CN1344418A - 稳定的通信电缆绝缘组合物 - Google Patents
稳定的通信电缆绝缘组合物 Download PDFInfo
- Publication number
- CN1344418A CN1344418A CN00805381A CN00805381A CN1344418A CN 1344418 A CN1344418 A CN 1344418A CN 00805381 A CN00805381 A CN 00805381A CN 00805381 A CN00805381 A CN 00805381A CN 1344418 A CN1344418 A CN 1344418A
- Authority
- CN
- China
- Prior art keywords
- butyl
- cable
- component
- tert
- phenyl
- 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
- 238000009413 insulation Methods 0.000 title abstract description 19
- 229920000098 polyolefin Polymers 0.000 claims abstract description 41
- 239000004519 grease Substances 0.000 claims abstract description 27
- 239000006078 metal deactivator Substances 0.000 claims abstract description 18
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- -1 isocyanuric acid ester Chemical class 0.000 claims description 94
- 229910052757 nitrogen Inorganic materials 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 44
- 239000000945 filler Substances 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 235000006708 antioxidants Nutrition 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 238000010276 construction Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012212 insulator Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims description 6
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 6
- 150000002429 hydrazines Chemical class 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229940080818 propionamide Drugs 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001589 carboacyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002530 phenolic antioxidant Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 abstract 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 abstract 1
- 239000007983 Tris buffer Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 31
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 23
- 239000002585 base Substances 0.000 description 22
- 238000011049 filling Methods 0.000 description 22
- 150000001412 amines Chemical class 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 238000004891 communication Methods 0.000 description 6
- 229940035422 diphenylamine Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 4
- UUABJBNMBCIBFA-UHFFFAOYSA-N 1-hydroxy-2-(2-hydroxyethoxy)ethanesulfonic acid Chemical compound OCCOCC(O)S(O)(=O)=O UUABJBNMBCIBFA-UHFFFAOYSA-N 0.000 description 4
- QYSPWTBYSZPOCJ-UHFFFAOYSA-N 1-hydroxypentadecane-3-sulfonic acid Chemical compound CCCCCCCCCCCCC(CCO)S(O)(=O)=O QYSPWTBYSZPOCJ-UHFFFAOYSA-N 0.000 description 4
- BGQNNKZAJXZSPQ-UHFFFAOYSA-N 5,6-dimethylheptane-1,6-diol Chemical compound CC(O)(C)C(C)CCCCO BGQNNKZAJXZSPQ-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- 229920000305 Nylon 6,10 Polymers 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229940051250 hexylene glycol Drugs 0.000 description 4
- UYBZRNZWRIJUEB-UHFFFAOYSA-N n'-ethoxyoxamide Chemical class CCONC(=O)C(N)=O UYBZRNZWRIJUEB-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical class ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 3
- KMWIPXLIKIAZMT-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanehydrazide Chemical compound CC(C)(C)C1=CC(CCC(=O)NN)=CC(C(C)(C)C)=C1O KMWIPXLIKIAZMT-UHFFFAOYSA-N 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000002690 malonic acid derivatives Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229960005137 succinic acid Drugs 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229940099259 vaseline Drugs 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- MSGFMKMFGGXSTO-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC Chemical compound C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC MSGFMKMFGGXSTO-UHFFFAOYSA-N 0.000 description 2
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- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
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- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 239000001273 butane Substances 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical class CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VEZIKIAGFYZTCI-UHFFFAOYSA-N methyl 3-(4-methoxyphenyl)prop-2-enoate Chemical compound COC(=O)C=CC1=CC=C(OC)C=C1 VEZIKIAGFYZTCI-UHFFFAOYSA-N 0.000 description 2
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Abstract
在烃类油脂填充的通信电缆中的随后暴露于户外互连盒中的聚烯烃质导线绝缘体尤其容易受热、氧和潮湿等不利条件的损害。从N,N’-己烷-1,6-二基双-(3-(3,5-二叔丁基-4-羟基苯基丙酰胺))、三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯和三(2-(3,5-二叔丁基-4-羟基氢化肉桂酰氧基)乙基)异氰脲酸酯中选择的一种或多种主抗氧化剂与一种或多种烷基羟基苯基链烷酰基肼金属减活剂的结合物,在这些条件下,为聚烯烃质导线绝缘体提供氧化稳定性是非常有效的。
Description
本发明涉及用作电线和电缆绝缘体的聚烯烃组合物,它具有改进的耐热、氧和潮湿等有害作用的性能。稳定的组合物适于用作通信(电信)电缆。
典型的电信电缆是由捆扎在一起的和由电缆护套加以保护的聚烯烃绝缘铜线的扭绞线对构成。该电缆护套由金属箔和/或铠装层与聚合物护套材料两者组成。整个系统称为“电信电缆”。
为了减少水透入到电缆系统中的危险和最大程度地减少水汽对聚烯烃绝缘效果的有害作用,该系统是通过用疏水性油脂填充电缆内的空隙来实施水密封的。例如在美国专利No.3,888,709,4,044,200,4,218,577,5,502,288和欧洲专利申请565,868 A2,和其中的参考文献中描述了这一类型的电缆系统。已知的是该电缆填充油脂可以浸出被加入到导线绝缘层中的稳定剂。例如在“塑料添加剂手册”,第三版,R.Gchter,H.Müller编,Hanser Publishers,116-119页(1990)对此进行了讨论。
两根或多根电信电缆的连接常常是需要的,这可在已知为台座或互连盒的户外包封盒中实现。在台座内,电缆护套被去掉,电缆填充油脂被擦去,并根据需要来连接传输线。暴露出来的绝缘线就受到热、氧和湿气等不利条件的破坏。因填料油脂的浸出作用而损失了一部分稳定剂的该聚烯烃绝缘体,在这些环境条件下尤其容易受损,并显示出过早的氧化破坏。这一破坏作用将表现在绝缘体的物理性能的损失,最终导致电输送性能的损失。
在电信应用中,聚烯烃质导线绝缘体用位阻酚抗氧化剂来稳定的方法是已知的。现有技术的稳定剂体系包括受阻酚与金属减活剂的一起使用,如IrganoxMD 1024,1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼或NaugardXL-1,2,2’-草酰二胺基-双-[乙基3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。典型的稳定剂包装料包括作为主要抗氧化剂的Irganox1010,季戊四醇四[3-(3,5-二叔丁基-4-羟苯基)丙酸酯],和作为金属减活剂的IrganoxMD 1024。这一体系公开于欧洲专利申请565,868 A2和美国专利No.4,044,200,5,380,591和5,575,952中。Irganox是Ciba Specialty Chemicals Corp.的受保护的商品名,Naugard是Uniroyal的受保护商品名。
美国专利No.4,044,200公开了在防潮填料存在下,用烷基羟基苯基链烷酰肼和/或取代的酰胺基三唑与高分子量位阻酚抗氧化剂一起的结合物来稳定聚乙烯质导线绝缘体。特别地公开的是IrganoxMD1024和Irganox1010的结合物。
美国专利No.4,812,500公开了当接触热的充氧水、加氯水和紫外线辐射时,具有改进的耐破坏性能的聚烯烃组合物。该组合物包含位阻胺紫外线稳定剂,位阻酚热稳定剂和螯合(金属减活)剂。该位阻酚选自包括Irgano1010,季戊四醇四(3-(3,5-二叔丁基-4-羟苯基)丙酸酯],和Irganox3114,三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯的一特定组。该螯合剂选自IrganoxMD 1024,1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼。Irganox是Ciba SpecialtyChemicals Corp的商标。该发明被设想可用于各种存在水或湿气的体系中,包括电线和电缆涂料。没有提及到存在着添加剂被浸出的可能性的油脂填充电缆系统。
美国专利No 5,380,591,5,453,322,5,575,952,5,766,761和5,807,635公开了用烷基羟基苯基链烷酰肼与官能化位阻胺的混合物的结合物来稳定烃类油脂填充的电话电缆。IrganoxMD 1024是在每种情况下作为肼来特别地公开的。
美国专利No.5,474,847教导了用位阻酚类或位阻胺的酰肼衍生物或位阻胺的氨基衍生物与醌的反应产物来稳定油脂填充电话电缆中的聚烯烃质导线绝缘体。
美国专利No.5,502,288公开了利用IrganoxMD 1024或NaugardXL-1或其混合物与所选择的抗氧化剂一起来稳定在电话电缆中的聚烯烃质导线绝缘体。
欧洲专利申请565,868 A2教导了用酚的羧酸或膦酸的二价金属盐类与金属减活剂一起的结合物来稳定接触阻水电缆填料的聚烯烃质导线绝缘组合物。特别地提出的金属减活剂是IrganoxMD 1024和NaugardXL-1。优选的组合物还包括使用Irganox1010。
WO 93/24935教导了用不饱和脂肪族二酸的酸酐与一种或多种官能化位阻胺和/或官能化位阻酚的反应产物来稳定在油脂填充电话电缆中的聚烯烃质导线绝缘体。
WO93/24938公开了填充油脂电缆结构,其中聚烯烃质导线绝缘体通过脂肪族二酸的酸酐、一种或多种官能化位阻胺和/或官能化位阻酚键接于它。
为了保护暴露于互连盒中的环境条件的聚烯烃质导线绝缘体和抵消电缆填充油脂对稳定剂的浸出作用,曾建议使用高填充量的稳定剂体系。因此需要寻找比现有技术的那些更高效的主抗氧化剂/金属减活剂结合物,以降低与稳定剂的这些用量有关的高成本。就这一点而言的稳定剂效率是稳定剂体系抵抗从聚烯烃质导线绝缘体中被浸出到电缆填充油脂中和提供给聚烯烃一种耐热、氧和湿气等有害作用的综合能力。
令人惊讶地发现,选自Irganox1098,N,N’-己烷-1,6-二基双-(3-(3,5-二叔丁基-4-羟基苯基丙酰胺)),Irganox3114,三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯,和Irganox3125,三(2-(3,5-二叔丁基-4-羟基氢化肉桂酰氧基)乙基)异氰脲酸酯的一种或多种主酚类抗化氧剂与一种或多种烷基羟基苯基链烷酰肼类金属减活剂的结合物,对于为填充油脂的电信电缆中的聚烯烃质导线绝缘体提供氧化稳定性来说是尤其有效的。Irganox是Ciba Specialty ChemicalsCorp的商标。
本发明涉及新型烃类油脂填充的电缆结构体,其中聚烯烃质导线绝缘体具有改进的氧化稳定性。
更具体地,本发明的新型电缆结构体包括
(i)彼此之间有空隙的多根绝缘的电导线,
该绝缘体包括
(a)一种或多种聚烯烃,和
(b)一种或多种选自N,N’-己烷-1,6-二基双-(3-(3,5-二叔丁基-4-羟基苯基丙酰胺)),三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯和三(2-(3,5-二叔丁基-4-羟基氢化肉桂酰氧基)乙基)异氰脲酸酯的主抗氧化剂,和
(c)一种或多种选自烷基羟基苯基链烷酰肼类的金属减活剂,和
(ii)在空隙内的烃类电缆填充油脂,和
(iii)包围组分(i)和(ii)的护套。
组分(a)的聚烯烃一般是可交联的热塑性树脂。它们可以是从两种或多种共聚单体生产的均聚物或共聚物,或两种或多种这些聚合物的共混物,通常用于薄膜、片材和管材,和用作电线和电缆应用中的抱套材料和/或绝缘材料。用于生产这些均聚物和共聚物的单体可具有2-20个碳原子,优选具有2-12个碳原子。这些单体的例子是α-烯烃如乙烯,丙烯,1-丁烯,1-己烯,4-甲基-1-戊烯,和1-辛烯;不饱和酯类如乙酸乙烯酯,丙烯酸乙酯,丙烯酸甲酯,甲基丙烯酸甲酯,丙烯酸叔丁酯,丙烯酸正丁基酯,甲基丙烯酸正丁基酯;丙烯酸2-乙基己基酯,和其它丙烯酸烷基酯;二烯烃如1,4-戊二烯,1,3-己二烯,1,5-己二烯,1,4-辛二烯,和亚乙基降冰片烯,在三元共聚物中常见的第三种单体;其它单体如苯乙烯,对-甲基苯乙烯,α-甲基苯乙烯,对-氯苯乙烯,乙烯基萘,和类似的芳基烯烃;腈类如丙烯腈,甲基丙烯腈,和α-氯丙烯腈;乙烯基甲基酮,乙烯基甲基醚,偏二氯乙烯,马来酸酐,氯乙烯,偏二氯乙烯,乙烯醇,四氟乙烯,和一氯三氟乙烯;和丙烯酸,甲基丙烯酸,和其它类似的不饱和酸。
这里所指的均聚物和共聚物可以是非卤化的,或按常规方式一般用氯或溴卤化的。卤化聚合物的例子是聚氯乙烯,聚偏氯乙烯,和聚四氟乙烯。乙烯和丙烯的均聚物和共聚物是优选的,无论是非卤化的或卤化形式。包括在这一优选组中的是三元共聚物如乙烯/丙烯/二烯单体的橡胶。
乙烯聚合物的其它例子是如下这些:乙烯的高压均聚物;乙烯和一种或多种具有3-12个碳原子的α-烯烃的共聚物;具有接枝到其骨架上的可水解的硅烷的乙烯均聚物或共聚物;乙烯和链烯基三烷氧基硅烷如三甲氧基乙烯基硅烷的共聚物;或具有2-12个碳原子的α-烯烃和具有4-20个碳原子的不饱和酯的共聚物,例如乙烯/丙烯酸乙酯或乙酸乙烯酯共聚物;乙烯/丙烯酸乙酯或乙酸乙烯酯/可水解硅烷三元共聚物;和具有接枝到其骨架上的可水解硅烷的乙烯/丙烯酸乙酯或乙酸乙烯酯共聚物。
对于聚丙烯而言:均聚物和丙烯和一种或多种其它α-烯烃的共聚物,其中共聚物的基于丙烯的部分是共聚物重量的至少约60wt%,可以用于提供本发明的聚烯烃。优选的聚丙烯α-烯烃共聚单体是具有2或4到12个碳原子的那些。
聚烯烃,即在前面例举的单烯烃的聚合物,例如聚乙烯和聚丙烯,可以通过不同的方法,特别是下面的方法来制备:
1) 自由基聚合反应(一般在高压和升高的温度下)。
2) 使用一般含有一种或一种以上的元素周期表的IVb,Vb,VIb或VIII族的金属的催化剂的催化聚合反应。这些金属通常有一个或一个以上的配位体,典型的可以是p-或s-配位的氧化物,卤化物,醇化物,酯类,醚类,胺类,烷基类,链烯基类和/或芳基类。这些金属配合物可以是游离形式或被固定在基质上,典型地被固定在活化氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以溶于或不溶于聚合反应介质中。上述催化剂本身可用于聚合反应或另外使用活化剂,典型的是金属烷基化物,金属氢化物,金属烷基卤化物,金属烷基氧化物或金属烷基环氧化物(alkyloxanes),所述金属是元素周期表的Ia,IIa和/或IIIa族的元素。活化剂可以方便地用另外的酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系通常被命名为 Phillips,Standard Oil Indiana,Ziegler(-Natta),TNZ(Dupont),金属茂或单位点催化剂(SSC)。
该均聚物或共聚物可以用有机过氧化物交联或固化,或为了使其具有可水解性,它们可以在用作自由基产生剂或催化剂的有机过氧化物存在下,用链烯基三烷氧基硅烷接枝。有用的链烯基三烷氧基硅烷包括乙烯基三烷氧基硅烷如乙烯基三甲氧基硅烷,乙烯基三乙氧基硅烷,和乙烯基三异丙氧基硅烷。该链烯基和烷氧基基团可以具有1-30个碳原子,优选具有1-12个碳原子。该可水解的聚合物可以在硅烷醇缩合催化剂如二月桂酸二丁基锡、马来酸二辛基锡、乙酸亚锡、辛酸亚锡、环烷酸铅、辛酸锌、2-乙基己酸铁和其它金属羰酸盐存在下进行湿固化。
其中乙烯是主要共聚单体的乙烯均聚物或共聚物,以及其中丙烯是主要单体的丙烯均聚物和共聚物,在这里可分别称作聚乙烯和和聚丙烯。
组分a)的聚烯烃优选地是聚乙烯或聚丙烯或它们的混合物。
组分(c)的烷基羟基苯基链烷酰肼在美国专利No3,660,438和3,773,722中被描述。优选地组分(c)的化合物具有以下结构:其中n是0或1到5的整数;
R1是具有1-6个碳原子的直链或支链烷基;
R2是氢或R1;和
基团R2优选地是处在OH基团的邻位。
优选地,组分(c)的金属减活剂是IrganoxMD 1024,1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼,Ciba SpecialtyChemicals Corp。
组分(ii)的烃类电缆填充油脂是烃化合物的混合物,它在使用温度下是半固体。它在工业上称为“电缆填充化合物”。对电缆填充化合物的典型要求是,在60℃或更高温度等级下,在电缆的切头处有最低量的渗漏。另一个典型要求是,当在一端施加水压时,该油脂防止水渗漏穿过较短长度的切割电缆。其它典型的要求是:成本竞争力;对信号传输的最小有害影响;对聚合物绝缘体和电缆护套材料的物理性能有最小的损害影响;热和氧化稳定性;和电缆制造可加工性。
通过将电缆填充化合物加热至大约100℃的温度,来进行电缆制造。这将液化该填充化合物,因此能够将它泵入到多股电缆芯材中以完全浸渍空隙和除去所有的气隙。另外,使用剪切诱导流动的触变型电缆填充化合物能够按同样的方式在降低的温度下加工。典型的成品填充油脂电缆传输芯材的截面是由大约52%绝缘线和大约48%空隙组成(就整个截面的面积而言)。由于空隙被电缆填充化合物完全填充,填充的电缆芯典型地含有大约48体积%的电缆填充化合物。
该电缆填充化合物或它的烃成分中的一种或多种通过从空隙中吸收而进入绝缘体中。通常,该绝缘体总共吸收大约3到大约30wt%电缆填充化合物或一种或多种它的烃成分,基于聚烯烃绝缘体的重量。典型的吸收率是在大约5到大约25wt%范围内,基于聚烯烃的重量。电缆填充化合物通常含有不同分子量的烃类。电缆填充化合物的低分子量成分,在电缆填充化合物吸收到聚烯烃绝缘体中或溶胀中是优先的。聚烯烃绝缘体的这一溶胀导致添加剂从绝缘体迁移到前面讨论的电缆填充化合物中。因此该电缆填充化合物的存在对于稳定该聚烯烃绝缘体设置了附加的障碍。
烃类电缆填充油脂(电缆填充化合物)的例子是矿脂;矿脂/聚烯烃蜡混合物;油改性的热塑性橡胶(ETPR或增量剂填充的热塑性橡胶);石蜡油;环烷油;矿物油;用残油、矿脂或蜡增稠的上述油;聚乙烯蜡;矿物油/橡胶嵌段共聚物混合物;润滑脂;和它们的各种混合物,所有这些满足与以上所述的那些类似的工业要求。
除了抵抗抗氧化剂的浸出之外,稳定的聚烯烃质导线绝缘体配制料必须能够承受从电缆填充化合物中吸收的各种成分的任何去稳作用。此外,该稳定用途的包装料必须能够抵抗住铜丝导体的影响(它是聚烯烃氧化降解的潜在催化剂),并且它还必须抵消在多孔性以及多孔/密实(泡沫/表皮)聚合物泡沫绝缘体中存在的化学发泡剂残余物的影响。
除了组分(b)和(c)之外,本发明的电缆结构的绝缘体可以包括附加的助稳定剂(添加剂),例如以下这些:
1.抗氧化剂
1.1.烷基化一元酚类,例如,2,6-二叔丁基-4-甲基苯酚,2-叔丁基-4,6-二甲基苯酚,2,6-二叔丁基-4-乙基苯酚,2,6-二叔丁基-4-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-双十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚;壬基苯酚类,它在支链上是线性或支化的,例如2,6-二壬基-4-甲基苯酚,2,4-二甲基-6-(1-甲基十一烷-1-基)苯酚,2,4-二甲基-6-(1-甲基十七烷-1-基)苯酚,2,4-二甲基-6-(1-甲基十三烷-1-基)苯酚;以及它们的混合物。
1.2.烷基硫代甲基酚类,例如2,4-二辛基硫代甲基-6-叔丁基苯酚,2,4-二辛基硫代甲基-6-甲基苯酚,2,4-二辛基硫代甲基-6-乙基苯酚,2,6-双十二烷基硫代甲基-4-壬基苯酚。
1.3.氢醌类或烷基化氢醌类,例如,2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基氢醌,2,5-二叔戊基氢醌,2,6-二苯基-4-十八烷氧基苯酚,2,6-二叔丁基氢醌,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯基硬脂酸酯,双(3,5-二叔丁基-4-羟基苯基)己二酸酯。
1.4.生育酚类,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚和它们的混合物(维生素E)。
1.5.羟基化硫代二苯基醚类,例如,2,2′-硫代双(6-叔丁基-4-甲基苯酚),2,2′-硫代双(4-辛基苯酚),4,4′-硫代双(6-叔丁基-3-甲基苯酚),4,4′-硫代双(6-叔丁基-2-甲基苯酚),4,4′-硫代双(3,6-二仲戊基苯酚),4,4’-双(2,6-二甲基-4-羟基苯基)二硫醚。
1.6.亚烷基双酚类,例如,2,2′-亚甲基双(6-叔丁基-4-甲基苯酚),2,2′-亚甲基双(6-叔丁基-4-乙基苯酚),2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚],2,2′-亚甲基双(4-甲基-6-环己基苯酚),2,2′-亚甲基双(6-壬基-4-甲基苯酚),2,2′-亚甲基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4′-亚甲基双(2,6-二叔丁基苯酚),4,4′-亚甲基双(6-叔丁基-2-甲基苯酚),1,1′-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚,1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1′-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,双[3,3-双(3-叔丁基-4-羟基苯基)丁酸]乙二醇酯,双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯,双[2-(3′-叔丁基-2-羟基-5-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯,1,1-双-(3,5-二甲基-2-羟基苯基)丁烷,2,2-双-(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-双-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷,1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-,N-和S-苄基化合物类,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚,十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯,十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯,三(3,5-二叔丁基-4-羟基苄基)胺,双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯,双(3,5-二叔丁基-4-羟基-苄基)硫醚,异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯。
1.8.羟苄基化丙二酸酯类,例如,二(十八烷基)-2,2-双-(3,5-二叔丁基-2-羟基苄基)丙二酸酯,二(十八烷基)-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯,二(十二烷基巯基乙基)-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯,双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳族羟苄基化合物类,例如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯,1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。
1.10.三嗪化合物类,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-异氰脲酸酯,2,4,6-三(3,5-二叔丁基-4-羟基苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11.苄基膦酸酯类,例如2,5-二叔丁基-4-羟基苄基膦酸二甲酯,3,5-二叔丁基-4-羟基苄基膦酸二乙酯,3,5-二叔丁基-4-羟基苄基膦酸二(十八烷基)酯,5-叔丁基-4-羟基-3-甲基苄基膦酸二(十八烷基)酯,3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.12.酰基氨基酚类,例如4-羟基月桂酰苯胺,4-羟基硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.13.β-(3.5-二叔丁基-4-羟基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.16.3,5-二叔丁基-4-羟基苯基乙酸的酯类,与单羟基或多羟基醇类,例如与甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫代十一烷醇,3-硫代十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯类。
1.17.β-(3.5-二叔丁基-4-羟基苯基)丙酸的酰胺类,例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,N,N’-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺(NaugardXL-1,由Uniroyal提供)。
1.18.抗坏血酸(维生素C)
1.19.胺类抗氧化剂,例如N,N′-二异丙基-对-亚苯基二胺,N,N′-二仲丁基-对-亚苯基二胺,N,N′-双(1,4-二甲基戊基)-对-亚苯基二胺,N,N′-双(1-乙基-3-甲基戊基)-对-亚苯基二胺,N,N’-双(1-甲基庚基)-对亚苯基二胺,N,N’-二环己基-对亚苯基二胺,N,N′-二苯基-对-亚苯基二胺,N,N′-双(2-萘基)-对-亚苯基二胺,N-异丙基-N′-苯基-对-亚苯基二胺,N-(1,3-二甲基丁基)-N′-苯基-对-亚苯基二胺,N-(1-甲基庚基)-N′-苯基-对-亚苯基二胺,N-环己基-N′-苯基-对-亚苯基二胺,4-(对甲苯氨磺酰基)二苯胺,N,N′-二甲基-N,N′-二仲丁基-对亚苯基二胺,二苯胺,N-烯丙基二苯胺,4-异丙氧基-二苯胺,N-苯基-1-萘基胺,N-(4-叔辛基苯基)-1-萘基胺,N-苯基-2-萘基胺,辛基化二苯胺(例如p,p′-二叔辛基二苯胺),4-正丁基氨基苯酚,4-丁酰氨基苯酚,4-壬酰氨基苯酚,4-十二酰氨基苯酚,4-十八酰氨基苯酚,双(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲氨基甲基苯酚,2,4′-二氨基二苯基甲烷,4,4′-二氨基二苯基甲烷,N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷,1,2-双[(2-甲基苯基)氨基]乙烷,1,2-双(苯基氨基)丙烷,(邻甲苯基)双胍,双[4-(1′,3′-二甲基丁基)苯基]胺,叔辛基化N-苯基-1-萘基胺,单和二烷基化叔丁基/叔辛基二苯基胺类的混合物,单和二烷基化壬基二苯基胺类的混合物,单和二烷基化十二烷基二苯基胺类的混合物,单和二烷基化异丙基/异己基二苯基胺类的混合物,单和二烷基化叔丁基二苯基胺类的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪,吩噻嗪,单和二烷基化叔丁基/叔辛基吩噻嗪的混合物,单和二烷基化叔辛基吩噻嗪的混合物,N-烯丙基吩噻嗪,N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯,N,N-双(2,2,6,6-四甲基-哌啶-4-基-六亚甲基二胺,双(2,2,6,6-四甲基-哌啶-4-基)癸二酸酯,2,2,6,6-四甲基哌啶-4-酮,2,2,6,6-四甲基哌啶-4-醇。
2.UV吸收剂和光稳定剂
2.1.2-(2-羟基苯基)苯并三唑类,例如2-(2-羟基-5-甲基苯基)苯并三唑,2-(3,5-二叔丁基-2-羟基苯基)苯并三唑,2-(5-叔丁基-2-羟基苯基)苯并三唑,2-(2-羟基-5-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3,5-二叔丁基-2-羟基苯基)-5-氯-苯并三唑,2-(3-叔丁基-2-羟基-5-甲基苯基)-5-氯-苯并三唑,2-(3-仲丁基-5-叔丁基-2-羟基苯基)苯并三唑,2-(2-羟基-4-辛氧基苯基)苯并三唑,2-(3,5-二叔戊基-2-羟基苯基)苯并三唑,2-(3,5-双-(α,α-二甲基苄基)-2-羟基苯基)苯并三唑,2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3-叔丁基-5-[2-(2-乙基己氧基)-羰基乙基]-2-羟基苯基)-5-氯-苯并三唑,2-(3-叔丁基-2-羟基-5-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3-叔丁基-2-羟基-5-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3-叔丁基-5-[2-(2-乙基己氧基)羰基乙基]-2-羟基苯基)苯并三唑,2-(3-十二烷基-2-羟基-5-甲基苯基)苯并三唑,2-(3-叔丁基-2-羟基-5-(2-异辛氧基羰基乙基)苯基苯并三唑,2,2’-亚甲基-双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3-叔丁基-5-(2-甲氧基羰基乙基)-2-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯基转移产物;[R-CH2CH2-COO-CH2CH2-]2-其中R=3’-叔丁基-4’-羟基-5’-2H-苯并三唑-2-基苯基,2-[2-羟基-3-(α,α-二甲基苄基)-5-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2-羟基-3-(1,1,3,3-四甲基丁基)-5-(α,α-二甲基苄基)苯基]苯并三唑。
2.2.2-羟基二苯甲酮类,例如4-羟基,4-甲氧基,4-辛氧基,4-癸氧基,4-十二烷氧基,4-苄氧基,4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3.取代的和未取代的苯甲酸的酯类,例如水杨酸4-叔丁基-苯基酯,水杨酸苯酯,水杨酸辛基苯酯,二苯甲酰基间苯二酚,双(4-叔丁基苯甲酰基)间苯二酚,苯甲酰基间苯二酚,3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯,3,5-二叔丁基-4-羟基苯甲酸十六烷基酯,3,5-二叔丁基-4-羟基苯甲酸十八烷基酯,3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯基酯。
2.4.丙烯酸酯类,例如α-氰基-β,β-二苯基丙烯酸乙酯,α-氰基-β,β-二苯基丙烯酸异辛酯,α-甲酯基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸丁酯,α-甲酯基-对甲氧基肉桂酸甲酯和N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚。
2.5.镍化合物类,例如2,2′-硫代-双-[4-(1,1,3,3-四甲基-丁基)苯酚]的镍配合物,如1∶1或1∶2配合比,有或没有附加的配位体如正丁基胺,三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯(例如甲酯或乙酯)类的镍盐,酮肟例如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物类,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,有或没有附加的配位体。
2.6.空间位阻胺;例如癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯,琥珀酸双(2,2,6,6-四甲基-4-哌啶基)酯,癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯,癸二酸双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯,双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯。1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的直链或环状缩合物,次氮基三乙酸三(2,2,6,6-四甲基-4-哌啶基)酯,1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯,1,1′-(1,2-亚乙基)双(3,3,5,5-四甲基哌嗪酮),4-苯甲酰基-2,2,6,6-四甲基哌啶,4-硬脂酰氧基-2,2,6,6-四甲基哌啶,2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,癸二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,琥珀酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,N,N′-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的直链或环状缩合物,2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-和4-硬脂酰氧基-2,2,6,6-四甲基哌啶的混合物,N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物,1,2-双(3-氨基-丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪的缩合物,以及4-丁基氨基-2,2,6,6-四甲基哌啶(CAS登记号[136504-96-6]);N-(2,2,6,6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺,N-(1,2,2,6,6-五甲基-4-哌啶基)正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4.5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷和表氯醇的反应产物,1,1-双(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯,N,N’-双甲酰基-N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺,4-甲氧基-亚甲基-丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
2.7.草酰胺类,例如4,4′-二辛氧基N,N′-草酰二苯胺,2,2′-二乙氧基N,N’-草酰二苯胺,2,2′-二辛氧基-5,5’-二叔丁基N,N’-草酰二苯胺,2,2’-二(十二烷氧基)-5,5’-二叔丁基N,N’-草酰二苯胺,2-乙氧基-2 ′-乙基N,N’-草酰二苯胺,N,N′-双(3-二甲氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2′-乙基N,N’-草酰二苯胺和它与2-乙氧基-2′-乙基-5,4′-二叔丁基N,N’-草酰二苯胺的混合物以及邻-和对-甲氧基双取代的N,N’-草酰二苯胺类的混合物和邻-和对-乙氧基-二取代的N,N’草酰二苯胺类的混合物。
2.8.2-(2-羟基苯基)-1,3,5-三嗪类,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛氧基-丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基-苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷氧基-丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2(2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,4,6-双(2,4-二甲基苯基)-2-[2-羟基-4-(2-羟基-3-壬基氧基丙氧基)-5-(1-甲基-1-苯基乙基)苯基-1,3,5-三嗪。
3.金属减活剂类,例如N,N′-二苯基草酰胺,N-水杨醛-N′-水杨酰基肼,N,N′-双(水杨酰基)肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,3-水杨酰基氨基-1,2,4-三唑,双(亚苄基)草酰二肼,N,N’-草酰二苯胺,间苯二甲酰二肼,癸二酰双(苯基肼),N,N′-二乙酰基己二酰二肼,N,N′-双(水杨酰基)草酰二肼,N,N′-双(水杨酰基)硫代丙酰基二肼。
4.亚磷酸酯类和亚膦酸酯类,例如亚磷酸三苯酯,亚磷酸二苯基烷基酯,亚磷酸苯基二烷基酯,亚磷酸三(壬基苯基)酯,亚磷酸三月桂基酯,亚磷酸三(十八烷基)酯,二亚磷酸二硬脂基季戊四醇酯,亚磷酸三(2,4-二叔丁基苯基)酯,二亚磷酸二异癸基季戊四醇酯,二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯,二亚磷酸双(2,6-二叔丁基-4-甲基苯基)-季戊四醇酯,二亚磷酸二异癸基氧基季戊四醇酯,二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯,二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯,三亚磷酸三硬脂基山梨糖醇酯,二亚膦酸四(2,4-二叔丁基苯基)4,4′-亚联苯基酯,6-异辛氧基-2,4,8,10-四叔丁基-二苯并[d,f][1,3,2]-dioxaphosphepin,6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g][1,3,2]-dioxaphosphocin,亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲基酯,亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙基酯,2,2′,2″-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)亚磷酸酯],亚磷酸2-乙基己基(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)酯。
尤其优选的是以下亚膦酸酯:
5.羟基胺类,例如N,N-二苄基羟基胺,N,N-二乙基羟基胺,N,N-二辛基羟基胺,N,N-二月桂基羟基胺,N,N-二(十四烷基)羟基胺,N,N-二(十六烷基)羟基胺,N,N-二(十八烷基)羟基胺,N-十六烷基-N-十八烷基羟基胺,N-十七烷基-N-十八烷基羟基胺,从氢化牛油脂肪胺得到的N,N-二烷基羟基胺,由N,N-二(氢化牛脂基)胺的直接氧化生产的N,N-二(烷基)羟基胺。
6.硝酮类,例如N-苄基-α-苯基-硝酮,N-乙基-α-甲基-硝酮,N-辛基-α-庚基-硝酮,N-月桂基-α-十一烷基-硝酮,N-十四烷基-α-十三烷基-硝酮,N-十六烷基-α-十五烷基-硝酮,N-十八烷基-α-十七烷基-硝酮,N-十六烷基-α-十七烷基-硝酮,N-十八烷基-α-十五烷基-硝酮,N-十七烷基-α-十七烷基-硝酮,N-十八烷基-α-十六烷基-硝酮,从氢化牛油脂肪胺衍生而来的N,N-二烷基羟基胺获得的硝酮。
7.苯并呋喃酮类和二氢吲哚酮类,例如在US 4,325,863,US4,338,244,US 5,175,312,US 5,216,052,US 5,252,643,DE-A-4,316,611,DE-A-4,316,622,DE-A-4,316,876,EP-A-0589839或EP-A-0591102中公开的那些,或3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基-苯并呋喃-2-酮,5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]苯并呋喃-2-酮,3,3′-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮],5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮,3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(3,4-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮,3-(2,3-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮。
8.硫代协合剂,例如硫代二丙酸二月桂基酯或硫代二丙酸二硬脂基酯。
9.过氧化物清除剂,例如β-硫代二丙酸的酯类,例如月桂基、硬脂基、十四烷基或十三烷基酯类,巯基苯并咪唑或2-巯基苯并咪唑的锌盐,二丁基二硫代氨基甲酸锌,二(十八烷基)二硫醚,四(β-十二烷基巯基)丙酸季戊四醇酯。
10.聚酰胺稳定剂,例如铜盐与碘化物和/或磷化合物结合,和二价锰的盐。
11.碱性助稳定剂,例如三聚氰胺,聚乙烯基吡咯烷酮,双氰胺,三烯丙基氰脲酸酯,脲衍生物,肼衍生物,胺类,聚酰胺类,聚氨酯类,高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙,硬脂酸锌,二十二烷酸镁,硬脂酸镁,蓖麻酸钠和棕榈酸钾,邻苯二酚锑或邻苯二酚锡。
12.成核剂,例如无机物如滑石,金属氧化物如二氧化钛或氧化镁,磷酸盐、碳酸盐或硫酸盐(优选碱土金属的这些盐);有机化合物如单或多羧酸及其盐,例如4-叔丁基苯甲酸,己二酸,二苯基乙酸,琥珀酸钠或苯甲酸钠;聚合物如离子共聚物(离聚物)。
13.填料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃泡,石棉,滑石,高岭土,云母,硫酸钡,金属氧化物和氢氧化物,炭黑,石墨,木粉或其它天然产品的粉末或纤维,合成纤维。
14.其它添加剂,例如增塑剂,润滑剂,乳化剂,颜料,染料,荧光增白剂,流变添加剂,催化剂,流动控制剂,滑爽剂,交联剂,交联促进剂,卤素清除剂,烟雾抑制剂,防火剂,抗静电剂,澄清剂和发泡剂。
填料(以上清单中的项目13.)例如是金属氢氧化物,尤其氢氧化镁和氢氧化铝。它们能够以基于聚烯烃重量的大约0.01到大约60wt%的浓度添加。
发泡剂(以上清单中的项目14.),如偶氮甲酰胺,能够用于提供泡沫体而不是密实绝缘体。
组分(b)的主抗氧化剂,组分(c)的金属减活剂和任选的其它添加剂能够通过已知方法引入到组分(a)的聚烯烃中,例如在模塑加工之前或之后,或也可通过将溶解或分散的稳定剂混合物施加于聚烯烃中,有或没有随后的溶剂蒸发操作。
组分(b)和(c)和任选的其它添加剂还能够以母料形式加入到聚烯烃中,该母料含有例如大约2.5%到大约25wt%浓度的这些组分。
组分(b)的抗氧化剂总共以例如大约0.01wt%至大约1.5wt%范围内的量使用,基于聚烯烃(a)的重量。优选地,组分(b)的化合物总共以大约0.05wt%至1.0wt%范围内的量使用,基于聚烯烃(a)的重量。
组分(c)的金属减活剂总共以例如大约0.1wt%至大约2.5wt%范围内的量使用,基于聚烯烃(a)的重量。优选地,组分(c)的化合物总共以大约0.1wt%至2.0wt%范围内的量使用,基于聚烯烃(a)的重量。
在本发明中使用的组分(c)的金属减活剂与组分(b)的抗氧化剂的重量比是在例如大约0.5∶1至大约20∶1之间。优选地,组分(c)与组分(b)的比率是在大约1∶1到大约10∶1范围内。
下面实施例用于更详细地说明本发明。它们不被认为以任何方式限制本发明。
实施例1:填充油脂电缆结构中聚烯烃的稳定化
将100份高密度聚乙烯与0.4份IrganoxMD1024(1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼)和0.2份的下表1中列出的主抗氧化剂中的一种进行干混。该混合物通过使用24∶1 L/D螺杆,在Superior/MPM挤出机中用Maddock混合头以60 rpm在230℃下进行热熔混合,制成粒料。
将含有稳定剂混合物的已造粒的聚乙烯,在204℃(400°F)下压塑成具有Mylar衬材的0.254mm(0.01英寸)厚度膜。对这些试验膜测量“初始氧化诱导时间”(OIT)。
将样品膜然后浸泡在购自Witco公司的Witcogel中,它是一种用于电信电缆中的典型烃类电缆填充油脂。该Witco填充化合物含有0.6%Irganox1035,硫代二亚乙基双(3-(3,5-二叔丁基-4-羟苯基)丙酸酯]。将在填充化合物中浸泡的样品膜,在70℃的热空气干燥炉中暴露14天。然后擦净样品的电缆填充油脂。对这些样品测量“老化氧化诱导时间”。
OIT测试是按照ASTM标准测试方法D3895,通过使用差示扫描量热仪来完成的。测试条件是:无褶皱铝盘;无屏蔽;在氮气氛围下加热到200℃,随后切换至100毫升/分的氧气流。氧化诱导时间(OIT)是在氧气流的开始和测试样品的放热分解之间的时间间隔。OIT是以分钟报告的;OIT越长,稳定剂混合物在防止氧化降解上越有效。稳定剂混合物在油脂填充的电缆应用中的相对性能,能够通过对比初始OIT值和老化后的OIT值来预测。
表1
主抗氧化剂 | 初始OIT(分钟) | 老化OIT(分钟) |
Irganox1010 | 77 | 25 |
Irganox1098 | 161 | 90 |
Irganox3114 | 91 | 44 |
Irganox3125 | 126 | 51 |
Irgano1098、Irganox3114、Irganox3125的稳定剂混合物,各个具有金属减活剂IrganoMD 1024(1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼),在初始和老化OIT方面超过现有技术的Irgano1010/IrganoMD 1024的稳定剂混合物。Irganox1098是N,N’-己烷-1,6-二基双-(3-(3,5-二叔丁基-4-羟基苯基丙酰胺)),Irganox3114是三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯,Irgano3125是三(2-(3,5-二叔丁基-4-羟基氢化肉桂酰氧基)乙基)异氰脲酸酯。Irganox是Ciba Specialty Chemicals Corporation的商标。
Claims (8)
1.稳定化的电缆结构,它包括
(i)彼此之间有空隙的多个被绝缘的电导线,该绝缘体包括
(a)一种或多种聚烯烃,和
(b)选自N,N’-己烷-1,6-二基双-(3-(3,5-二叔丁基-4-羟基苯基丙酰胺)),三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯和三(2-(3,5-二叔丁基-4-羟基氢化肉桂酰氧基)乙基)异氰脲酸酯的一种或多种主抗氧化剂,和
(c)选自烷基羟基苯基链烷酰肼类的一种或多种金属减活剂,和
(ii)在该空隙内的烃类电缆填充油脂,和
(iii)包围组分(i)和(ii)的护套。
2.根据权利要求1的电缆结构,其中所述组分(a)的聚烯烃是聚乙烯或聚丙烯或它们的混合物。
4.根据权利要求1的电缆结构,其中所述组分(c)的金属减活剂是1,2-双(3,5-二叔丁基-4-羟基氢化肉桂酰基)肼。
5.根据权利要求1的电缆结构,其中所述组分(b)的抗氧化剂总共以大约0.05wt%至大约1.0wt%范围内的量存在,基于组分(a)的聚烯烃的重量。
6.根据权利要求1的电缆结构,其中所述组分(c)的金属减活剂总共以大约0.1wt%至大约2.0wt%范围内的量存在,基于组分(a)的聚烯烃的重量。
7.根据权利要求1的电缆结构,其中组分(ii)的烃类电缆填充油脂或其烃成分的一种或多种存在于组分(a)的聚烯烃中。
8.根据权利要求1的电缆结构,其中组分(ii)的烃类电缆填充油脂或其烃成分中的一种或多种,总共以基于组分(a)重量的大约3至大约30wt%范围内的量存在于组分(a)的聚烯烃中。
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- 2000-02-21 AU AU31579/00A patent/AU752917B2/en not_active Ceased
- 2000-02-21 WO PCT/EP2000/001403 patent/WO2000058975A1/en active IP Right Grant
- 2000-02-21 EP EP00909224A patent/EP1171890B1/en not_active Expired - Lifetime
- 2000-02-21 DE DE60038549T patent/DE60038549T2/de not_active Expired - Lifetime
- 2000-02-21 ES ES00909224T patent/ES2302688T3/es not_active Expired - Lifetime
- 2000-02-21 CA CA002363375A patent/CA2363375C/en not_active Expired - Fee Related
- 2000-02-21 AT AT00909224T patent/ATE391995T1/de active
- 2000-02-21 KR KR1020017012231A patent/KR100596078B1/ko not_active IP Right Cessation
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2001
- 2001-09-05 NO NO20014321A patent/NO328133B1/no not_active IP Right Cessation
Cited By (6)
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CN100457815C (zh) * | 2003-04-16 | 2009-02-04 | 普瑞曼聚合物有限公司 | 聚烯烃树脂组合物和使用它的树脂成形体的组合体 |
CN101540219B (zh) * | 2008-03-19 | 2012-04-18 | 上海金友电线电缆有限公司 | 125℃辐照交联电力电缆的制造方法 |
CN103198903A (zh) * | 2013-04-12 | 2013-07-10 | 常州市新东方电缆有限公司 | 一种光伏电缆的生产工艺 |
CN103198903B (zh) * | 2013-04-12 | 2016-12-28 | 常州市新东方电缆有限公司 | 一种光伏电缆的生产工艺 |
CN105609194A (zh) * | 2016-02-03 | 2016-05-25 | 安徽南洋电缆有限公司 | 一种抗拖拽抗干扰电缆 |
CN105670148A (zh) * | 2016-02-03 | 2016-06-15 | 安徽华海特种电缆集团有限公司 | 一种防火抗拖拽井下电缆 |
Also Published As
Publication number | Publication date |
---|---|
US6228495B1 (en) | 2001-05-08 |
AU752917B2 (en) | 2002-10-03 |
EP1171890A1 (en) | 2002-01-16 |
WO2000058975A1 (en) | 2000-10-05 |
AU3157900A (en) | 2000-10-16 |
NO20014321D0 (no) | 2001-09-05 |
DE60038549T2 (de) | 2009-06-10 |
ATE391995T1 (de) | 2008-04-15 |
CA2363375A1 (en) | 2000-10-05 |
CA2363375C (en) | 2007-12-04 |
DE60038549D1 (de) | 2008-05-21 |
NO328133B1 (no) | 2009-12-14 |
NO20014321L (no) | 2001-09-05 |
CN1175431C (zh) | 2004-11-10 |
KR20010110692A (ko) | 2001-12-13 |
KR100596078B1 (ko) | 2006-07-03 |
ES2302688T3 (es) | 2008-08-01 |
EP1171890B1 (en) | 2008-04-09 |
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