CN1250636C - 稳定的中电压和高电压电缆绝缘组合物 - Google Patents
稳定的中电压和高电压电缆绝缘组合物 Download PDFInfo
- Publication number
- CN1250636C CN1250636C CNB021060223A CN02106022A CN1250636C CN 1250636 C CN1250636 C CN 1250636C CN B021060223 A CNB021060223 A CN B021060223A CN 02106022 A CN02106022 A CN 02106022A CN 1250636 C CN1250636 C CN 1250636C
- Authority
- CN
- China
- Prior art keywords
- uncle
- alkyl
- butyl
- tertiary butyl
- sulphomethyl
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000009413 insulation Methods 0.000 title abstract description 4
- -1 polyethylene Polymers 0.000 claims abstract description 105
- 239000003112 inhibitor Substances 0.000 claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 claims abstract description 20
- 229920000573 polyethylene Polymers 0.000 claims abstract description 20
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 claims description 29
- 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 claims description 22
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 11
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 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 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- DMLLDZGHGNLZNW-UHFFFAOYSA-N 4-octyl-n-phenylaniline Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=CC=C1 DMLLDZGHGNLZNW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 claims 1
- 239000004703 cross-linked polyethylene Substances 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 150000001451 organic peroxides Chemical class 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 27
- 150000002431 hydrogen Chemical class 0.000 description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 3
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960003328 benzoyl peroxide Drugs 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001400 nonyl 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])[H] 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CIGIRZIOSVQVKQ-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCCCC CIGIRZIOSVQVKQ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- JNSWFNBIZLIBPH-UHFFFAOYSA-N 4-tert-butylperoxy-4-methylpentan-2-ol Chemical class CC(O)CC(C)(C)OOC(C)(C)C JNSWFNBIZLIBPH-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000010754 BS 2869 Class F Substances 0.000 description 1
- KIQCTMKOAYVJOI-UHFFFAOYSA-N C(C)C(COC(=O)CC(S(=O)(=O)O)C1=C(C=CC(=C1)C1CCCCC1)O)CCCC Chemical compound C(C)C(COC(=O)CC(S(=O)(=O)O)C1=C(C=CC(=C1)C1CCCCC1)O)CCCC KIQCTMKOAYVJOI-UHFFFAOYSA-N 0.000 description 1
- KWEKUPVGRQSEJA-UHFFFAOYSA-N C(C)C(COC(=O)CSCC1=C(C(=CC=C1)C)O)CCCC Chemical class C(C)C(COC(=O)CSCC1=C(C(=CC=C1)C)O)CCCC KWEKUPVGRQSEJA-UHFFFAOYSA-N 0.000 description 1
- XBLGAOKJSIENON-UHFFFAOYSA-N CCN(CC)SC(NC(CNC(S)=S)=C=O)=S Chemical compound CCN(CC)SC(NC(CNC(S)=S)=C=O)=S XBLGAOKJSIENON-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- RILYLANXKIYNSE-UHFFFAOYSA-N OC(CC(S(=O)(=O)O)C1=C(C=CC(=C1)C)O)CO Chemical class OC(CC(S(=O)(=O)O)C1=C(C=CC(=C1)C)O)CO RILYLANXKIYNSE-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- QHZUXKKDHLFUEF-UHFFFAOYSA-N chloro benzenecarboperoxoate Chemical compound ClOOC(=O)C1=CC=CC=C1 QHZUXKKDHLFUEF-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical class CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- NMUXPVMDAYGGGN-UHFFFAOYSA-N n-(1,3-benzothiazol-2-yl)-2-(4-chlorophenoxy)-2-methylpropanamide Chemical group N=1C2=CC=CC=C2SC=1NC(=O)C(C)(C)OC1=CC=C(Cl)C=C1 NMUXPVMDAYGGGN-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000009288 screen filtration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
本发明涉及一种用作电线和电缆绝缘材料的聚乙烯组合物,它具有改进的耐焦烧性,组合物包括:(a)聚乙烯,(b)在大气压下熔点低于50℃的焦烧抑制剂,和(c)有机过氧化物。
Description
技术领域
本发明涉及一种用作电线和电缆绝缘材料的聚乙烯组合物,它具有改进的耐焦烧性。稳定的组合物适于作为中电压和高电压电源电缆的电缆绝缘材料。
背景技术
绝缘组合物一般包括聚乙烯、过氧化物交联剂和稳定剂。包含过氧化物的聚合物易于焦烧,即在挤出工艺期间发生过早的交联。
当选择合适的稳定体系时,有几个必须考虑的关键因素。这些因素包括交联速度和交联程度、在挤出温度下的耐焦烧性、在高温老化之前和之后机械性能的有效保留、没有向聚合物表面的渗出和高的清洁度。
US专利6,191,230描述了一种聚乙烯组合物,该组合物包含作为焦烧抑制剂的取代对苯二酚、4,4’-硫代双(2-甲基-6-叔丁基苯酚)、4,4’-硫代双(2-叔丁基-5-甲基苯酚)、或其混合物。
为除去导电杂质,欧洲专利申请EP-A-613154描述了一种聚乙烯组合物的制备方法,由此在低密度聚乙烯进行纯化过程之后,将交联剂和/或稳定剂共混入低密度聚乙烯中。
清洁度是关键的参数和仍然需要提供清洁的绝缘材料,该材料包含聚乙烯可交联组合物,该组合物可以在过早交联最小的情况下挤出,和还显示足够的交联速度。
发明内容
已经发现,通过使用液体稳定体系可以获得改进的绝缘材料。
因此,本发明涉及一种组合物,其包括:
(a)聚乙烯,
(b)在大气压下熔点低于50℃的焦烧抑制剂,和
(c)有机过氧化物。
在大气压下熔点低于50℃的焦烧抑制剂是例如:
在US 4,759,862和US 4,857,572中描述的酚,
在US 5,008,459中描述的酚或这些酚的混合物;
包含芳族胺和酚的混合物,如在US 5,091,099中描述的。
术语“焦烧抑制剂”也包括在US 5,091,099中描述的混合物,该混合物另外包含在US 4,759,862、US 4,857,572和5,008,459中描述的酚。
参见US 4,759,862和US 4,857,572,焦烧抑制剂是如下通式的化合物:
其中
R1是C1-20烷基或被苯基取代的C1-20烷基、C2-20烯基、C3-20炔基、C5-9环烷基、苯基或甲苯基;
R2和R3每个彼此独立地是:
C1-20烷基或被以下基团取代的C1-20烷基:苯基、一个或两个羟基、氰基、甲酰基、乙酰基、-O-COR5;R5是C1-20烷基;
C2-20烯基或C3-20炔基;
C5-7环烷基或被羟基取代的C5-7环烷基;
苯基、4-氯苯基、2-甲氧基羰基苯基、对甲苯基、
1,3-苯并噻唑-2-基、或
-(CHR6)nCOOR7或-(CHR6)nCONR8R9,其中
n 是1或2,
R6 是氢或C1-6烷基,
R7 是C1-20烷基、被1-5个O或S间隔的C1-20烷基、C5-7环烷基、苯基、苄基、甲苯基,
R8和R9是氢或C1-6烷基;
R4是氢或甲基。
C1-20烷基是,例如,甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、异戊基、正己基、正庚基、1,1-二甲基丁基、正辛基、2-乙基己基、异辛基(伯辛基的异构体混合物)、正壬基、叔壬基(异构体混合物)、正癸基、1,1,3,3-四甲基丁基(叔辛基)、正十二烷基、叔十二烷基(包含作为主要组分的1,1,3,3,5,5-六甲基己基和1,1,4,6,6-五甲基庚-4-基)、正十四烷基、正十六烷基、正十八烷基或正二十烷基。
C2-20烯基是,例如,乙烯基、烯丙基(丙-2-烯基)、丁-3-烯基、戊-4-烯基、己-5-烯基、辛-7-烯基、癸-9-烯基或十二烷-11-烯基。优选烯丙基。
C3-20炔基是,例如,炔丙基、丁-3-炔基、己-5-炔基、辛-7-炔基、癸-9-炔基、十二烷-11-炔基、十四烷-13-炔基、十六烷-15-炔基、十八烷-17-炔基或二十烷-19-炔基。优选炔丙基。
C5-9环烷基是,例如,环戊基、环己基、环庚基、环辛基、环壬基,和特别是环己基。
被苯基取代的C1-20烷基是,例如,苄基、苯乙基、α-甲基苄基、α,α-二甲基苄基、苯基丁基、苯基-α,α-二甲基丙基、苯基己基、苯基-(α,α-二甲基丁基、苯基辛基或苯基-α,α-二甲基己基、。
优选苄基、α-甲基苄基和α,α-二甲基苄基。
被一个或两个羟基取代的C1-20烷基是,例如,2-羟乙基、2-羟丙基、2-羟丁基、2-羟己基、2-羟辛基、2-羟癸基、2-羟基十二烷基、2-羟基十四烷基、2-羟基十六烷基、2-羟基十八烷基、2-羟基二十烷基或2,3-二羟基丙基。
优选2-羟乙基、2-羟丙基和2,3-二羟基丙基。
被苯基和羟基取代的C1-20烷基是,例如,1-苯基-2-羟乙基。
被氰基取代的C1-20烷基是,例如,2-氰乙基。
被1-5个0或S间隔的C1-20烷基是,例如,3-氧杂丙基、3-硫杂丙基、3-氧杂丁基、3-硫杂丁基、3-氧杂戊基、3-硫杂戊基、3,6-二氧杂庚基、3,6,9-三氧杂癸基或3,6,9,12,15,18六氧杂十九烷基。
基团R1优选是C1-20烷基,更优选是甲基或叔丁基,最优选是甲基,基团R2和R3优选相同和是C1-20烷基或被一个或两个羟基取代的C1-20烷基,优选C8-14烷基,和特别是正辛基、叔壬基、正十二烷基或叔十二烷基、2-羟乙基或2,3-二羟基丙基。
以下所列的物质可以认为是通式I化合物的代表性例子:
a)通式I的化合物,其中
R1=烷基(甲基、叔丁基、异丙基、2-乙基己基、1,1-二甲基丙基或1,1-二甲基丁基)
2,4-双(2’-羟基乙基硫代甲基)-6-甲基苯酚,
2,4-双(2’,3’-二羟基丙基硫代甲基)-3,6-二甲基苯酚,
2,4-双(2’-乙酰氧基乙基硫代甲基)-3,6-二甲基苯酚,
2,4-双(2’-正癸酰氧基乙基硫代甲基)-6-甲基苯酚,
2,4-双(正辛基硫代甲基)-6-甲基苯酚,
2,4-双(正十二烷基硫代甲基)-6-甲基苯酚,
2,4-双(叔十二烷基硫代甲基)-6-甲基苯酚,
2,4-双(苄基硫代甲基)-6-甲基苯酚,
2,4-双(2’-乙基己氧基羰基甲基硫代甲基)-6-甲基苯酚,
2,4-双(正十八烷氧基羰基甲基硫代甲基)-3,6-二甲基苯酚,
2,4-双(甲基硫代甲基)-6-叔丁基苯酚,
2,4-双(乙基硫代甲基)-6-叔丁基苯酚,
2,4-双(正丙基硫代甲基)-6-叔丁基苯酚,
2,4-双(正丁基硫代甲基)-6-叔丁基苯酚,
2,4-双(正己基硫代甲基)-6-叔丁基苯酚,
2,4-双(正辛基硫代甲基)-6-叔丁基苯酚,
2,4-双(正癸基硫代甲基)-6-叔丁基苯酚,
2,4-双(正十二烷基硫代甲基)-6-叔丁基苯酚,
2,4-双(正十四烷基硫代甲基)-6-叔丁基苯酚,
2,4-双(正十六烷基硫代甲基)-6-叔丁基苯酚,
2,4-双(正十八烷基硫代甲基)-6-叔丁基苯酚,
2,4-双(正二十烷基硫代甲基)-6-叔丁基苯酚,
2,4-双(异丙基硫代甲基)-6-叔丁基苯酚,
2,4-双(仲丁基硫代甲基)-6-叔丁基苯酚,
2,4-双(叔丁基硫代甲基)-6-叔丁基苯酚,
2,4-双(2-乙基己基硫代甲基)-6-叔丁基苯酚,
2,4-双(1,1,3,3-四甲基丁基硫代甲基)-6-叔丁基苯酚,
2,4-双(1,1,3,3,5,5-六甲基己基硫代甲基)-6-叔丁基苯酚,
2,4-双[4-(2,2,4,6,6-五甲基庚基)-硫代甲基]-6-叔丁基苯酚,
2,4-双(丙-2-烯基硫代甲基)-6-叔丁基苯酚,
2,4-双(丙-2-炔基硫代甲基)-6-叔丁基苯酚,
2,4-双(环己基硫代甲基)-6-叔丁基苯酚,
2,4-双(2-羟基环己基硫代甲基)-6-叔丁基苯酚,
2,4-双(苯基硫代甲基)-6-叔丁基苯酚,
2,4-双(苯基硫代甲基)-3-甲基-6-叔丁基苯酚,
2,4-双(苄基硫代甲基)-6-叔丁基苯酚,
2,4-双(对甲苯基硫代甲基)-6-叔丁基苯酚,
2,4-双[2’-(2”-乙基己氧基羰基)乙基硫代甲基]-3-甲基-6-叔丁基苯酚,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二甲酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二丁酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二辛酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的双十二烷基酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的单甲酯,
2,4-双(4-羧基-2-硫杂丁基)-6-叔丁基苯酚的二甲酯,
2,4-双(4-羧基-2-硫杂丁基)-6-叔丁基苯酚的二辛酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二(2-乙基己)酯,
2,4-双(3-羧基-2-硫杂丁基)-6-叔丁基苯酚的二甲酯,
2,4-双(4-羧基-3-甲基-2-硫杂戊基)-6-叔丁基苯酚的二甲酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的N,N-二甲基酰胺,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的N,N-二己基酰胺,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的N,N-双十二烷基酰胺,
2,4-双(4-羧基-2-硫杂丁基)-6-叔丁基苯酚的N,N-二甲基酰胺,
2,4-双[3-羧基-2-硫杂丁基]-6-叔丁基苯酚的N,N-二甲基酰胺,
2,4-双(4-羧基-3-甲基-2-硫杂戊基)-6-叔丁基苯酚的N,N-二丁基酰胺,
2,4-双[3-羧基-2-硫杂丙基]-6-叔丁基苯酚的二环己酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二苯酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二苄酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二对甲苯酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二(3-硫杂丁)酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二(3-氧杂丁)酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二(N,N-二甲基氨基-2-乙)酯,
2,4-双(3-羧基-2-硫杂丙基)-6-叔丁基苯酚的二酰胺,
2,4-双(4-羧基-2-硫杂丁基)-6-叔丁基苯酚的二酰胺,
2,4-双(丙-2-烯基硫代甲基)-6-叔丁基苯酚,
2,4-双(丙-2-炔基硫代甲基)-6-叔丁基苯酚,
2,4-双(2-羟基乙基硫代甲基)-6-叔丁基苯酚,
2,4-双(2-氰基乙基硫代甲基)-6-叔丁基苯酚,
2,4-双[(4-甲氧基苯基)-硫代甲基]-6-叔丁基苯酚,
2,4-双[(4-氯苯基)-硫代甲基]-6-叔丁基苯酚,
2,4-双[(2-甲氧基羰基苯基)-硫代甲基]-6-叔丁基苯酚,
2,4-双[(1,3-苯并噻唑-2-基)-硫代甲基]-6-叔丁基苯酚,
2,4-双[2,3-二羟基丙基硫代甲基]-6-叔丁基苯酚,
2,4-双[(3,5-二叔丁基-4-羟苯基)硫代甲基]-6-叔丁基苯酚,
2,4-双[4-(3,5-二叔丁基-4-羟苯基)-2-硫杂丁基]-6-叔丁基苯酚,
2,4-双[4-乙酰氧基-2-硫杂丁基]-6-叔丁基苯酚,
2,4-双[3-甲酰基-2-硫杂丁基]-6-叔丁基苯酚,和
2,4-双[3-乙酰基-2-硫杂丁基]-6-叔丁基苯酚。
2,4-双(正辛基硫代甲基)-6-异丙基苯酚,
2,4-双(正十二烷基硫代甲基)-6-异丙基苯酚,
2,4-双(正辛基硫代甲基)-6-(2-乙基己基)-苯酚,
2,4-双(正十二烷基硫代甲基)-6-(2-乙基己基)-苯酚,
2,4-双(正十二烷基硫代甲基)-6-(1,1-二甲基丙基)-苯酚,
2,4-双(正辛基硫代甲基)-6-(1,1-二甲基丁基)-苯酚,
2,4-双(正十二烷基硫代甲基)-6-(1,1-二甲基丁基)-苯酚,
b)通式I的化合物,其中R1=环烷基(环己基)
2,4-双(正辛基硫代甲基)-6-环己基苯酚,
2,4-双(正十二烷基硫代甲基)-6-环己基苯酚,
c)通式I的化合物,其中R1=苯基或甲苯基
2,4-双(正辛基硫代甲基)-6-苯基苯酚,
2,4-双(正十二烷基硫代甲基)-6-苯基苯酚,
2,4-双(正辛基硫代甲基)-6-对甲苯基苯酚,
2,4-双(正十二烷基硫代甲基)-6-对甲苯基苯酚,
d)通式I的化合物,其中R1=被苯基取代的烷基(苄基,α,α-二甲基苄基)
2,4-双(正辛基硫代甲基)-6-苄基苯酚,
2,4-双(正十二烷基硫代甲基)-6-苄基苯酚,
2,4-双(正十二烷基硫代甲基)-6-(α,α-二甲基苄基)-苯酚,
e)通式I的化合物,其中R1=烯基(丙-2-烯基)或炔基(丙-2-炔基)
2,4-双(正辛基硫代甲基)-6-丙-2-烯基苯酚,
2,4-双(正十二烷基硫代甲基)-6-丙-2-烯基苯酚,
2,4-双(正十二烷基硫代甲基)-6-丙-2-炔基苯酚,
特别合适的是在US 4,857,572中公开的通式I的那些化合物,其中
R1 | R2和R3 | R4 | Mp℃ |
甲基甲基甲基甲基叔丁基甲基甲基甲基甲基甲基 | 正辛基正辛基正十二烷基正十二烷基正十二烷基苄基-CH2COOR7,R7=2-乙基己基-CH2CH2OH-C(CH3)2-CH2-(CH3)2-CH2-C(CH3)3-C(CH3)2-CH2-C(CH3)3 | 氢甲基氢甲基甲基氢氢氢氢氢 | <20<20284340<20<20<20<20<20 |
或在US 4,759,862中公开的通式I的那些化合物,其中
R1 | R2和R3 | R4 | mp℃ |
叔丁基叔丁基叔丁基叔丁基苯基叔丁基叔丁基叔丁基叔丁基 | 2-乙基己基正辛基正十二烷基-CH2COOR7,R7=2-乙基己基-CH2COOR7,R7=2-乙基己基叔-C8H17-叔-C9H19--CH2CH2OH-CH2CH(OH)CH2OH | 氢氢氢氢甲基氢氢氢氢 | <20<20<20<20<20<20<20<20<20 |
通式I的最优选液体焦烧抑制剂是2,4-双(正辛基硫代甲基)-6-甲基苯酚和2,4-双(正十二烷基硫代甲基)-6-甲基苯酚。
参见US 5,008,459,焦烧抑制剂是通式II或III的化合物或其混合物
其中R1,R2,R3和R4如上所定义,和Z是-S-、-CH2-、-CH(CH3)-或-C(CH3)2-。
以下所列的物质可以认为是通式II化合物的代表性例子:
2,6-双(2’-羟基乙基硫代甲基)-4-甲基苯酚,
2,6-双(2’,3’-二羟基丙基硫代甲基)-4-甲基苯酚,
2,6-双(2’-甲基氨基羰基乙基硫代甲基)-4-苯基苯酚,
2,6-双(N,N-二乙基氨基羰基-乙基硫代甲基)-4-烯丙基苯酚,
2,6-双(正辛基硫代甲基)-4-甲基苯酚,
2,6-双(正十二烷基硫代甲基)-4-甲基苯酚,
2,6-双(正辛基硫代甲基)-4-叔丁基苯酚,
2,6-双(正十二烷基硫代甲基)-4-叔丁基苯酚,
2,6-双(正辛基硫代甲基)-4-(1’,1’,3’,3’-四甲基丁基)苯酚,
2,6-双(叔壬基硫代甲基)-4-叔丁基苯酚,
2,6-双(叔十二烷基硫代甲基)-4-叔辛基苯酚,
2,6-双(苄基硫代甲基)-6-甲基苯酚,
2,6-双(苯基硫代甲基)-4-叔丁基苯酚,
2,6-双(2’-乙基己氧基羰基甲基-硫代甲基)-4-环己基苯酚,
2,6-双(2’-异辛氧基羰基甲基-硫代甲基)-4-环己基苯酚,
2,6-双(正十八烷氧基羰基甲基-硫代甲基)-4-炔丙基苯酚,
2,6-双[2”-(2”-乙基己氧基羰基)-乙基硫代甲基)-4-叔丁基苯酚。
以下所列的物质可以认为是通式III化合物的代表性例子:
2,2-双[4’,4”-二羟基-3’,3”,5’,5”-四(正辛基硫代甲基)-苯基]-丙烷,
2,2-双[4’,4”-二羟基-3’,3”,5’,5”-四(正十二烷基硫代甲基)-苯基]-丙烷,
双[4,4’-二羟基-3,3’,5,5’-四(正辛基硫代甲基)-苯基]-甲烷,
双[4,4’-二羟基-3,3’,5,5’-四(正十二烷基硫代甲基)-苯基]-甲烷,
2,2-双[4’,4”-二羟基-3’,3”,5’,5”-四(2-乙基己氧基羰基-甲基硫代甲基)-苯基]-丙烷,
2,2-双[4’,4”-二羟基-3’,3”,5’,5”-四(2-异辛氧基羰基-甲基硫代甲基)-苯基]-丙烷。
参见US 5,091,099,焦烧抑制剂是混合物,该混合物包含选自如下的胺:二苯胺、4-叔丁基二苯胺、4-叔辛基二苯胺、4,4’-二-叔丁基二苯胺、2,4,4’-三-叔丁基二苯胺、4-叔丁基-4’-叔辛基二苯胺、o,o’-,m,m’-或p,p’-二-叔辛基二苯胺、2,4-二-叔丁基-4’-叔辛基二苯胺、4,4’-二-叔辛基二苯胺、2,4-二-叔辛基-4’-叔丁基二苯胺,和另外根据以上通式I,II,或III的酚,或选自如下的酚:
酚P
酚W
酚S
酚X
酚U
酚V
混合物中芳族胺的量是:
不大于5wt%的二苯胺(a),
8-15wt%的4-叔-二丁基-二苯胺(b),
24-34wt%选自(c)的化合物,
(c)(i)4-叔辛基二苯胺
(c)(ii)4,4’-二叔丁基二苯胺
(c)(iii)2,4,4’-三叔丁基二苯胺23-34wt%选自(d)的化合物,
(d)(i)4-叔丁基-4’-叔辛基二苯胺
(d)(ii)o,o’-,m,m’-或p,p’-二-叔辛基二苯胺
(d)(iii)2,4-二-叔丁基-4’-叔辛基二苯胺;和21-34wt%选自(e)的化合物,
(e)(i)4,4’-二-叔辛基二苯胺
(e)(ii)2,4-二-叔辛基-4’-叔丁基二苯胺,
在每种情况下基于胺的总量。
优选的胺是4,4’-二-叔辛基二苯胺或胺(A),胺(A)是如下物质的混合物:3wt%二苯胺、14wt%的4-叔丁基二苯胺、30wt%的(4-叔辛基二苯胺、4,4’-二-叔丁基二苯胺和2,4,4’-三-叔丁基二苯胺)、29wt%(4-叔丁基-4’-叔辛基二苯胺、o,o’-,m,m’-或p,p’-二-叔辛基二苯胺和2,4-二-叔丁基-4’-叔辛基二苯胺)、18wt%的4,4’-二-叔辛基二苯胺和6wt%的2,4-二-叔辛基-4’-叔丁基二苯胺。
适于作为焦烧抑制剂的混合物例子是:
胺(A)和酚(P)
4,4’-二-叔辛基二苯胺和酚(P)
4,4’-二-叔辛基二苯胺和酚(S)
胺(A)和酚(U)
胺(A)和酚(V)
胺(A)和酚(W)
胺(A)和酚(X)
胺对酚的重量比是4-5∶1。
特别适于作为焦烧抑制剂的是80wt%4,4’-二-叔辛基二苯胺和20wt%酚P的混合物。
通式I,II和III的化合物是通过自身已知的方法制备的,这些方法描述在US 4,759,862和US 4,857,572(通式I)中或在US 5,008,459中(通式II和III)。
在此使用的术语聚乙烯是乙烯均聚物,或乙烯和较小比例的一种或多种α-烯烃及非必要的二烯烃的共聚物,α-烯烃含有3-12个碳原子,和优选4-8个碳原子,或这样均聚物和共聚物的混合物或共混物。混合物可以是机械共混物或原位共混物。α-烯烃的例子是丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、和1-辛烯。聚乙烯也可以是乙烯和如下物质的共聚物:不饱和酯,如乙烯基酯,如醋酸乙烯酯或丙烯酸酯或甲基丙烯酸酯。
合适的聚乙烯是所谓的高压聚乙烯。各种这样的聚合物是可以市购的。高压聚乙烯优选是密度为0.910-0.930g/cm3的乙烯均聚物。均聚物的熔融指数也可以为约1-约5g/10分钟,和优选为约0.75-约3g/10分钟。熔融指数按ASTM D-1238测量。
交联剂是有机过氧化物,包括二烷基过氧化物如过氧化二枯基、过氧化二叔丁基、过氧化叔丁基枯基、2,5-二甲基-2,5-二(叔丁基过氧)-己烷、2,5-二甲基-2,5-二(叔戊基过氧)-己烷、2,5-二甲基-2,5-二(叔丁基过氧)-己烷-3、2,5-二甲基-2,5-二(叔戊基过氧)-己烷-3、α,α-二[(叔丁基过氧)-异丙基]-苯、过氧化二叔戊基、1,3,5-三[(叔丁基过氧)-异丙基]苯、1,3-二甲基-3-(叔丁基过氧)-丁醇、1,3-二甲基-3-(叔戊基过氧)-丁醇及其混合物。其它合适的有机过氧化物是:过氧化琥珀酸、过氧化苯甲酰、叔丁基过氧-2-乙基己酸酯、过氧化对氯苯甲酰、叔丁基过氧异丁酸酯、叔丁基过氧异丙基碳酸酯、叔丁基过氧月桂酸酯、2,5-二甲基-2,5-二(苯甲酰过氧)-己烷、叔丁基过氧乙酸酯、二-叔丁基二过氧邻苯二甲酸酯、叔丁基过氧马来酸、过氧化环己酮、叔丁基过氧苯甲酸酯。优选二烷基过氧化物。
有机过氧化物的分解温度为100-200℃。特别优选的是过氧化二枯基,它的分解温度为150℃。
通过已知方法,例如在低于过氧化物分解温度的温度下,通过在开炼机,捏合挤出机或混合机中的熔融共混,或通过浸渍方法,其中混合液体焦烧抑制剂/过氧化物共混物直到整个液相浸入聚合物中,将过氧化物和焦烧抑制剂引入到聚乙烯中。
也可以在加工之前或期间,将焦烧抑制剂和/或过氧化物加入到聚乙烯中。
焦烧抑制剂的量为0.01-1wt%,优选0.1-0.5wt%。
过氧化物的量为0.5-5wt%,优选1-3wt%。
非必要地,可以1-3wt%,优选2wt%的量,将环氧大豆油加入到聚合物中以稳定聚合物防止变色。
在优选的实施方案中,方法在挤出机中进行。将聚乙烯或聚乙烯/过氧化物共混物引入到挤出机中,和非必要地在过滤之后,通过挤出机的侧进料口,加入熔点低于50℃的焦烧抑制剂或焦烧抑制剂和过氧化物。
然后,通过将挤出物曝露于高于有机过氧化物分解温度的温度,而使挤出物交联。挤出可以在一个或多个导电体周围进行,以形成中电压或高电压电缆。导体是裸导体或被初级绝缘材料和/或半导体层包围的导体。然后将电缆曝露于交联温度下。
可以按任何常规的方式,如在烘箱中或在连续硫化管中,非必要地,但不是必须地在氮气气氛和增加的压力下,进行交联。
稳定的组合物适于用作中电压和高电压电源电缆的电缆绝缘材料。中电压的范围是1kV-40kV。“高电压”指的是超过约40kV,特别是40-110kV的电子管电压。
本发明的优点是在挤出温度下令人惊奇的高的耐焦烧性,同时保持令人满意的交联速度和交联密度。在热老化之前和之后的机械性能满足工业标准的要求。
具体实施方式
如下实施例更详细地说明本发明。
复合物制备
在静态烘箱中,将低密度聚乙烯(d=0.923g/cm3),来自ExxonMobil Chemical的Escorene LD 100MED型,加热到90℃。通过曝露于水浴,而将稳定剂和过氧化物加热到70℃。将透明的稳定剂/过氧化物熔体加入到温热的聚合物粒料中和保持在烘箱中大约60min。每十分钟,将混合物快速取出和充分摇动。重复程序直到整个液相浸入聚合物中。
实验室实施例的结果:
耐焦烧性
为模拟电缆挤出条件,将43g每种复合物称重和在120℃的初始本体温度下,在Brabender Plasticorder 814 300型实验室捏合机中,在30rpm下搅拌熔融。在2.0kg的恒定负荷下将材料捏合直到获得最小扭矩,和可以观察到随后的显著扭矩增加。焦烧时间确定为在最小扭矩和从最小扭矩开始增加1Nm之间的时间。较长的焦烧时间表示由于挤出期间过早交联引起的问题较少发生。结果如表1所示。
交联程序
在三个压缩模塑机中,在不同的温度下,进行交联PE-LD试验样板(厚度:1.5mm)的生产。在第一个模具中,将确定重量的材料在框架中铺展和加热到120℃,持续6分钟。在此时间期间,压力逐渐从0增加到150巴。在下一个步骤中,将带有试验样板的框架转移到第二压缩模塑机中和在180℃放置15min用于完成交联。最后,在十分钟内将试验样板从180℃冷却到室温。
在流变仪中的交联速度
在Moving Die Rheometer(Monsanto MDR 2000)中将5g每种样品加热到180℃。在测试温度下,将样品曝露于恒定振幅的周期性交替应力(在1.66Hz下3°转矩)下,直到获得最大扭矩。标准是恒定交联速度,它是在交联剂和抗氧剂之间的相互作用的量度。
表1
产物 | 填充量 | 焦烧时间 | 固化效率指数 | 最大扭矩 |
对比 | 0.20% | 7.2分钟 | 0.34dNm | 2.8dNm |
发明A | 0.20% | 11.1分钟 | 0.25dNm | 2.6dNm |
发明A | 0.25% | 17.3分钟 | 0.26dNm | 2.1dNm |
发明A | 0.30% | 19.1分钟 | 0.29dNm | 2.0dNm |
发明B | 0.20% | 9.4分钟 | 0.31dNm | 3.1dNm |
发明B | 0.25% | 10.4分钟 | 0.28dNm | 2.9dNm |
发明B | 0.30% | 13.1分钟 | 0.27dNm | 2.7dNm |
对比=4,4’-硫代双(2-甲基-6-叔丁基苯酚)
发明A=2,4-双(正辛基硫代甲基)-6-甲基苯酚
发明B=80wt%4,4’-二-叔辛基二苯胺和20wt%酚P的混合物。
凝胶含量
不溶物的量一般是获得的交联程度的量度。在90℃下,将确定重量的交联试验样板曝露于溶剂(甲苯、二甲苯或十氢化萘)中24h。通过筛网过滤溶解部分,和将筛网和样品两者用相应溶剂洗涤。其后将两者在真空干燥器中干燥直到获得恒定重量。
根据以下公式确定凝胶含量:
凝胶含量(%)=100(W1-W2)/W3
W1=在真空干燥之后筛网和不溶物的重量
W2=在过滤之前退火的,空筛网重量
W3=聚合物样品的重量。
所有结果(表2)处在对于此种应用希望的典型范围内。
表2
产物 | 填充量 | 凝胶含量(二甲苯) | 凝胶含量(萘烷) |
对比 | 0.20% | 89.3% | 90.9% |
发明A | 0.20% | 89.8% | 91.7% |
发明A | 0.25% | 88.5% | 90.5% |
发明A | 0.30% | 87.6% | 89.6% |
发明B | 0.20% | 91.0% | 92.2% |
发明B | 0.25% | 89.8% | 91.1% |
发明B | 0.30% | 88.8% | 90.7% |
对比=4,4’-硫代双(2-甲基-6-叔丁基苯酚)
发明A=2,4-双(正辛基硫代甲基)-6-甲基苯酚
发明B=80wt%4,4’-二-叔辛基二苯胺和20wt%酚P的混合物。
热老化和机械测试
从交联试验样板冲压出拉伸棒(尺寸根据DIN 53-504-82)和将拉伸棒分成四组在150℃下老化0,3,10和14天。评价拉伸棒的拉伸强度和伸长(屈服;断裂)的保留情况。所有结果(表3和4)在用于此种应用的希望的典型范围内。
表3
产物 | 填充量 | 交联后的拉伸强度 | 在150℃/10天热老化之后保留的拉伸强度 | 在150℃/14天热老化之后保留的拉伸强度 |
对比 | 0.20% | 21.7MPa | 18.9Mpa | 17.5Mpa |
发明A | 0.20% | 20.5Mpa | 17.1Mpa | 17.6Mpa |
发明A | 0.25% | 20.7Mpa | 18.1Mpa | 18.8Mpa |
发明A | 0.30% | 21.9Mpa | 20.0Mpa | 18.9Mpa |
发明B | 0.20% | 21.2Mpa | 17.6Mpa | 16.5Mpa |
发明B | 0.25% | 20.4Mpa | 18.0Mpa | 19.2Mpa |
发明B | 0.30% | 19.9MPa | 18.2MPa | 17.6Mpa |
表4
产物 | 填充量 | 交联后的伸长 | 在150℃/10天热老化之后保留的伸长 | 在150℃/14天热老化之后保留的伸长 |
对比 | 0.20% | 478% | 486% | 479% |
发明A | 0.20% | 457% | 461% | 466% |
发明A | 0.25% | 465% | 474% | 485% |
发明A | 0.30% | 486% | 499% | 494% |
发明B | 0.20% | 475% | 461% | 459% |
发明B | 0.25% | 470% | 470% | 485% |
发明B | 0.30% | 458% | 476% | 471% |
对比=4,4’-硫代双(2-甲基-6-叔丁基苯酚)
发明A=2,4-双(正辛基硫代甲基)-6-甲基苯酚
发明B=80wt%4,4’-二-叔辛基二苯胺和20wt%酚P的混合物。
降低的稳定剂渗出
和固体体系相比,检验液体体系的表现情况。稳定剂向聚合物表面的高迁移倾向可引起各种问题,如活性自由基清除剂的损失和粘性表面,该表面在贮存期间将颗料结块在一起。也已知稳定剂和过氧化物的渗出对挤出工艺和电缆产品有负面影响,和渗出粉尘可淤塞过滤器和引起挤出工艺中的滑移和不稳定性。
实施例比较了在55℃下老化之后,不同体系的透出和渗出行为。发明A和发明B两者显示了在与聚合物相容性方面显著的改进。这样提供了进一步使转化器增加添加剂填充量的可能性,如果合适,特别是需要更高的耐焦烧性而不希望严重的渗出问题时。
在55℃下将每种配制剂保持在烘箱中,以模拟抗氧剂起霜。在合适的收回间隔下,从烘箱中取出等分试样和测量表面渗出。采用二氯甲烷洗涤样品(与聚合物接触约15秒)和然后将溶液转移到圆底烧瓶中和蒸发到干燥。将获得的残余物采用标准溶液重新配制和通过液相色谱定量分析。
表5
产物 | 填充量 | 7天之后渗出的稳定剂的份数/百万份 |
对比 | 0.20% | 1430 |
发明A | 0.20% | 30 |
发明A | 0.25% | 40 |
发明A | 0.30% | 50 |
发明B | 0.20% | 50 |
发明B | 0.25% | 60 |
发明B | 0.30% | 60 |
对比=4,4’-硫代双(6-叔丁基-3-甲基苯酚)
发明A=2,4-双(正辛基硫代甲基)-6-甲基苯酚
发明B=80wt%4,4’-二-叔辛基二苯胺和20wt%酚P的混合物。
本发明的另外优选实施方案涉及上述焦烧抑制剂在防止从基材敷霜(透出或渗出)中的用途。
Claims (8)
1.一种组合物,其包括:
(a)聚乙烯,
(b)在大气压下熔点低于50℃的焦烧抑制剂,该焦烧抑制剂是通式I的化合物
其中
R1是C1-20烷基或被苯基取代的C1-20烷基、C2-20烯基、C3-20炔基、C5-9环烷基、苯基或甲苯基;
R2和R3每个彼此独立地是C1-20烷基或被以下基团取代的C1-20烷基:苯基、一个或两个羟基、氰基、甲酰基、乙酰基、-O-COR5;
R5是C1-20烷基;C2-20烯基;C3-20炔基;C5-7环烷基或被羟基取代的C5-7环烷基;苯基、4-氯苯基、2-甲氧基羰基苯基、对甲苯基、1,3-苯并噻唑-2-基、或-(CHR6)nCOOR7或-(CHR6)nCONR8R9,其中
n是1或2,
R6是氢或C1-6烷基,
R7是C1-20烷基、被1-5个O或S间隔的C1-20烷基、C5-7环烷基、苯基、苄基、甲苯基,
R8和R9是氢或C1-6烷基;
R4是氢或甲基;和
(c)有机过氧化物,
该组合物不含空间位阻胺和并非式I化合物的另一种酚型抗氧化剂。
2.根据权利要求1的组合物,其中
R1是C1-20烷基,和
R2和R3相同,是C1-20烷基或被一个或两个羟基取代的C1-20烷基。
3.根据权利要求1的组合物,其中通式I的焦烧抑制剂是2,4-双(正辛基硫代甲基)-6-甲基苯酚或2,4-双(正十二烷基硫代甲基)-6-甲基苯酚。
4.根据权利要求1的组合物,其中该混合物另外包含选自如下的胺:二苯胺、4-叔丁基二苯胺、4-叔辛基二苯胺、4,4’-二-叔丁基二苯胺、2,4,4’-三-叔丁基二苯胺、4-叔丁基-4’-叔辛基二苯胺、o,o’-,m,m’-或p,p’-二-叔辛基二苯胺、2,4-二-叔丁基-4’-叔辛基二苯胺、4,4’-二-叔辛基二苯胺、2,4-二-叔辛基-4’-叔丁基二苯胺。
5.根据权利要求4的组合物,其中胺是4,4’-二-叔辛基二苯胺或胺(A),胺(A)是如下物质的混合物:3wt%二苯胺、14wt%的4-叔丁基二苯胺、30wt%的(4-叔辛基二苯胺、4,4’-二-叔丁基二苯胺和2,4,4’-三-叔丁基二苯胺)、29wt%(4-叔丁基-4’-叔辛基二苯胺、o,o’-,m,m’-或p,p’-二-叔辛基二苯胺和2,4-二-叔丁基-4’-叔辛基二苯胺)、18wt%的4,4’-二-叔辛基二苯胺和6wt%的2,4-二-叔辛基-4’-叔丁基二苯胺。
6.根据权利要求1的组合物,其中焦烧抑制剂的量为0.01-1wt%,过氧化物的量为0.5-5wt%。
7.一种交联聚乙烯组合物的制备方法,其中将聚乙烯或聚乙烯/过氧化物共混物引入到挤出机中,并将权利要求1定义的熔点低于50℃的焦烧抑制剂,或将该焦烧抑制剂和过氧化物加入到该挤出机中,然后通过将挤出物曝露于高于有机过氧化物分解温度的温度下而使挤出物交联。
8.根据权利要求1的组合物作为中电压和高电压电缆的电缆绝缘材料的用途。
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SK287686B6 (sk) | 2011-06-06 |
SK4702002A3 (en) | 2002-11-06 |
CA2380987C (en) | 2011-03-15 |
US20020198344A1 (en) | 2002-12-26 |
BR0201173A (pt) | 2003-06-10 |
AU784703B2 (en) | 2006-06-01 |
MXPA02003611A (es) | 2002-11-07 |
SG103854A1 (en) | 2004-05-26 |
NO20021657D0 (no) | 2002-04-08 |
KR100923284B1 (ko) | 2009-10-23 |
NO20021657L (no) | 2002-10-11 |
US7056967B2 (en) | 2006-06-06 |
JP2002363351A (ja) | 2002-12-18 |
CN1381522A (zh) | 2002-11-27 |
JP4051667B2 (ja) | 2008-02-27 |
CZ20021236A3 (cs) | 2002-11-13 |
NO333375B1 (no) | 2013-05-13 |
CA2380987A1 (en) | 2002-10-10 |
CZ305019B6 (cs) | 2015-04-01 |
BR0201173B1 (pt) | 2012-01-10 |
MY133253A (en) | 2007-10-31 |
AR033211A1 (es) | 2003-12-10 |
AU3299802A (en) | 2002-10-17 |
KR20020079525A (ko) | 2002-10-19 |
TWI239019B (en) | 2005-09-01 |
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