JPH04118808A - Highly water-tree resistant ethylene-based polymer or ethylene-based polymer composition and power cable using it - Google Patents
Highly water-tree resistant ethylene-based polymer or ethylene-based polymer composition and power cable using itInfo
- Publication number
- JPH04118808A JPH04118808A JP23781190A JP23781190A JPH04118808A JP H04118808 A JPH04118808 A JP H04118808A JP 23781190 A JP23781190 A JP 23781190A JP 23781190 A JP23781190 A JP 23781190A JP H04118808 A JPH04118808 A JP H04118808A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- weight
- based polymer
- copolymer
- polymer composition
- 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.)
- Pending
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000005977 Ethylene Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 240000005572 Syzygium cordatum Species 0.000 title abstract description 12
- 235000006650 Syzygium cordatum Nutrition 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 18
- 125000000468 ketone group Chemical group 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims description 33
- 125000002560 nitrile group Chemical group 0.000 claims description 10
- 239000012212 insulator Substances 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 2
- 125000004185 ester group Chemical group 0.000 claims 2
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 16
- 238000009413 insulation Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 55
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 45
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 43
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 24
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 24
- 239000010410 layer Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 150000002148 esters Chemical group 0.000 description 10
- 238000010292 electrical insulation Methods 0.000 description 7
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 5
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- CFEYBLWMNFZOPB-UHFFFAOYSA-N pent-4-enenitrile Chemical compound C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- VKVLTUQLNXVANB-UHFFFAOYSA-N 1-ethenyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=C VKVLTUQLNXVANB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- NKKMVIVFRUYPLQ-NSCUHMNNSA-N crotononitrile Chemical compound C\C=C\C#N NKKMVIVFRUYPLQ-NSCUHMNNSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- RKJGQMJOEDIVQQ-UHFFFAOYSA-N (2,4-dinitrophenyl) prop-2-enoate Chemical compound [O-][N+](=O)C1=CC=C(OC(=O)C=C)C([N+]([O-])=O)=C1 RKJGQMJOEDIVQQ-UHFFFAOYSA-N 0.000 description 1
- UTISFCFKPMKVKR-UHFFFAOYSA-N (3-nitrophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC([N+]([O-])=O)=C1 UTISFCFKPMKVKR-UHFFFAOYSA-N 0.000 description 1
- LABTWGUMFABVFG-ONEGZZNKSA-N (3E)-pent-3-en-2-one Chemical compound C\C=C\C(C)=O LABTWGUMFABVFG-ONEGZZNKSA-N 0.000 description 1
- NACSMDAZDYUKMU-UHFFFAOYSA-N (4-nitrophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C([N+]([O-])=O)C=C1 NACSMDAZDYUKMU-UHFFFAOYSA-N 0.000 description 1
- ZYBPSQSGQRMLDY-MBXJOHMKSA-N (e)-2-phenylbut-2-enenitrile Chemical compound C\C=C(\C#N)C1=CC=CC=C1 ZYBPSQSGQRMLDY-MBXJOHMKSA-N 0.000 description 1
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- WXOZSJIRHYARIF-UHFFFAOYSA-N 1-cyclohexylprop-2-en-1-one Chemical compound C=CC(=O)C1CCCCC1 WXOZSJIRHYARIF-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 1
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 1
- LABTWGUMFABVFG-UHFFFAOYSA-N 1-propenyl methyl ketone Natural products CC=CC(C)=O LABTWGUMFABVFG-UHFFFAOYSA-N 0.000 description 1
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical group COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- PEIBTJDECFEPAF-UHFFFAOYSA-N 2-methoxyprop-2-enenitrile Chemical compound COC(=C)C#N PEIBTJDECFEPAF-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- XVTXLKJBAYGTJS-UHFFFAOYSA-N 2-methylpenta-1,4-dien-3-one Chemical compound CC(=C)C(=O)C=C XVTXLKJBAYGTJS-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- MUOKXXOKLLKNIE-UHFFFAOYSA-N 4,4-dimethylpent-1-en-3-one Chemical compound CC(C)(C)C(=O)C=C MUOKXXOKLLKNIE-UHFFFAOYSA-N 0.000 description 1
- SNOYUTZWILESAI-UHFFFAOYSA-N 4-methylpent-1-en-3-one Chemical compound CC(C)C(=O)C=C SNOYUTZWILESAI-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- ZBGRMWIREQJHPK-UHFFFAOYSA-N ethenyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC=C ZBGRMWIREQJHPK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は耐水トリー性、電気絶縁性に優れるエチレン系
重合体または該エチレン系重合体組成物およびこれを用
いた高圧電カケ−プルに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ethylene polymer or an ethylene polymer composition having excellent water resistance and electrical insulation properties, and a high voltage electric cable using the same.
更に詳しくは、水トリーの発生を防止し、かつ電気絶縁
性も高いエチレン系重合体または該エチレン系重合体組
成物、およびこれを用いた高圧電カケ−プルに関するも
のである。More specifically, the present invention relates to an ethylene polymer or an ethylene polymer composition that prevents the occurrence of water trees and has high electrical insulation properties, and a high-voltage electric cable using the same.
［従来技術］
従来、高圧電カケ−プル用絶縁体としては高圧法ポリエ
チレンや架橋ポリエチレンが電気特性に優れているため
広く用いられている。[Prior Art] Hitherto, high-voltage polyethylene and cross-linked polyethylene have been widely used as insulators for high-voltage electric cables because of their excellent electrical properties.
しかし、ポリエチレンや架橋ポリエチレンを用いた高圧
電カケ−プルは長期にわたり使用されると水トリーの発
生などにより絶縁破壊が起こるため改良が求められてい
る。However, when high-voltage electrical cables made of polyethylene or cross-linked polyethylene are used for a long period of time, dielectric breakdown occurs due to water trees, etc., so improvements are needed.
また、高圧電カケ−プルの重要課題として高圧送電中の
電力損失が挙げられるが、この電力損失の低減は絶縁材
の電気絶縁抵抗を高めることにより達成することができ
るため、電気絶縁抵抗の低下を防ぐことが望まれている
。In addition, power loss during high-voltage power transmission is an important issue for high-voltage electrical cables, and reduction of this power loss can be achieved by increasing the electrical insulation resistance of the insulating material. It is desired to prevent
上記問題点を改良するため種々の方法が試みられている
。Various methods have been attempted to improve the above problems.
例えば、ポリエチレンに対して、エチレンと酢酸ビニル
（ＶＡ）の共重合体であるエチレン−酢酸ビニル共重合
体（ＥＶＡ）、エチレンとエチルアクリレート（ＥＡ）
の共重合体であるエチレン−エチルアクリレート共重合
体（ＥＥＡ）などの極性ポリマーをブレンドする方法が
ある。For example, for polyethylene, ethylene-vinyl acetate copolymer (EVA), which is a copolymer of ethylene and vinyl acetate (VA), and ethylene and ethyl acrylate (EA)
There is a method of blending polar polymers such as ethylene-ethyl acrylate copolymer (EEA), which is a copolymer of
この方法によれば、ミクロボイドおよび異物部分より生
ずる水トリー（ボウタイ状トリー）の発生が抑制される
結果が得られているが、一方、極性基の導入によって電
気絶縁抵抗が低下する欠点がある。According to this method, the generation of water trees (bowtie-like trees) generated from microvoids and foreign matter parts has been suppressed, but on the other hand, there is a drawback that electrical insulation resistance is reduced due to the introduction of polar groups.
［本発明が解決しようとする課題］
本発明は、上記問題点に鑑み鋭意検討した結果なされた
ものであって、その第１目的は、電気絶縁性を低下させ
ずに水トリーの発生を防止したエチレン系重合体または
該エチレン系重合体組成物を提供するものであり、第２
目的は、それを絶縁体として用いたことを特徴とする高
圧電カケ−プルを提供するものである。[Problems to be Solved by the Present Invention] The present invention was developed as a result of intensive studies in view of the above-mentioned problems, and its first purpose is to prevent the occurrence of water trees without reducing electrical insulation properties. The present invention provides an ethylene polymer or a composition of the ethylene polymer, and a second
The object of the present invention is to provide a high voltage electrical cable characterized by using the same as an insulator.
［課題を解決するための手段］
本発明の第１発明は、
次の（ａ）、（ｂ）、（ｃ）からなるエチレン系重合体
または該エチレン系重合体組成物である。[Means for Solving the Problems] A first aspect of the present invention is an ethylene polymer or an ethylene polymer composition comprising the following (a), (b), and (c).
（ａ）エチレン単位 ８９．２〜９８．９９８重量
％（ｂ）不飽和カルボン酸エステルおよび／またはビニ
ルエステル単位 １〜Ｉｏ ｆｒ１％（ｃ）ケ
トン基、ニトリル基、ニトロ基を含む単量体からなる群
から選ばれる少なくとも一種の極性基単位
０．００２〜０．８重量％本発明の第２発明は、
次の（ａ）、（ｂ）、（ｃ）からなるエチレン系重合体
または該エチレン系重合体組成物を絶縁体として用いた
ことを特徴とする電力ケーブルである。(a) Ethylene units 89.2 to 98.998% by weight (b) Unsaturated carboxylic acid ester and/or vinyl ester units 1 to Io fr1% (c) From monomers containing ketone groups, nitrile groups, and nitro groups at least one polar group unit selected from the group
0.002 to 0.8% by weight The second invention of the present invention uses an ethylene polymer or the ethylene polymer composition consisting of the following (a), (b), and (c) as an insulator. This is a power cable that is characterized by:
（ａ）エチレン単位 ８９．２〜Ｈ，９９８重量％
（ｂ）不飽和カルボン酸エステルおよび／またはビニル
エステル単位 １〜１０重量％（ｃ）ケトン基
、ニトリル基、ニトロ基を含む単量体からなる群から選
ばれる少なくとも一種の極性基単位 ０
．００２〜０．８重量％以下本発明を詳述する。(a) Ethylene unit 89.2-H, 998% by weight
(b) Unsaturated carboxylic acid ester and/or vinyl ester unit 1 to 10% by weight (c) At least one polar group unit selected from the group consisting of monomers containing a ketone group, a nitrile group, and a nitro group 0
．． 002 to 0.8% by weight or less The present invention will be described in detail.
本発明者等は、エチレン単位に非常に少量の不飽和カル
ボン酸エステルおよび／またはビニルエステル単位、お
よび特定の極性基単位をランダムに含むエチレン系重合
体が、驚くべきことに、電気絶縁抵抗を犠牲にすること
なく、かつ水トリーも防止されることを見いだし本発明
をなすに至った。The present inventors have surprisingly demonstrated that an ethylene polymer randomly containing a very small amount of unsaturated carboxylic acid ester and/or vinyl ester units and specific polar group units in the ethylene unit has a high electrical insulation resistance. It was discovered that water trees can be prevented without any sacrifice, and the present invention was completed.
本発明で使用する（ｂ）成分の不飽和カルボン酸エステ
ル単位はα、β−不飽和カルボン酸エステルから誘導さ
れる単位であり、その具体的な例としでは、アクリル酸
メチル、メタクリル酸メチル、アクリル酸エチル、メタ
クリル酸エチル、アクリル酸プロピル、メタクリル酸プ
ロピル、アクリル酸イソプロピル、メタクリル酸イソプ
ロピル、アクリル酸−ｎ−ブチル、メタクリル酸−ｎ−
ブチル、アクリル酸シクロヘキシル、メタクリル酸シク
ロヘキシル、アクリル酸ラウリル、メタクリル酸ラウリ
ル、アクリル酸ステアリル、メタクリル酸ステアリル、
マレイン酸モノメチルエステル、マレイン酸モノエチル
エステル、マレイン酸ジエチルエステル、フマル酸モノ
メチルエステル、アクリル酸グリシジル、メタクリル酸
グリシジル等の不飽和カルボン酸エステル類を挙げるこ
とができる。この中でも特に好ましいものとして（メタ
）アクリル酸アルキルエステルを挙げることができる。The unsaturated carboxylic acid ester unit of component (b) used in the present invention is a unit derived from α,β-unsaturated carboxylic acid ester, and specific examples thereof include methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-methacrylate
Butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Examples include unsaturated carboxylic acid esters such as monomethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, glycidyl acrylate, and glycidyl methacrylate. Among these, (meth)acrylic acid alkyl esters are particularly preferred.
更に好ましくはアクリル酸メチルやアクリル酸エチルを
挙げることができる。More preferred are methyl acrylate and ethyl acrylate.
本発明で使用する（ｂ）成分のビニルエステル単位を誘
導する具体的な単量体の例としては、プロピオン酸ビニ
ル、酢酸ビニル、カプロン酸ビ二ル、カプリル酸ビニル
、ラウリル酸ビニル、ステアリン酸ビニル、トリフルオ
ル酢酸ビニルなどのビニルエステル単量体を挙げること
ができる。これらの中でも特に好ましいものとしては、
酢酸ビニルを挙げることができる。Examples of specific monomers for inducing the vinyl ester unit of component (b) used in the present invention include vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, and stearic acid. Vinyl ester monomers such as vinyl and vinyl trifluoroacetate can be mentioned. Among these, particularly preferable ones are:
Vinyl acetate may be mentioned.
本発明で使用する（ｂ）成分の不飽和カルボン酸エステ
ルおよび／またはビニルエステル単位の含有量は１−１
０重量％である。含を量が１重量％以下であると効果が
少なく、１０重量％以上であると絶縁性が悪化するので
好ましくない。The content of unsaturated carboxylic acid ester and/or vinyl ester units of component (b) used in the present invention is 1-1
It is 0% by weight. If the amount is less than 1% by weight, the effect will be small, and if it is more than 10% by weight, the insulation will deteriorate, which is not preferable.
本発明で使用する（ｃ）成分はケトン基、ニトリル基、
ニトロ基を含む単量体からなる群から選ばれる少なくと
も一種の極性基単位である。しかし、その中でもケトン
基、ニトリル基等が好ましい。Component (c) used in the present invention is a ketone group, a nitrile group,
At least one polar group unit selected from the group consisting of monomers containing a nitro group. However, among these, ketone groups, nitrile groups, etc. are preferred.
本発明で使用しうる（ｃ）成分の極性基単位を誘導する
単量体としては、−酸化炭素、メチルビニルケトン、イ
ソプロペニルビニルケトン、エチルビニルケトン、フェ
ニルビニルケトン、ｔ−ブチルビニルケトン、イソプロ
ピルビニルケトン、メチルプロペニルケトン、メチルイ
ソプロペニルケトン、シクロヘキシルビニルケトン、ア
クリロニトリル、メタアクリロニトリル、α−メトキシ
アクリロニトリル、ビニリデンシアニド、シナモニトリ
ル、クロトノニトリル、α−フェニルクロトノニトリル
、フマロニトリル、アリルアセトニトリル、２−ブテン
ニトリル、３−ブテンニトリル、２．４−ジニトロフェ
ニルアクリレート、２−ニトロスチレン、ｍ−ニトロス
チレン、Ｏ−ニトロスチレン、ｐ−ニトロスチレン、ｐ
−ニトロフェニルメタクリレート、ｍ−ニトロフェニル
メタクリレ−）、２．４−ジニトロフェニルメタクリレ
−）、２．４．８−）リニトロフェニルメタクリレート
等を挙げることができる。Monomers for inducing the polar group unit of component (c) that can be used in the present invention include -carbon oxide, methyl vinyl ketone, isopropenyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, t-butyl vinyl ketone, Isopropyl vinyl ketone, methyl propenyl ketone, methyl isopropenyl ketone, cyclohexyl vinyl ketone, acrylonitrile, methacrylonitrile, α-methoxyacrylonitrile, vinylidene cyanide, cinnamonitrile, crotononitrile, α-phenylcrotononitrile, fumaronitrile, allyl acetonitrile, 2-butenenitrile, 3-butenenitrile, 2,4-dinitrophenyl acrylate, 2-nitrostyrene, m-nitrostyrene, O-nitrostyrene, p-nitrostyrene, p
-nitrophenyl methacrylate, m-nitrophenyl methacrylate), 2.4-dinitrophenyl methacrylate), 2.4.8-) linitrophenyl methacrylate, and the like.
本発明における、ケトン基、ニトリル基、ニトロ基など
の極性基単位を０．００２〜０．８重量％含むエチレン
系重合体の該極性基単位の含有量が０．００２重量％以
下であると極性基としての効果が少なく、０．８重量％
以上であると絶縁性が悪化するので好ましくない。In the present invention, the content of polar group units such as ketone groups, nitrile groups, nitro groups, etc. in the ethylene polymer containing 0.002 to 0.8 weight% of polar group units is 0.002% by weight or less. Less effective as a polar group, 0.8% by weight
If it is more than that, the insulation properties will be deteriorated, which is not preferable.
本発明のエチレン系重合体である、不飽和カルボン酸エ
ステルおよび／またはビニルエステル単位、詔よび該極
性基単位を誘導する単量体とエチレンとの共重合体の具
体例としては、エチレン／ＶＡ／−酸化炭素共重合体、
エチレン／ＶＡ／メチルビニルケトン共重合体、エチレ
ン／ＶＡ／エチルビニルケトン共重合体、エチレン／Ｖ
Ａ／アクリロニトリル共重合体、エチレン／’ＶＡ／メ
タアクリロニトリル共重合体、エチレン／ＶＡ／アリル
アセトニトリル共重合体、エチレン／ＶＡ／２−ニトロ
スチレン共重合体、エチレン／ＶＡ／ｍ−二トロスチレ
ン共重合体、エチレン／ＶＡ／ｐ−ニトロフェニルメタ
クリレート共重合体、エチレン／ＶＡ／メチルイソプロ
ペニルケトン共重合体等、エチレン／ＥＡ／−酸化炭素
共重合体、エチレン／ＥＡ／メチルビニルケトン共重合
体、エチレン／ＥＡ／エチルビニルケトン共重合体、エ
チレン／ＥＡ／アクリロニトリル共重合体、エチレン／
ＥＡ／メタアクリロニトリル共重合体、エチレン／ＥＡ
／アリルアセトニトリル共重合体、エチレン／ＥＡ／２
−二トロスチレン共重合体、エチレン／ＥＡ／ｍ−ニト
ロスチレン共重合体、エチレン／Ｅ Ａ／１）−二トロ
フェニルメタクリレート共重合体、エチレン／ＥＡ／メ
チルイソプロペニルケトン共重合体等、エチレン／ＶＡ
／ＥＡ／−酸化炭素共重合体、エチレン／ＶＡ／ＥＡ／
メチルビニルケトン共重合体、エチレン／ＶＡ／ＥＡ／
エチルビニルケトン共重合体、エチレン／ＶＡ／ＥＡ／
アクリロニトリル共重合体、エチレン／ＶＡ／ＥＡ／メ
タアクリロニトリル共重合体、エチレン／ＶＡ／ＥＡ／
アリルアセトニトリル共重合体、エチレン／ＶＡ／ＥＡ
／２−二トロスチレン共重合体、エチレン／ＶＡ／ＥＡ
／ｍ−二トロスチレン共重合体、エチレン／ＶＡ／ＥＡ
／ｐ−ニトロフェニルメタクリレート共重合体、エチレ
ン／ＶＡ／ＥＡ／メチルイソプロペニルケトン共重合体
等を挙げることができる。Specific examples of copolymers of ethylene and monomers that induce unsaturated carboxylic acid ester and/or vinyl ester units, and polar group units, which are the ethylene polymers of the present invention, include ethylene/VA /-carbon oxide copolymer,
Ethylene/VA/methyl vinyl ketone copolymer, ethylene/VA/ethyl vinyl ketone copolymer, ethylene/V
A/acrylonitrile copolymer, ethylene/VA/methacrylonitrile copolymer, ethylene/VA/allylacetonitrile copolymer, ethylene/VA/2-nitrostyrene copolymer, ethylene/VA/m-nitrostyrene copolymer Polymers, ethylene/VA/p-nitrophenyl methacrylate copolymers, ethylene/VA/methyl isopropenyl ketone copolymers, etc., ethylene/EA/-carbon oxide copolymers, ethylene/EA/methyl vinyl ketone copolymers , ethylene/EA/ethyl vinyl ketone copolymer, ethylene/EA/acrylonitrile copolymer, ethylene/
EA/methacrylonitrile copolymer, ethylene/EA
/allylacetonitrile copolymer, ethylene/EA/2
- Nitrostyrene copolymer, ethylene/EA/m-nitrostyrene copolymer, ethylene/EA/1)-nitrophenyl methacrylate copolymer, ethylene/EA/methyl isopropenyl ketone copolymer, etc. /VA
/EA/-carbon oxide copolymer, ethylene/VA/EA/
Methyl vinyl ketone copolymer, ethylene/VA/EA/
Ethyl vinyl ketone copolymer, ethylene/VA/EA/
Acrylonitrile copolymer, ethylene/VA/EA/methacrylonitrile copolymer, ethylene/VA/EA/
Allyl acetonitrile copolymer, ethylene/VA/EA
/2-nitrostyrene copolymer, ethylene/VA/EA
/m-nitrostyrene copolymer, ethylene/VA/EA
/p-nitrophenyl methacrylate copolymer, ethylene/VA/EA/methyl isopropenyl ketone copolymer, and the like.
不飽和カルボン酸エステル単量体および／またはビニル
エステル単量体、および該極性基を有する単量体とエチ
レンとを共重合させるに際しては他の不飽和単量体を必
要に応じてさらに共重合させることができる。When copolymerizing an unsaturated carboxylic acid ester monomer and/or vinyl ester monomer, and the monomer having a polar group with ethylene, other unsaturated monomers may be further copolymerized as necessary. can be done.
該他の不飽和単量体の一例としては、プロピレン、゛ブ
テンー１、ヘキセン−１、デセン−１、オクテン−１、
スチレン等のオレフィン類が挙げられる。Examples of the other unsaturated monomers include propylene, butene-1, hexene-1, decene-1, octene-1,
Examples include olefins such as styrene.
本発明のエチレン共重合体を製造する好ましい方法とし
て、触媒残渣として金属化合物が残らず、電気特性に悪
影響を与えないとされる高圧ラジカル重合法が挙げられ
る。A preferred method for producing the ethylene copolymer of the present invention is a high-pressure radical polymerization method, which does not leave any metal compound as a catalyst residue and is said to have no adverse effect on electrical properties.
該高圧ラジカル重合法は、例えばエチレン８９．２〜９
８．１１９８重量％、不飽和カルボン酸エステル単量体
および／またはビニルエステル単量体１〜ｌＯ重量％お
よび該極性基含有単量体０゜００２〜０．８重量％の単
量体混合物を、それらの全単量体の総重量に基づいて０
．０００１〜１重量％のラジカル重合開始剤の存在下で
重合圧力５００〜４０００ｋｇ／ｃｌＩ２、好ましくは
１０００〜３５００ｋｇ／ｃｍ”、反応温度５０〜４０
０℃、好ましくは１００〜３５０℃の条件下、連鎖移動
剤、必要に応じて助剤の存在下に種型または管空反応器
内で該単量体を同時に、あるいは段階的に接触、重合さ
せる方法である。The high-pressure radical polymerization method uses, for example, ethylene 89.2 to 9
8. A monomer mixture of 1198% by weight, 1 to 10% by weight of unsaturated carboxylic acid ester monomer and/or vinyl ester monomer, and 0°002 to 0.8% by weight of the polar group-containing monomer. , based on the total weight of all their monomers
．． 0001 to 1% by weight of a radical polymerization initiator, a polymerization pressure of 500 to 4000 kg/clI2, preferably 1000 to 3500 kg/cm, and a reaction temperature of 50 to 40%.
The monomers are contacted and polymerized simultaneously or in stages at 0°C, preferably from 100 to 350°C, in the presence of a chain transfer agent and optionally an auxiliary agent in a seed type or tube reactor. This is the way to do it.
上記ラジカル重合開始剤としては、ペルオキシド、ヒド
ロペルオキシド、アゾ化合物、アミンオキシド化合物、
酸素などの通例の開始剤が挙げられる。Examples of the radical polymerization initiators include peroxides, hydroperoxides, azo compounds, amine oxide compounds,
Common initiators such as oxygen may be mentioned.
また連鎖移動剤としては、水素、プロピレン、ブテン−
ＬＣＩ＃Ｃ２０またはそれ以上の飽和脂肪族炭化水素お
よびハロゲン置換炭化水素、例えばメタン、エタン、プ
ロパン、ブタン、イソブタン、ｎ−ヘキサン、ｎ−へブ
タン、シクロパラフィン類、クロロホルム、および四塩
化炭素、芳香族化合物、例えばトルエン、ジエチルベン
ゼンおよびキシレンのような化合物等が挙げられる。In addition, as a chain transfer agent, hydrogen, propylene, butene-
Saturated aliphatic and halogenated hydrocarbons with LCI #C20 or higher, such as methane, ethane, propane, butane, isobutane, n-hexane, n-hebutane, cycloparaffins, chloroform, and carbon tetrachloride, aromatic Examples include compounds such as toluene, diethylbenzene and xylene.
本発明のエチレン系重合体を製造するもう一つの方法に
従来のエチレン単独重合体または共重合体に前記の極性
基を有する単量体や、不飽和カルボン酸エステル単量体
および／またはビニルエステル単量体をグラフト反応さ
せる方法がある。Another method for producing the ethylene polymer of the present invention is to add monomers having the above-mentioned polar groups, unsaturated carboxylic acid ester monomers and/or vinyl esters to conventional ethylene homopolymers or copolymers. There is a method of grafting monomers.
上記エチレン単独または共重合体には、低密度、中密度
ポリエチレンなどの単独重合体、エチレン／プロピレン
共重合体、エチレン／ブテン−１共重合体、エチレン／
ヘキセン−１共重合体、エチレン／４−メチルペンテン
−１共重合体、エチレン／オクテン−１共重合体などの
エチレンを主成分とする他のα−オレフィンとの共重合
体およびこれらの混合物を用いることができる。The above ethylene homopolymers or copolymers include homopolymers such as low density and medium density polyethylene, ethylene/propylene copolymers, ethylene/butene-1 copolymers, and ethylene/butene-1 copolymers.
Copolymers containing ethylene as a main component with other α-olefins, such as hexene-1 copolymer, ethylene/4-methylpentene-1 copolymer, ethylene/octene-1 copolymer, and mixtures thereof. Can be used.
該グラフト法は、一般に良く知られている、有機過酸化
物等の架橋剤などの存在下に無溶媒または溶媒中でグラ
フト変性するなどの連鎖移動法、電離放射線照射などい
ずれの方法によってもよい。The grafting method may be carried out by any of the generally well-known methods, such as a chain transfer method such as graft modification without a solvent or in a solvent in the presence of a crosslinking agent such as an organic peroxide, or irradiation with ionizing radiation. .
架橋剤としては、ヒドロペルオキシド、ジアルキルペル
オキシド、ジアシルペルオキシド、ペルオキシエステル
、ケトンペルオキシド等の有機過酸化物、ジヒドロ芳香
族化合物、硫黄等の加硫剤を挙げることができる。Examples of crosslinking agents include organic peroxides such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, and ketone peroxides, dihydroaromatic compounds, and vulcanizing agents such as sulfur.
該極性基を含む単量体のグラフト量は樹脂成分に対して
０．００２〜０．８重量％であることが肝要である。It is important that the amount of the monomer containing the polar group grafted is 0.002 to 0.8% by weight based on the resin component.
本発明のエチレン系重合体組成物とは、該極性基を有す
るエチレン（共）重合体とエチレン単独重合体または共
重合体をブレンドしたもの、該極性基を有する重合体を
所定量該エチレン単独重合体または共重合体にブレンド
したものを包含するものである。The ethylene polymer composition of the present invention refers to a blend of the ethylene (co)polymer having the polar group and an ethylene homopolymer or copolymer, and a predetermined amount of the ethylene polymer having the polar group. This includes blends with polymers or copolymers.
具体的には、（ａ）エチレン単位、（ｂ）不飽和カルボ
ン酸エステルおよび／またはビニルエステル単位および
（ｃ）ケトン基、ニトリル基、ニトロ基を含む単量体か
らなる群から選ばれる少なくとも一種の極性基単位を含
む三元共重合体をエチレン単独重合体にブレンドしたり
、あるいは（ａ）Ｘチレン単位と（ｂ）不飽和カルボン
酸エステルおよび／またはビニルエステル単位とを含む
二元共重合体と、（ａ）エチレン単位と（ｃ）ケトン基
、ニトリル基、ニトロ基を含む単量体からなる群から選
ばれる少なくとも一種の極性基単位を含む二元共重合体
とをブレンドするなどによって作ってもよい。Specifically, at least one member selected from the group consisting of (a) ethylene units, (b) unsaturated carboxylic acid ester and/or vinyl ester units, and (c) monomers containing ketone groups, nitrile groups, and nitro groups. A terpolymer containing a polar group unit of is blended with an ethylene homopolymer, or a binary copolymer containing (a) an X tyrene unit and (b) an unsaturated carboxylic acid ester and/or vinyl ester unit. By blending (a) an ethylene unit and (c) a binary copolymer containing at least one polar group unit selected from the group consisting of monomers containing a ketone group, a nitrile group, and a nitro group. You can make it.
然しいずれの場合もブレンド物中の（ａ）エチレン単位
が８９．２〜９８．１１９８重量％、（ｂ）不飽和カル
ボン酸エステル＄よヒ／またはビニルエステル単位が１
〜１０重量％、（ｃ）ケトン基、ニトリル基、ニトロ基
を含む単量体からなる群から選ばれる少なくとも一種の
極性基単位が０．００２〜０．８重量％となることが肝
要である。However, in either case, (a) ethylene units in the blend are 89.2 to 98.1198% by weight, and (b) unsaturated carboxylic acid ester units and/or vinyl ester units are 1% by weight.
It is important that the content of at least one polar group unit selected from the group consisting of monomers containing (c) ketone groups, nitrile groups, and nitro groups is 0.002 to 0.8% by weight. .
、本発明のエチレン系重合体やエチレン系重合体組成物
は通常のクロスヘツドタイプ押出被覆法などにより導体
上に絶縁被覆して電力ケーブルを製造することができる
。この際、内部および外部半導電層を設けるのが好まし
い。The ethylene polymer or ethylene polymer composition of the present invention can be insulated and coated onto a conductor by a conventional crosshead type extrusion coating method to produce a power cable. In this case, it is preferable to provide an inner and an outer semiconducting layer.
本発明では、該エチレン系重合体やエチレン系重合体組
成物に本発明の主旨を逸脱しない範囲において、酸化防
止剤、架橋剤、紫外線吸収剤、顔料、染料、滑剤等を添
加してもよい。In the present invention, antioxidants, crosslinking agents, ultraviolet absorbers, pigments, dyes, lubricants, etc. may be added to the ethylene polymer or ethylene polymer composition without departing from the gist of the present invention. .
上述した本発明のエチレン系重合体またはエチレン系重
合体組成物は、通例の電線・電力ケーブル等の絶縁層と
して使用されるのみでなく、単独または他の合成樹脂、
ゴム等とブレンドされて、フィルムまたはシート、テー
プ、ヤーン等に加工され、必要により他の基材と積層さ
れ、絶縁フィルムやシート、絶縁テープ、絶縁カバー、
絶縁衣等に活用される。The above-mentioned ethylene polymer or ethylene polymer composition of the present invention is not only used as an insulating layer of ordinary electric wires and power cables, but also used alone or with other synthetic resins,
Blended with rubber, etc., processed into films, sheets, tapes, yarns, etc., and laminated with other base materials as necessary to create insulating films, sheets, insulating tapes, insulating covers, etc.
Used for insulation clothing, etc.
本発明の第２発明である電力ケーブルとは、押出しによ
る内部半導電層および／または外部半導電層、あるいは
所望により銅、アルミニウム、鉛等の外部金属遮蔽層や
アルミニウムテープ等を巻回した遮水層等の通例電力ケ
ーブルにおいて設けられる被覆層と共に上記エチレン系
重合体またはエチレン系重合体組成物よりなる絶縁層を
有するものである。The power cable, which is the second aspect of the present invention, includes an extruded inner semiconducting layer and/or outer semiconducting layer, or optionally an outer metal shielding layer made of copper, aluminum, lead, etc., or a shielding layer wrapped with aluminum tape or the like. It has an insulating layer made of the above-mentioned ethylene polymer or ethylene polymer composition together with a coating layer, such as a water layer, which is usually provided in power cables.
該絶縁層は、架橋体、未架橋体のいずれでもよい。The insulating layer may be either a crosslinked or uncrosslinked body.
また、架橋においては、パーオキサイド、イオウ等の架
橋剤または加硫剤等の他、シラン架橋、電子線架橋等の
通例の方法を用いることができる。For crosslinking, in addition to crosslinking agents such as peroxide and sulfur or vulcanizing agents, conventional methods such as silane crosslinking and electron beam crosslinking can be used.
［実施例コ
次に実施例により本発明を更に詳しく説明するが、本発
明はこれらによって限定されるものではない。[Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
第１表に、実施例１としてエチレン／酢酸ビニル（ＶＡ
）／メチルビニルケトン（ＭＶＫ）共重合体（ＶＡ含有
量３重量％、ＭＶＫ含有量０．０２重量％）、実施例２
としてエチレン／酢酸ビニル（ＶＡ）共重合体（ＶＡ含
有量１０重量％）とエチレン／メチルビニルケトン（Ｍ
ＶＫ）共重合体（ＭＶＫ含有量０．０５重量％）とのブ
レンド物（１：１重量比）、実施例３としてエチレン／
酢酸ビニル（ＶＡ）／メチルビニルケトン（ＭＶＫ）共
重合体（ＶＡ含有量１０重量％、ＭＶＫ含有量０．０５
重量％）と低密度ホモポリエチレン（商品名二日石しク
スロンＷ２Ｏ００、日本石油化学（株）製）（ＬＤＰＥ
）とのブレンド物（１；１重量比）、実施例４としてエ
チレン／酢酸ビニル（ＶＡ）／メチルビニルケトン（Ｍ
ＶＫ） 共重合体（ＶＡ含有量１０重量％、ＭＶＫ含育
量０．０２重量％）、実施例５としてエチレン／酢酸ビ
ニル（ＶＡ）／メチルビニルケトン（ＭＶＫ）共重合体
（ＶＡ含有量３重量％、ＭＶＫ含有量０．５重量％）、
比較例１として低密度ホモポリエチレン（商品名＝白石
レクスロンＷ２０００．日本石油化学（株）製）、比較
例２として低密度ホモポリエチレン（商品名＝白石レク
スロンＷ２Ｏ００，日本石油化学（株）製）にエチレン
／酢酸ビニル共重合体（ＥＶＡ）（ＶＡ含有量１５重量
％）をブレンドしてブレンド物のＶＡ含を量を３重量％
としたもの、比較例３としてエチレン／酢酸ビニル（Ｖ
Ａ’）／メチルビニルケトン（ＭＶＫ）共重合体（ＶＡ
含有量１．５重量％、ＭＶＫ含有量０．０５重量％）、
比較例４としてエチレン／酢酸ビニル（ＶＡ）／メチル
ビニルケトン（ＭＶＫ） 共重合体（ＶＡ含有量５重量
％、ＭＶＫ含有量１重量％）、の水トリー発生率、体積
固有抵抗および絶縁破壊電圧の測定結果を示す。Table 1 shows ethylene/vinyl acetate (VA
)/methyl vinyl ketone (MVK) copolymer (VA content 3% by weight, MVK content 0.02% by weight), Example 2
As ethylene/vinyl acetate (VA) copolymer (VA content 10% by weight) and ethylene/methyl vinyl ketone (M
VK) copolymer (MVK content 0.05% by weight) (1:1 weight ratio), as Example 3, ethylene/
Vinyl acetate (VA)/methyl vinyl ketone (MVK) copolymer (VA content 10% by weight, MVK content 0.05
weight%) and low-density homopolyethylene (trade name Nippon Seishi Xuron W2O00, manufactured by Nippon Petrochemical Co., Ltd.) (LDPE
) (1:1 weight ratio), Example 4 was a blend of ethylene/vinyl acetate (VA)/methyl vinyl ketone (M
VK) copolymer (VA content 10% by weight, MVK content 0.02% by weight), Example 5 was an ethylene/vinyl acetate (VA)/methyl vinyl ketone (MVK) copolymer (VA content 3 weight%, MVK content 0.5% by weight), Comparative Example 1 was low-density homopolyethylene (product name = Shiraishi Rexron W2000. manufactured by Nippon Petrochemical Co., Ltd.), Comparative Example 2 was low-density homopolyethylene (product name = Shiraishi Rexron W2O00 (manufactured by Nippon Petrochemical Co., Ltd.) was blended with ethylene/vinyl acetate copolymer (EVA) (VA content 15% by weight) to bring the VA content of the blend to 3% by weight.
and as Comparative Example 3, ethylene/vinyl acetate (V
A')/methyl vinyl ketone (MVK) copolymer (VA
content 1.5% by weight, MVK content 0.05% by weight),
As Comparative Example 4, water tree generation rate, volume resistivity, and dielectric breakdown voltage of ethylene/vinyl acetate (VA)/methyl vinyl ketone (MVK) copolymer (VA content 5% by weight, MVK content 1% by weight) The measurement results are shown below.
［絶縁抵抗、絶縁破壊電圧の測定方法コ第１表に示すエ
チレン系重合体（組成物）を０．３ｍｍ厚のプレスシー
トとし、直流１０００Ｖ印加１０分後の絶縁抵抗を求め
た。[Measurement method of insulation resistance and dielectric breakdown voltage] The ethylene polymer (composition) shown in Table 1 was made into a press sheet with a thickness of 0.3 mm, and the insulation resistance was determined after applying 1000 V DC for 10 minutes.
また、インパルス破壊試験の方法は次の通りである。電
極系には固定電極、いわゆるマ、ケオン電極（第１図）
を使用した。電極系の基板はポリメチルメタクリレート
４製でその中央部には直径１７２インチの穴がおいてい
る。電極は１７２インチのステンレス球１を用いた。試
料２は約８〜１０ｍｍ角に切ったものを電極の間にはさ
んだ。Moreover, the method of the impulse destruction test is as follows. The electrode system includes fixed electrodes, so-called Ma and Keon electrodes (Figure 1).
It was used. The electrode system substrate was made of polymethyl methacrylate 4 and had a 172 inch diameter hole in its center. A 172-inch stainless steel bulb 1 was used as the electrode. Sample 2 was cut into approximately 8 to 10 mm squares and sandwiched between the electrodes.
試料２と電極の間には脱気したエポキシ樹脂３を充てん
し硬化させた。このようなマツケオン電極をシリコンオ
イルで満たされた容器に浸し、恒温槽に入れて測定を行
なった。破壊に用いた電圧波形は負極性％ ｌＸ４０μ
ｓのインパルス波形で、波形をオッシロスコープで観察
し、波頭で破壊したものをデータとして採用し、２０点
以上の平均値を取った。A degassed epoxy resin 3 was filled between the sample 2 and the electrode and cured. The Matsukeon electrode was immersed in a container filled with silicone oil and placed in a constant temperature bath for measurements. The voltage waveform used for destruction was negative polarity% lX40μ
The impulse waveform of s was observed with an oscilloscope, and the data broken at the wave front was used as data, and the average value of 20 points or more was taken.
［水トリー発生率の測定方法〕
７０℃の水中に厚さ３−一のシートを入れて電圧ＳＫＹ
、周波数Ｉ Ｋｌ、の正弦波交流を３２０時間荷電した
後、試料をメチレンブルーで染色し、水トリー数を数え
た。[Measurement method of water tree occurrence rate] A sheet with a thickness of 3-1 is placed in water at 70°C and the voltage SKY is
After being charged with a sinusoidal alternating current of frequency I Kl for 320 hours, the samples were stained with methylene blue and the number of water trees was counted.
［発明の効果］
上述のように本発明のエチレン系重合体または該エチレ
ン系重合体組成物は、非常に少ない量の特定の極性基単
位と、不飽和カルボン酸エステルおよび／またはビニル
エステル単位とを含有せしめたことにより、水トリー性
が改良され、電気絶縁抵抗が飛躍的に高められた効果が
得られ、電力ケーブルの絶縁層として使用した場合にお
いて、絶縁層を厚くしないで高電圧伝送時の電力損失を
低減することができる。[Effects of the Invention] As described above, the ethylene polymer or the ethylene polymer composition of the present invention contains very small amounts of specific polar group units and unsaturated carboxylic acid ester and/or vinyl ester units. By incorporating the above, the water tree properties are improved and the electrical insulation resistance is dramatically increased.When used as an insulation layer for power cables, it is possible to maintain high voltage transmission without making the insulation layer thick. power loss can be reduced.
第１図は本発明におけるインパルス破壊試験用マツケオ
ン電極を示す略側面図である。
１、ステンレス球
２、試料
８、エポキシ樹脂
４、ポリメチルメタクリレート
出願人 日本石油化学株式会社FIG. 1 is a schematic side view showing a Matsukeon electrode for impulse breakdown testing according to the present invention. 1. Stainless steel bulb 2. Sample 8. Epoxy resin 4. Polymethyl methacrylate Applicant Nippon Petrochemical Co., Ltd.
Claims (2)
重合体または該エチレン系重合体組成物。 （ａ）エチレン単位８９．２〜９８．９９８重量％ （ｂ）不飽和カルボン酸エステルおよび／またはビニル
エステル単位１〜１０重量％ （ｃ）ケトン基、ニトリル基、ニトロ基を含む単量体か
らなる群から選ばれる少なくとも一種の極性基単位０．
００２〜０．８重量％(1) An ethylene polymer or an ethylene polymer composition consisting of the following (a), (b), and (c). (a) 89.2 to 98.998% by weight of ethylene units (b) 1 to 10% by weight of unsaturated carboxylic acid ester and/or vinyl ester units (c) From monomers containing ketone groups, nitrile groups, and nitro groups At least one polar group unit selected from the group 0.
002-0.8% by weight
重合体または該エチレン系重合体組成物を絶縁体として
用いたことを特徴とする電力ケーブル。 （ａ）エチレン単位８９．２〜９８．９９８重量％ （ｂ）不飽和カルボン酸エステルおよび／またはビニル
エステル単位１〜１０重量％ （ｃ）ケトン基、ニトリル基、ニトロ基を含む単量体か
らなる群から選ばれる少なくとも一種の極性基単位０．
００２〜０．８重量％(2) A power cable characterized in that an ethylene polymer or an ethylene polymer composition comprising the following (a), (b), and (c) is used as an insulator. (a) 89.2 to 98.998% by weight of ethylene units (b) 1 to 10% by weight of unsaturated carboxylic acid ester and/or vinyl ester units (c) From monomers containing ketone groups, nitrile groups, and nitro groups At least one polar group unit selected from the group 0.
002-0.8% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23781190A JPH04118808A (en) | 1990-09-07 | 1990-09-07 | Highly water-tree resistant ethylene-based polymer or ethylene-based polymer composition and power cable using it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23781190A JPH04118808A (en) | 1990-09-07 | 1990-09-07 | Highly water-tree resistant ethylene-based polymer or ethylene-based polymer composition and power cable using it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04118808A true JPH04118808A (en) | 1992-04-20 |
Family
ID=17020759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23781190A Pending JPH04118808A (en) | 1990-09-07 | 1990-09-07 | Highly water-tree resistant ethylene-based polymer or ethylene-based polymer composition and power cable using it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04118808A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0674325A2 (en) * | 1994-03-24 | 1995-09-27 | Nippon Petrochemicals Co., Ltd. | Electrically insulating polymer composition and wire or cable using the same |
| KR19990077535A (en) * | 1998-03-30 | 1999-10-25 | 조셉 에스. 바이크 | Tree Resistant Cable and Composition therefor |
| WO2002052582A1 (en) * | 2000-12-27 | 2002-07-04 | Pirelli S.P.A. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
| JP2004535500A (en) * | 2001-07-17 | 2004-11-25 | トタル・フランス | Polymers based on olefins and alkenyl alkylates and their use as multifunctional additives in fuels and combustibles |
| US6903263B2 (en) | 2000-12-27 | 2005-06-07 | Pirelli, S.P.A. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
-
1990
- 1990-09-07 JP JP23781190A patent/JPH04118808A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0674325A2 (en) * | 1994-03-24 | 1995-09-27 | Nippon Petrochemicals Co., Ltd. | Electrically insulating polymer composition and wire or cable using the same |
| EP0674325A3 (en) * | 1994-03-24 | 1995-12-20 | Nippon Petrochemicals Co Ltd | Electrically insulating polymer composition and wire or cable using the same. |
| KR19990077535A (en) * | 1998-03-30 | 1999-10-25 | 조셉 에스. 바이크 | Tree Resistant Cable and Composition therefor |
| WO2002052582A1 (en) * | 2000-12-27 | 2002-07-04 | Pirelli S.P.A. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
| US6903263B2 (en) | 2000-12-27 | 2005-06-07 | Pirelli, S.P.A. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
| AU2002237234B2 (en) * | 2000-12-27 | 2005-11-24 | Prysmian Cavi E Sistemi Energia S.R.L. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
| AU2002237234B8 (en) * | 2000-12-27 | 2005-12-22 | Prysmian Cavi E Sistemi Energia S.R.L. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
| JP2004535500A (en) * | 2001-07-17 | 2004-11-25 | トタル・フランス | Polymers based on olefins and alkenyl alkylates and their use as multifunctional additives in fuels and combustibles |
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