agent N-phenyl-N`-cyclohexyl Ursol D, anti-aging agent N-Phenyl beta naphthylamine, the hard esteramides of stablizer ethylene, stablizer silicone powder and hydrolysis-resisting agent carbodiimide mix in high-speed mixer, obtain compound.
Second step, by compound in the screw machine of 170-200 ℃, extrude, traction, granulation, the rotating speed of screw machine is 250 rev/mins, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
The low-smoke halogen-free flame-retardant thermoplastic polyurethane elastomer of embodiment 1 to 6 is made into to the crust of cable, the wire gauge diameter is 3.0mm, and skin depth is 0.4mm, is numbered respectively S1-S6, and its key technical indexes (typical performance) is as shown in table 1.Wherein, pull-off force and elongation are tested with reference to the UL1581 standard, and its flame retardant properties is tested by the UL1581 standard.
Table 1: the key technical indexes (typical performance) that is numbered the cable sheath of S1-S6.
The announcement of book and elaboration according to the above description, those skilled in the art in the invention can also be changed and be revised above-mentioned embodiment.Therefore, the present invention is not limited to embodiment disclosed and described above, also should be in the protection domain of claim of the present invention to equivalent modifications more of the present invention and change.In addition, although used some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, is characterized in that, by weight percentage, it comprises following component:
Thermoplastic polyurethane 28.9-88.9%;
Halogen-free flame retardants 10-70%;
Crosslinking component 1-30%;
Oxidation inhibitor 0.025-0.5%;
Anti-aging agent 0.025-0.5%;
Stablizer 0.025-0.5%;
Hydrolysis-resisting agent 0.025-0.5%;
Described halogen-free flame retardants is at least one in ammonium phosphate, ammonium polyphosphate, trimeric cyanamide and compound thereof, zinc borate, polynite, clay, metal hydroxides, organophosphorus compounds, organic phosphinate compound and polyvalent alcohol;
Described crosslinking component is cross-linking vulcanized rubber, or the mixture of the rubber of uncrosslinked sulfuration and at least one following material: isocyanic ester, superoxide, sulphur, sulfide and resol.
2. cable according to claim 1 high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, is characterized in that, by weight percentage, it comprises following component:
Thermoplastic polyurethane 35-82%;
Halogen-free flame retardants 10-30%;
Crosslinking component 5-15%;
Oxidation inhibitor 0.075-0.2%;
Anti-aging agent 0.075-0.2%;
Stablizer 0.075-0.2%;
Hydrolysis-resisting agent 0.075-0.2%.
3. cable according to claim 2 high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, is characterized in that, by weight percentage, it comprises following component:
Thermoplastic polyurethane 70%;
Halogen-free flame retardants 20%;
Crosslinking component 9.6%;
Oxidation inhibitor 0.1%;
Anti-aging agent 0.1%;
Stablizer 0.1%;
Hydrolysis-resisting agent 0.1%.
4. according to the described cable of claims 1 to 3 any one high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, it is characterized in that: described metal oxide is ferric oxide and/or zinc oxide.
5. according to the described cable of claims 1 to 3 any one high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer; it is characterized in that: described oxidation inhibitor is four [methylene radical-3; 3 '; 5-(di-t-butyl-4-hydroxyl-phenyl) propionic ester] pentaerythritol ester, N; [[3-(3 for N '-bis-; 5)-di-t-butyl-4 hydroxy phenyl] propionyl] hexanediamine, three [2; the 4-di-tert-butyl-phenyl] at least one in the stearic alcohol ester of phosphorous acid ester, diphosphorous acid tetramethylolmethane and β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid.
6. according to the described cable of claims 1 to 3 any one high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, it is characterized in that: described anti-aging agent is N-phenyl-α-aniline, N-Phenyl beta naphthylamine, N-phenyl-N`-cyclohexyl Ursol D and N, at least one in N`-phenylbenzene-Ursol D.
7. according to the described cable of claims 1 to 3 any one high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, it is characterized in that: described stablizer is at least one in Zinic stearas, calcium stearate, the hard esteramides of ethylene and silicone powder.
8. according to the described cable of claims 1 to 3 any one high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, it is characterized in that: described hydrolysis-resisting agent is at least one in carbodiimide, two carbodiimide and polycarbodiimide.
9. according to the described cable of claims 1 to 3 any one high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer, it is characterized in that: the rubber of described uncrosslinked sulfuration is terpolymer EP rubber or acrylic elastomer; Described cross-linking vulcanized rubber is Thermoplastic Vulcanizate, crosslinked terpolymer EP rubber powder or cross linked acrylic rubber powder.
10. a cable claimed in claim 1 high temperature resistant halogen-free flame-retardant method for preparing thermoplastic polyurethane elastomer, is characterized in that, comprises the following steps:
The first step, by weight ratio, be (28.9-88.9): (10-70): (1-30): (0.025-0.5): (0.025-0.5): (0.025-0.5): thermoplastic polyurethane (0.025-0.5), halogen-free flame retardants, crosslinking component, oxidation inhibitor, anti-aging agent, stablizer and hydrolysis-resisting agent mix in high-speed mixer, obtain compound;
Second step, by compound in the screw machine of 170-210 ℃, extrude, traction, granulation, the rotating speed of screw machine is 180-600 rev/min, obtains cable high temperature resistant halogen-free flame-retardant Polyurethane Thermoplastic Elastomer.
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Address after: 523000 Dongcheng District Tongsha Science Park Guanghui Industrial Zone, Dongguan City, Guangdong Province Patentee after: Guangdong Antopu Polymer Technology Co.,Ltd. Address before: 523000 Area B and E, Building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng District, Dongguan City, Guangdong Province Patentee before: ADVANCED THERMOPLASTIC POLYMER TECHNOLOGY Co.,Ltd. |
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| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 523000 Dongcheng Street Tongsha Science Park Guanghui Industrial Zone, Dongguan City, Guangdong Province Patentee after: Guangdong Antopu Polymer Technology Co.,Ltd. Address before: 523000 Dongcheng District Tongsha Science Park Guanghui Industrial Zone, Dongguan City, Guangdong Province Patentee before: Guangdong Antopu Polymer Technology Co.,Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 523000 area B2, D and E2, building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng Street, Dongguan City, Guangdong Province Patentee after: Guangdong Antop Polymer Technology Co.,Ltd. Address before: 523000 area B2, D and E2, building 2, Guanghui Industrial Zone, Tongsha Science Park, Dongcheng Street, Dongguan City, Guangdong Province Patentee before: Guangdong Antopu Polymer Technology Co.,Ltd. |