JPH0552606B2 - - Google Patents
Info
- Publication number
- JPH0552606B2 JPH0552606B2 JP4605985A JP4605985A JPH0552606B2 JP H0552606 B2 JPH0552606 B2 JP H0552606B2 JP 4605985 A JP4605985 A JP 4605985A JP 4605985 A JP4605985 A JP 4605985A JP H0552606 B2 JPH0552606 B2 JP H0552606B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- aromatic
- formula
- compounds
- 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.)
- Expired - Lifetime
Links
- 229920000573 polyethylene Polymers 0.000 claims description 37
- 150000001491 aromatic compounds Chemical class 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000011810 insulating material Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- -1 polyethylene Polymers 0.000 description 30
- 238000000034 method Methods 0.000 description 20
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 238000006356 dehydrogenation reaction Methods 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000004795 grignard reagents Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KLFWUSCMFSYYOJ-UHFFFAOYSA-N 1-phenyl-2-prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC=C1C1=CC=CC=C1 KLFWUSCMFSYYOJ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KFPGHAYIXYYRIO-UHFFFAOYSA-N 3-prop-1-en-2-ylphenanthrene Chemical compound C1=CC=C2C3=CC(C(=C)C)=CC=C3C=CC2=C1 KFPGHAYIXYYRIO-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
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- OVZXISBUYCEVEV-OUKQBFOZSA-N [(e)-1-phenylprop-1-en-2-yl]benzene Chemical compound C=1C=CC=CC=1C(/C)=C/C1=CC=CC=C1 OVZXISBUYCEVEV-OUKQBFOZSA-N 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000005724 cycloalkenylene group Chemical group 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012777 electrically insulating material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011953 free-radical catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 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
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DDUWNZVBKPLCPB-UHFFFAOYSA-N (2-benzylcyclohexen-1-yl)benzene Chemical compound C=1C=CC=CC=1CC(CCCC1)=C1C1=CC=CC=C1 DDUWNZVBKPLCPB-UHFFFAOYSA-N 0.000 description 1
- SOPOITUZEUADTJ-UHFFFAOYSA-N (2-phenylcyclohexen-1-yl)benzene Chemical compound C1CCCC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 SOPOITUZEUADTJ-UHFFFAOYSA-N 0.000 description 1
- FLTIZNYOOOPPHQ-UHFFFAOYSA-N 1,1-diphenylprop-1-en-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)=C(C=1C=CC=CC=1)C1=CC=CC=C1 FLTIZNYOOOPPHQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- JHWLBELAPPNSJH-UHFFFAOYSA-N 1,3-diphenylbut-1-enylbenzene Chemical compound C=1C=CC=CC=1C(C)C=C(C=1C=CC=CC=1)C1=CC=CC=C1 JHWLBELAPPNSJH-UHFFFAOYSA-N 0.000 description 1
- RVSOBEHRLISDLD-UHFFFAOYSA-N 1-(1-phenyl-2h-naphthalen-1-yl)ethanol Chemical compound C1C=CC2=CC=CC=C2C1(C(O)C)C1=CC=CC=C1 RVSOBEHRLISDLD-UHFFFAOYSA-N 0.000 description 1
- DMMHJGCQMUODLJ-UHFFFAOYSA-N 1-(1-phenylethenyl)naphthalene Chemical group C=1C=CC2=CC=CC=C2C=1C(=C)C1=CC=CC=C1 DMMHJGCQMUODLJ-UHFFFAOYSA-N 0.000 description 1
- XBHXCOBZJNOMAT-UHFFFAOYSA-N 1-(1-phenylethyl)-2-prop-1-en-2-ylbenzene Chemical compound C=1C=CC=C(C(C)=C)C=1C(C)C1=CC=CC=C1 XBHXCOBZJNOMAT-UHFFFAOYSA-N 0.000 description 1
- NCINPWYIMJVYQM-UHFFFAOYSA-N 1-(1-phenylethyl)-4-prop-1-en-2-ylbenzene Chemical compound C=1C=C(C(C)=C)C=CC=1C(C)C1=CC=CC=C1 NCINPWYIMJVYQM-UHFFFAOYSA-N 0.000 description 1
- AZGVYQZXBPBCBQ-UHFFFAOYSA-N 1-(1-phenylethyl)naphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1C(C)C1=CC=CC=C1 AZGVYQZXBPBCBQ-UHFFFAOYSA-N 0.000 description 1
- FWFYWUILSDQGJQ-UHFFFAOYSA-N 1-(cyclohexen-1-yl)-2-phenylbenzene Chemical group C1CCCC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 FWFYWUILSDQGJQ-UHFFFAOYSA-N 0.000 description 1
- VBJKIZIHKVZRSV-UHFFFAOYSA-N 1-(cyclopenten-1-yl)-2-phenylbenzene Chemical group C1CCC=C1C1=CC=CC=C1C1=CC=CC=C1 VBJKIZIHKVZRSV-UHFFFAOYSA-N 0.000 description 1
- YCYYEFZRVLGSGX-UHFFFAOYSA-N 1-[2-(1-phenylethyl)phenyl]ethanone Chemical compound C=1C=CC=C(C(C)=O)C=1C(C)C1=CC=CC=C1 YCYYEFZRVLGSGX-UHFFFAOYSA-N 0.000 description 1
- JFYOSUYIDPDIAI-UHFFFAOYSA-N 1-[2-(2-methylphenyl)ethenyl]naphthalene Chemical group CC1=CC=CC=C1C=CC1=CC=CC2=CC=CC=C12 JFYOSUYIDPDIAI-UHFFFAOYSA-N 0.000 description 1
- NQPXLFULXJAXCH-UHFFFAOYSA-N 1-benzyl-2-(cyclohexen-1-yl)benzene Chemical compound C=1C=CC=C(C=2CCCCC=2)C=1CC1=CC=CC=C1 NQPXLFULXJAXCH-UHFFFAOYSA-N 0.000 description 1
- ZPALEWLHIOOJCY-UHFFFAOYSA-N 1-benzyl-4-(1-phenylprop-1-en-2-yl)benzene Chemical compound C=1C=C(CC=2C=CC=CC=2)C=CC=1C(C)=CC1=CC=CC=C1 ZPALEWLHIOOJCY-UHFFFAOYSA-N 0.000 description 1
- LQFYYIVSWRRJOF-UHFFFAOYSA-N 1-benzyl-4-(2-phenylethenyl)benzene Chemical compound C=1C=C(C=CC=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 LQFYYIVSWRRJOF-UHFFFAOYSA-N 0.000 description 1
- RLBYCFQPKBFPDE-UHFFFAOYSA-N 1-benzyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1CC1=CC=CC=C1 RLBYCFQPKBFPDE-UHFFFAOYSA-N 0.000 description 1
- XMWJLKOCNKJERQ-UHFFFAOYSA-N 1-bromoanthracene Chemical compound C1=CC=C2C=C3C(Br)=CC=CC3=CC2=C1 XMWJLKOCNKJERQ-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- NSBVMSRQJLNUTB-UHFFFAOYSA-N 1-cyclopent-2-en-1-ylnaphthalene Chemical compound C1=CCCC1C1=CC=CC2=CC=CC=C12 NSBVMSRQJLNUTB-UHFFFAOYSA-N 0.000 description 1
- JJWIXGDIWGGMTQ-UHFFFAOYSA-N 1-ethenyl-2-(1-phenylethyl)benzene Chemical compound C=1C=CC=C(C=C)C=1C(C)C1=CC=CC=C1 JJWIXGDIWGGMTQ-UHFFFAOYSA-N 0.000 description 1
- YOBUVNADBSHNMO-UHFFFAOYSA-N 1-ethenyl-4-(1-phenylethyl)benzene Chemical compound C=1C=C(C=C)C=CC=1C(C)C1=CC=CC=C1 YOBUVNADBSHNMO-UHFFFAOYSA-N 0.000 description 1
- OXSRPYAZKHDLAQ-UHFFFAOYSA-N 1-ethenyl-4-[1-(4-methylphenyl)ethyl]benzene Chemical compound C=1C=C(C=C)C=CC=1C(C)C1=CC=C(C)C=C1 OXSRPYAZKHDLAQ-UHFFFAOYSA-N 0.000 description 1
- UGMRKNAZEKUAQS-UHFFFAOYSA-N 1-ethenylphenanthrene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C=C)=CC=C2 UGMRKNAZEKUAQS-UHFFFAOYSA-N 0.000 description 1
- GUPIKZAAELPHQW-UHFFFAOYSA-N 1-ethylanthracene Chemical compound C1=CC=C2C=C3C(CC)=CC=CC3=CC2=C1 GUPIKZAAELPHQW-UHFFFAOYSA-N 0.000 description 1
- MDRVHDXASYPUCB-VAWYXSNFSA-N 1-methyl-4-[(e)-2-phenylethenyl]benzene Chemical compound C1=CC(C)=CC=C1\C=C\C1=CC=CC=C1 MDRVHDXASYPUCB-VAWYXSNFSA-N 0.000 description 1
- LMVGEYSKRCKNJY-UHFFFAOYSA-N 1-methyl-4-[1-(4-phenylphenyl)ethenyl]benzene Chemical group C1=CC(C)=CC=C1C(=C)C1=CC=C(C=2C=CC=CC=2)C=C1 LMVGEYSKRCKNJY-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- CBJPRTGKMYOVJO-UHFFFAOYSA-N 1-phenyl-2-(2-phenylethenyl)benzene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1C1=CC=CC=C1 CBJPRTGKMYOVJO-UHFFFAOYSA-N 0.000 description 1
- CBJPRTGKMYOVJO-FOCLMDBBSA-N 1-phenyl-2-[(e)-2-phenylethenyl]benzene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1C1=CC=CC=C1 CBJPRTGKMYOVJO-FOCLMDBBSA-N 0.000 description 1
- HKTCLPBBJDIBGF-UHFFFAOYSA-N 1-phenyl-2-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC=C1C1=CC=CC=C1 HKTCLPBBJDIBGF-UHFFFAOYSA-N 0.000 description 1
- QZZIRQGSGMIJNA-UHFFFAOYSA-N 1-phenyl-4-(2-phenylprop-1-enyl)benzene Chemical compound C=1C=CC=CC=1C(C)=CC(C=C1)=CC=C1C1=CC=CC=C1 QZZIRQGSGMIJNA-UHFFFAOYSA-N 0.000 description 1
- RTCXQMFXAWOHKN-VAWYXSNFSA-N 1-phenyl-4-[(e)-2-phenylethenyl]benzene Chemical compound C=1C=CC=CC=1/C=C/C(C=C1)=CC=C1C1=CC=CC=C1 RTCXQMFXAWOHKN-VAWYXSNFSA-N 0.000 description 1
- STSHXUNZIQVXJL-UHFFFAOYSA-N 1-phenyl-4-prop-1-en-2-ylbenzene Chemical group C1=CC(C(=C)C)=CC=C1C1=CC=CC=C1 STSHXUNZIQVXJL-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- LCJNYCWJKAWZKZ-UHFFFAOYSA-N 1-prop-1-en-2-ylnaphthalene Chemical compound C1=CC=C2C(C(=C)C)=CC=CC2=C1 LCJNYCWJKAWZKZ-UHFFFAOYSA-N 0.000 description 1
- CFSHAILOZWNBBL-UHFFFAOYSA-N 1-propan-2-yl-4-(2-prop-1-en-2-ylphenyl)benzene Chemical group C1=CC(C(C)C)=CC=C1C1=CC=CC=C1C(C)=C CFSHAILOZWNBBL-UHFFFAOYSA-N 0.000 description 1
- LYZJKMDLTZKRML-UHFFFAOYSA-N 1-propylanthracene Chemical compound C1=CC=C2C=C3C(CCC)=CC=CC3=CC2=C1 LYZJKMDLTZKRML-UHFFFAOYSA-N 0.000 description 1
- JXIMXDWYILVTRJ-UHFFFAOYSA-N 2-(1-phenylethyl)benzaldehyde Chemical compound C=1C=CC=C(C=O)C=1C(C)C1=CC=CC=C1 JXIMXDWYILVTRJ-UHFFFAOYSA-N 0.000 description 1
- PEKVJPCSQNGHGN-UHFFFAOYSA-N 2-(1-phenylprop-1-en-2-yl)naphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1C(C)=CC1=CC=CC=C1 PEKVJPCSQNGHGN-UHFFFAOYSA-N 0.000 description 1
- LEPXWRCEUYBFAX-UHFFFAOYSA-N 2-(1-phenylprop-1-enyl)naphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1C(=CC)C1=CC=CC=C1 LEPXWRCEUYBFAX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JDUGHUNNMFYNFM-UHFFFAOYSA-N 2-anthracen-1-ylethanol Chemical compound C1=CC=C2C=C3C(CCO)=CC=CC3=CC2=C1 JDUGHUNNMFYNFM-UHFFFAOYSA-N 0.000 description 1
- JYBJXKVJBAHQNF-UHFFFAOYSA-N 2-ethenylanthracene Chemical compound C1=CC=CC2=CC3=CC(C=C)=CC=C3C=C21 JYBJXKVJBAHQNF-UHFFFAOYSA-N 0.000 description 1
- UIUTYKKZYFMBHJ-UHFFFAOYSA-N 2-ethenylphenanthrene Chemical compound C1=CC=C2C3=CC=C(C=C)C=C3C=CC2=C1 UIUTYKKZYFMBHJ-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- KNOSFUPOBWJKGG-UHFFFAOYSA-N 2-phenylprop-2-enylbenzene Chemical compound C=1C=CC=CC=1C(=C)CC1=CC=CC=C1 KNOSFUPOBWJKGG-UHFFFAOYSA-N 0.000 description 1
- RVHYGRQVQKCJPX-UHFFFAOYSA-N 2-prop-1-en-2-ylanthracene Chemical compound C1=CC=CC2=CC3=CC(C(=C)C)=CC=C3C=C21 RVHYGRQVQKCJPX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OGOYZCQQQFAGRI-UHFFFAOYSA-N 9-ethenylanthracene Chemical compound C1=CC=C2C(C=C)=C(C=CC=C3)C3=CC2=C1 OGOYZCQQQFAGRI-UHFFFAOYSA-N 0.000 description 1
- KTPLMACSFXCPHL-UHFFFAOYSA-N 9-ethenylphenanthrene Chemical compound C1=CC=C2C(C=C)=CC3=CC=CC=C3C2=C1 KTPLMACSFXCPHL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SNXFIUCZUODSCP-UHFFFAOYSA-N C1(=CC=CC=C1)C1(CC=CC2=CC=CC=C12)C=C Chemical group C1(=CC=CC=C1)C1(CC=CC2=CC=CC=C12)C=C SNXFIUCZUODSCP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- GNQWHYWLSGTMSL-OUKQBFOZSA-N [(e)-3-phenylbut-1-enyl]benzene Chemical compound C=1C=CC=CC=1C(C)\C=C\C1=CC=CC=C1 GNQWHYWLSGTMSL-OUKQBFOZSA-N 0.000 description 1
- AIMDYNJRXHEXEL-KPKJPENVSA-N [(e)-3-phenylprop-1-enyl]benzene Chemical compound C=1C=CC=CC=1C\C=C\C1=CC=CC=C1 AIMDYNJRXHEXEL-KPKJPENVSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical class C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000010735 electrical insulating oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- QGEFGPVWRJCFQP-UHFFFAOYSA-M magnesium;methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC=C1 QGEFGPVWRJCFQP-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 150000001911 terphenyls Chemical class 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
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Insulating Materials (AREA)
Description
(イ) 産業上の利用分野
本発明は衝撃電圧に対する優れた耐破壊強度を
有する電気絶縁材料に関するものである。
(ロ) 従来技術
従来から電力ケーブル等の電気絶縁材料として
種々のプラスチツク材料が使用されている。特に
オレフイン重合体は電気特性、機械特性および化
学的安定性などの諸特性に優れている。なかでも
高圧法ラジカル重合による低密度ポリエチレンは
安価で誘電損失も少なく加工性が良く、かつ架橋
させてその耐熱性を大巾に向上させるうるほかに
イオン重合に比較して触媒残渣等の異物の混入に
よるトリー現象の懸念が少ない等の多くの利点を
有しているところから電線、電力ケーブル用とし
て広く利用されている。
このような電力ケーブル用絶縁材料における現
在の問題点は、今後予想される送電容量の増大に
伴なつて送電電圧が上昇すると絶縁体の厚さを上
昇電圧に見合う分だけ厚くしなければならないこ
とである。即ち、現在のポリエチレン等の材料で
は高電圧化に対して、絶縁層を非常に厚くしなけ
れば絶縁破壊を起こしてしまうのである。
かかる問題に対して種々の改良方法が提案され
ている。例えば、衝撃電圧に対する耐破壊強度を
特に高温域で改善するためにポリエチレンにスチ
レンをグラフト重合させる方法がいくつか提案さ
れている。特公昭54−18760号公報に、その一つ
が示されているがこの方法ではポリエチレンの架
橋が不可避でありまた低温域のインパルス強度が
低下するという問題点を有する。特開昭57−
80605号公報には水性懸濁液中で芳香族ビニルモ
ノマーをエチレン重合体粒子に含浸、重合させる
方法が提案されているがプロセスが非常に複雑で
あるという欠点を有する。
またポリエチレンまたはオレフイン重合体にポ
リスチレン等の芳香族重合体を配合する方法（特
公昭38−20717号、特開昭50−142651号、特開昭
52−54187号公報）が提案されているが、ポリエ
チレンもしくはオレフイン重合体とスチレン重合
体との相溶性が悪いという欠点を有する。
ポリエチレンにスチレンと共役ジエン類とのブ
ロツク共重合体を配合する方法（特開昭52−
41884号公報）も提案されているが、この方法で
は耐熱性や押出加工性が低下してしまう。
その他、ポリエチレンに電気絶縁油を含浸させ
る方法（特開昭49−33938号公報）が提案されて
いるが、この方法では長期使用した場合、あるい
は環境の変化によつて練り込んだ電気絶縁油がブ
リードして効果がそこなわれるという欠点を有す
る。
(ハ) 発明が解決しようとする問題点
本発明は上記の問題点を解決するために鋭意検
討した結果、上記の如き従来技術の欠点を有せ
ず、衝撃電圧に対する耐破壊強度の増大した電気
絶縁材料を提供するものである。
(ニ) 問題を解決するための手段
本発明の要旨は１分子中に炭素−炭素２重結合
を１個有する２〜３環芳香族化合物（ただし、下
記ａ〜ｅの化合物を除く）から選ばれた少なくと
も１種の存在下、エチレンもしくはエチレンと他
の単量体との混合物を、重合圧力500〜4000Kg／
cm2、重合温度50〜400℃の条件下にて高圧ラジカ
ル重合して得られた、重合体成分として該芳香族
化合物に由来する単位を0.005〜１モル％含むこ
とを特徴とするエチレン系重合体から成る電気絶
縁材料にある。
(a)
(b)
(c)
(d)
(e)
〔式中、R1は炭素数が１または２のアルキ
レン基、R2，R3は水素原子、塩素原子または
炭素数１〜４の直鎖もしくは分岐のアルキル
基、R4，R5は水素原子またはメチル基をそれ
ぞれ表わす〕
１分子中に炭素−炭素２重結合を１個、ベンゼ
ン環を２〜３個有する芳香族化合物は各種のもの
が好ましく使用できる。代表的な化合物を以下に
例示するが、本発明はこれらに限定されるもので
はない。
まず、縮合または非縮合型の２環芳香族環を有
するオレフインが挙げられる。
このオレフインには、シクロペンテン、シクロ
ヘキセンなどの環状オレフイン誘導体と鎖状オレ
フイン誘導体とがあり、たとえば、このようなオ
レフインには、次の一般式（）ないし（）で
表わされるような化合物がある。
一般式
〔式中、R1は不飽和２重結合を１個有する
ところのアルケニレン基またはシクロアルケニ
レン基である。また、ｍおよびｎは０から３の
整数であり、ｍ個のR2およびｎ個のR3はそれ
ぞれ同一もしくは異なり、それらは水素原子ま
たはアルキル基である〕
一般式
〔式中、R4はアルケニル基またはシクロア
ルケニル基であり、R5はアルキレン基または
シクロアルキレン基である。また、ｍおよびｎ
は０から３の整数であり、ｍ個のR2およびｎ
個のR3はそれぞれ同一もしくは異なり、それ
らは水素原子またはアルキル基である〕
一般式
ここで、R4はアルケニル基またはシクロア
ルケニル基である。また、ｍおよびｎは０から
３の整数であり、ｍ個のR2およびｎ個のR3は
それぞれ同一もしくは異なり、それらは水素原
子またはアルキル基である〕
一般式
〔ここで、R4はアルケニル基またはシクロ
アルケニル基である。また、ｍおよびｎは０か
ら３の整数であり、ｍ個のR2およびｎ個のR3
はそれぞれ同一もしくは異なり、それらは水素
原子またはアルキル基である〕
上記（）におけるR1のアルケニレン基もし
くはシクロアルケニレン基は、エチレン、プロピ
レン、ブテン、イソブテン、ペンテン、メチルペ
ンテン、ヘキセン、シクロペンテン、シクロヘキ
センまたはアルキルシクロヘキセンなどから２個
の水素原子を除いた２価の置換基であり、また、
アルキル基R2およびR3は、メチル、エチル、プ
ロピル、イソプロピル、ｎ−ブチル、イソブチ
ル、sec−ブチル、tert−ブチルおよびアミル基
などである。
式（）の具体的な化合物としては、スチルベ
ン、４−メチルスチルベン、１，２−ジフエニル
プロペン、１，３−ジフエニルプロペン、１，４
−ジフエニルブテン−１、１，４−ジフエニルブ
テン−２、１，１−ジフエニルプロペン−１、
２，３−ジフエニルプロペン、１，２−ジフエニ
ルブテン−２、１，３−ジフエニルブテン−１、
２，４−ジフエニル−４−メチルペンテン−１、
１，２−ジフエニルシクロヘキセン、フエニルベ
ンジルシクロヘキセンなどがある。
これらは、スチレンまたはα−メチルスチレン
やビニルトルエンなどのスチレン類の酸触媒によ
る二量化または共二量化によつて製造することが
できる。
また、１，２−ジフエニルエチレンなどはベン
ズアルデヒドと臭化ベンジルマグネシウムとを反
応させ、脱水させればよく、１，２−ジフエニル
プロペンも同様である。さらに１，１−ジフエニ
ルエチレンはジフエニルケトンにヨウ化メチルマ
グネシウムなどのグリニヤール試薬を反応させ脱
水することにより得られる。
式（）の化合物におけるR4は、ビニル、プ
ロペニル、イソプロペニル、アリル、ブテニル、
シクロペンテニル、シクロヘキセニルなどのアル
ケニル基またはシクロアルケニル基であり、R5
は、鎖状飽和脂肪族炭化水素またはシクロペンタ
ン、シクロヘキサン、シクロヘプタンなどの飽和
脂環式炭化水素から水素原子が２個除かれた２価
の置換基である。また、アルキル基であるR2お
よびR3は式（）におけるR2およびR3と同様で
ある。
式（）の具体的な化合物としては、１−フエ
ニル−１−（４−ビニルフエニル）エタン、１−
（４−メチルフエニル−１−（４−ビニルフエニ
ル）エタン、１−フエニル−１−（４−イソプロ
ペニルフエニル）エタン、フエニル−（４−ビニ
ルフエニル）メタン、フエニル−（シクロヘキセ
ニルフエニル）メタンなどである。
これらは種々の合成化学的手法で合成でき、た
とえば、フエニル−（ビニルフエニル）エタンな
どは、ジフエニルエタンにフリーデル・クラフツ
触媒によりアセチルクロライドを反応させ、フエ
ニル−（アセチルフエニル）エタンを得て、次い
で、水素化ホウ素ナトリウムなどで還元した後に
脱水させて得られる。フエニル−（イソプロペニ
ルフエニル）エタンなどは、フエニル−（ホルミ
ルフエニル）エタンにヨウ化メチルマグネシウム
などのグリニヤール試薬を反応させ、その後脱水
させることによつて得ることができる。
また、式（）におけるアルケニル基またはシ
クロアルケニル基であるR4は、式（）におけ
るR4と同様であり、また、アルキル基としての
R2およびR3も式（）におけるR2およびR3と同
様である。
この式（）の具体的化合物としては、２−イ
ソプロペニルビフエニル、４−イソプロペニルビ
フエニル、２−イソプロペニル−4′−イソプロピ
ルビフエニル、シクロヘキセニルビフエニル、シ
クロペンテニルビフエニルなどがある。これらの
うち、たとえば、イソプロペニルビフエニルは、
イソプロピルビフエニルの脱水素などにより得る
ことができる。
さらに、式（）におけるアルケニル基または
シクロアルケニル基としてのR4も、式（）に
おけるR4と同様であり、また、アルキル基とし
てのR2およびR3も、式（）におけるR2および
R3と同様である。
この式（）の具体的化合物としては、α−ビ
ニルナフタレン、イソプロペニルナフタレン、ア
リルナフタレン、１−シクロペント−２−エニル
ナフタレンなどがある。これらのうち、たとえ
ば、ビニルナフタレンはホルミルナフタレンにヨ
ウ化メチルマグネシウムなどのグリニヤール試薬
を反応させ、次いで脱水させることにより得るこ
とができる。
他の２環芳香族オレフインの例として、アリー
ルインデン類、アラルキルインデン類、アセナフ
チレン類が挙げられる。
３環芳香族オレフインの例としてつぎの一般式
（）〜（）で示されるものが挙げられる。
一般式
〔式中、R1，R2およびR3は水素原子または
炭素数１〜４のエチレン性２重結合を有するこ
とのある脂肪族性炭化水素残基であり、ｌ，ｍ
は０〜３の整数であり、ｎは０〜２の整数であ
る。但し、１個のR1、ｍ個のR2およびｎ個の
R3の有するエチレン性２重結合の合計は１で
ある〕
一般式（）で表される具体的な化合物の例と
しては、１−ビニルアンスラセン、２−ビニルア
ンスラセン、９−ビニルアンスラセン、２−イソ
プロペニルアンスラセン、９−プロペニル−10−
プロピルアンスラセンなどがある。
一般式
〔式中、R1，R2およびR3は水素原子または
炭素数１〜４のエチレン性２重結合を有するこ
とのある脂肪族性炭化水素残基であり、ｌ，ｍ
は０〜３の整数であり、ｎは０〜２の整数であ
る。但し、１個のR1、ｍ個のR2およびｎ個の
R3の有するエチレン性２重結合の合計は１で
ある〕
一般式（）で表される具体的な化合物の例と
しては、２−ビニルフエナンスレン、３−イソプ
ロペニルフエナンスレン、３−ビニルフエナンス
レン、９−ビニルフエナンスレンなどがある。
一般式
〔式中、R1は炭素数１〜４のエチレン性２
重結合を有することのある脂肪族炭化水素残基
であり、R2〜R4は水素原子もしくは炭素数１
〜４のエチレン性２重結合を含むことのある脂
肪族炭化水素残基である。ｋは０または１であ
り、ｌ，ｍ，ｎはそれぞれ０〜３の整数であ
る。但し、R1、ｌ個のR2、ｍ個のR3およびｎ
個のR4のエチレン性２重結合の合計は１であ
る〕
一般式（）で表される具体的な化合物の例と
しては、
１−フエニル−２−（１−ナフチル）エチレン、
１−フエニル−２−（２−ナフチル）エチレン、
１−フエニル−１−（１−ナフチル）エチレン、
１−フエニル−１−（２−ナフチル）エチレン、
１−フエニル−１−（１−ナフチル）プロペン、
１−フエニル−１−（２−ナフチル）プロペン、
１−フエニル−２−（２−ナフチル）プロペン、
１−（１−ナフチル）−２−ｏ−トリルエチレンな
どがある。
一般式
〔式中、R1およびR2は炭素数１〜４のエチ
レン性２重結合を有することのある脂肪族炭化
水素残基であり、R3〜R5は水素原子または炭
素数１〜４のエチレン性２重結合を有すること
のある脂肪族炭化水素残基である。ｊおよびｋ
は０または１であり、ｌ，ｍおよびｎは０〜３
の整数である。但し、R1，R2、ｌ個のR3、ｍ
個のR4およびｎ個のR5のエチレン性２重結合
の合計は１である］
上記一般式（）で表される具体的な化合物の
例としては、２−フエニルスチルベン、４−フエ
ニルスチルベン、１−フエニル−１−ビフエニル
エチレン、４−ベンジルスチルベン、１−ビフエ
ニル−４−イル−１−ｐ−トリルエチレン、１−
ビフエニル−４−イル−２−フエニルプロペン、
１−フエニル−２−（４−ベンジルフエニル）プ
ロペン、１−フエニル−１−（ベンジルフエニル）
エチレン、１−トリル−１−（ベンジルフエニル）
エチレン、１−フエニル−１−（フエニルエチル
−フエニル）エチレンなどがある。
一般式
〔式中、R1は炭素数１〜４のエチレン性２
重結合を有することのある脂肪族炭化水素残基
であり、R2〜R4は水素原子または炭素数１〜
４のエチレン性２重結合を有することのある脂
肪族炭化水素残基である。また、ｌ，ｍおよび
ｎは０〜３の整数である。但し、R1、ｌ個の
R2、ｍ個のR3およびｎ個のR4のエチレン性２
重結合の合計は１である〕
上記一般式（）で表される具体的な化合物の
例としては、１，１，２−トリフエニルエチレ
ン、１，１，２−トリフエニルプロペン、１，
１，３−トリフエニルブテン、１，１−ジフエニ
ル−２−ｏ−トリルエチレン、１，１−ジフエニ
ル−２−ｐ−トリルエチレンおよび３，３，３−
トリフエニルプロペン−１などがある。
上記の化合物は、本発明の電気絶縁材料の製造
に適用し得るものを例示したものであり、本発明
はこれらによつて限定されるものではない。
これらの芳香族オレフインは、種々の合成化学
的手法、例えばグリニヤール反応を利用してアル
コールを製造し、これを脱水することにより得る
ことができる。
例えば、１−フエニル−１−ナフチルエチレン
は、ブロモナフタレンからのグリニヤール試薬を
アセトフエノンに反応させ、得られた１−フエニ
ル−１−ナフチルエタノールを脱水することによ
り得られる。また、ビニルアンスラセンは、ブロ
モアンスラセンからのグリニヤール試薬とアセト
アルデヒドとを反応させ、得られたヒドロキシエ
チルアンスラセンを脱水することにより得ること
ができる。
さらに、前記の芳香族オレフインは、飽和、す
なわちエチレン性２重結合を有しない芳香族炭化
水素を脱水素することによつても製造することが
できる。
すなわち、脱水素反応を利用する方法として
は、縮合もしくは非縮合型の芳香族環を３つ以上
有する飽和芳香族炭化水素を、適宜の脱水素触媒
を用いて脱水素することにより製造することがで
きる。なお、ジオレフインはモノオレフインから
も製造することができる。脱水素の際は、重合な
どの副反応は抑制するが、縮合もしくは非縮合型
の芳香族環を３つ有する芳香族炭化水素が生成す
るならば、分解反応などの副反応が生じてもよ
い。
脱水素触媒は、特に限定されず任意の触媒を使
用できる。例えば、Cr、Fe、Cu、Ｋ、Mg、Ca
などの金属酸化物の１種もしくは２種以上の混合
物、Pt、Pd、などの貴金属、またはこれら金属
酸化物や貴金属をアルミナなどの担体に担持させ
た脱水素触媒などがある。
脱水素反応の温度は、350〜650℃、好ましくは
400〜600℃である。LHSVは、0.2〜10、好まし
くは0.5〜3.0である。また脱水素に際しては、分
圧を下げるためや、炭素の析出を防止するため
に、水蒸気、窒素、水素などのガスを存在させる
こともできる。また必要に応じて、適宜の稀釈剤
を使用することもできる。しかしながら、通常は
脱水素率をそれ程高くせずに行なえば、原料自体
が稀釈剤になり得るので好都合である。
上記の脱水素により、エチルアンスラセンから
ビニルアンスラセンが、また、フエニルナフチル
エタンからはフエニルナフチルエチレンが、さら
に、フエニルビフエニルエタンからはフエニルス
チルベンがそれぞれ製造される。
上記例示の他に、３環芳香族オレフインとして
は、ジアリールインデン類、ジアラルキルインデ
ン類、ターフエニル類等が挙げられる。
上記した２〜３環芳香族オレフインの誘導体と
して塩素、臭素のごときハロゲン置換体、メトキ
シ基、カルボキシル基、カルボニル基、エーテル
結合、エステル結合、フエノール性水酸基、アル
コール性水酸基等を有する含酸素誘導体、イオウ
原子、窒素原子を有する誘導体が挙げられる。
上記式（）〜（）の芳香族オレフインおよ
びその誘導体のほかに、アクリル酸、メタクリル
酸、マレイン酸、フマル酸のごとき不飽和のカル
ボン酸、あるいはビニルエステル等のごとき２重
結合を１個有する基にビフエニル、ナフタレン、
ジアリールアルカン、トリアリールアルカン、ト
リアリールジアルカン、アンスラセン、フエナン
スレン、アリールナフタレン、アラルキルナフタ
レン、ターフエニル等の２〜３環の芳香族環単位
もしくはこれらの誘導体が結合した芳香族化合物
も使用できる。
上記した各種の芳香族化合物はいずれも、エチ
レンもしくはエチレンを主成分とする他の単量体
との混合物の高圧ラジカル重合によつて、生成し
た重合体鎖中に重合体成分として含まれうる構造
的特徴を有している。
なお、上記した各種化合物から、前記(a)〜(e)の
化合物は除く。本発明者は、先に前記(a)〜(e)の化
合物を使用したエチレン系重合体および該エチレ
ン系重合体から成る電気絶縁材料について特願昭
59−207595〜207598号、同217924号、同233950〜
233951号として出願済みであるが、これら特定の
化合物(a)〜(e)以外にも、絶縁耐力の向上を達成し
得る芳香族化合物を見いだして本発明を完成する
に至つたものである。
従来から電力ケーブル等の絶縁材料として広く
用いられているポリエチレンは、結晶化度を低下
させると衝撃電圧に対する破壊強度（インパルス
破壊強度）が低下し、また結晶化度を上昇させる
と加工性が悪くなる欠点を有している。
一般にポリエチレン鎖に他の成分を導入すると
立体障害により結晶化度が低下することが知られ
ている。ところが本発明者らは、特定の芳香族化
合物に由来する単位を特定の割合で重合体鎖中に
含有させると、結晶化度が低下してもインパルス
破壊強度が上昇する範囲が存在することを見いだ
したのである。本発明は、エチレン系重合体中に
極めて少量の芳香族単位を導入することによつ
て、インパルス破壊強度の改良効果が達成できる
という予期せざる知見に基づくものである。この
改良効果は、低温から高温までの広い温度範囲に
おいて認められ、特に高温域において著るしい。
本発明のエチレン重合体中に、重合体成分とし
て含まれるべき上記芳香族化合物に由来する単位
の含有量は0.005〜1.0モル％であり、好ましくは
0.01〜0.7モル％である。0.005モル％未満におい
ては改良効果がほとんど認められず、1.0モル％
を越える場合においては該芳香族化合物に由来す
る単位を含まない場合よりもインパルス破壊強度
はかえつて低下するのみならず、高圧ラジカル重
合用開始剤の消費が大きいことおよび高価な芳香
族化合物を多量に使用することのために不経済で
あるし、連鎖移動反応が激しくなり、エチレン系
重合体の分子量の低下が著るしく電気絶縁材料と
して不適当な重合体になる。
本発明のエチレン系重合体の密度は、0.890〜
0.950ｇ／cm3の範囲が好ましい。また、メルトイ
ンデツクス（以下MIと略す）は、好ましくは
0.05〜50ｇ／10分、さらに好ましくは0.1〜20
ｇ／10分の範囲である。
本発明のエチレン系重合体は、エチレンの外に
他の不飽和単量体を含み得るものであつて、この
不飽和単量体としては、プロピレン、ブテン−
１、ペンテン−１、ヘキセン−１、４−メチルペ
ンテン−１、オクテン−１、デセン−１、酢酸ビ
ニル、アクリル酸エチル、メタアクリル酸または
そのエステルおよびこれらの混合物などを例示す
ることができる。
上記エチレン系重合体中の不飽和単量体の含有
量は０〜３モル％、特に１モル％以下が好まし
い。
本発明のエチレン系重合体は他の芳香族単位を
含まないエチレン系重合体を配合して使用するこ
とができる。他のエチレン系重合体を配合した組
成物も、本発明の好ましい実施態様であり、組成
物中の芳香族単位含量が上記範囲にあることによ
り、組成物のインパルス破壊強度が改良される。
本発明のエチレン系重合体に配合する他のエチ
レン系重合体としては、エチレン単独重合体、エ
チレンとプロピレン、ブテン−１、ペンテン−
１、ヘキセン−１、４−メチルペンテン−１、オ
クテン−１、デセン−１等の炭素数３〜12のα−
オレフインとの共重合体、エチレンと酢酸ビニ
ル、アクリル酸、アクリル酸エチル、メタクリル
酸、メタアクリル酸エチル、マレイン酸、無水マ
レイン酸等の極性基含有モノマーとの共重合体、
あるいは前記エチレン単独重合体もしくはエチレ
ンとα−オレフイン共重合体をアクリル酸、マレ
イン酸等の不飽和カルボンまたはその誘導体で変
性した重合体等およびそれらの混合物が挙げられ
る。
本発明のエチレン系重合体は、高圧下における
ラジカル重合法により製造される。すなわち、高
圧下におけるラジカル重合法とは、重合圧力500
〜4000Kg／cm2、好ましくは1000〜3500Kg／cm2、反
応温度50〜400℃、好ましくは100〜350℃の条件
下、遊離基触媒および連鎖移動剤、必要ならば助
剤の存在下に槽型または管型反応器内でエチレン
および芳香族化合物、さらに所望により他の単量
体を同時に、あるいは段階的に接触、重合させる
方法をいう。該芳香族化合物が固体の場合は適宜
溶剤に溶解して供給する。
上記遊離基触媒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、酸素等の通例の開始剤が挙げられる。
また連鎖移動剤としては水素、プロピレン、ブ
テン−１、C1〜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−ヘプタン、シクロパラフ
イン類、クロロホルムおよび四塩化炭素、C1〜
C20またはそれ以上の飽和脂肪族アルコール、例
えばメタノール、エタノール、プロパノールおよ
びイソプロパノール、C1〜C20またはそれ以上の
飽和脂肪族カルボニル化合物、例えばアセトンお
よびメチルエチルケトンならびに前記以外の芳香
族化合物、例えばトルエン、ジエチルベンゼンお
よびキシレンの様な化合物等が挙げられる。
(ホ) 作用および発明の効果
上述の如くして製造される本発明のエチレン系
重合体または該エチレン系重合体に他のエチレン
系重合体を配合したエチレン系重合体組成物は、
電気絶縁材料として絶縁耐力に優れ、特に、衝撃
電圧に対する耐破壊強度が高温領域で優れている
ので超高圧電力ケーブル用絶縁材料として非常に
有用である。
また、本発明は、高圧ラジカル重合という比較
的簡単なプロセスで製造でき、従来の複雑なグラ
フト、ブレンド工程を要しないという点において
も、非常に優れるものである。
本発明においては、エチレン系重合体またはエ
チレン系重合体組成物の性質を著しく損わない範
囲において、前記他のエチレン系重合体以外のオ
レフイン重合体（共重合体も含む）、ポリアクリ
ロニトリル、ポリアミド、ポリカーボネート、
ABS樹脂、ポリスチレン、ポリフエニレンオキ
サイド、ポリビニルアルコール系樹脂、塩化ビニ
ル系樹脂、塩化ビニリデン系樹脂、ポリエステル
系樹脂等の熱可塑性樹脂、石油樹脂、クマロン−
インデン樹脂、エチレン−プロピレン系共重合体
ゴム（EPR、EPDM等）、SBR、NBR、ブタジ
エンゴム、IIR、クロロプレンゴム、イソプレン
ゴム、スチレン−ブタジエン−スチレンブロツク
共重合体等の合成ゴムまたは天然ゴム等の少なく
とも１種と混合して用いることができる。
一方、本発明では、有機・無機系のフイラー、
酸化防止剤、滑剤、有機・無機系の各種顔料、紫
外線防止剤、分散剤、銅害防止剤、中和剤、発泡
剤、可塑剤、気泡防止剤、難燃剤、架橋剤、流れ
性改良剤、ウエルド強度改良剤、核剤等の添加剤
を本発明の効果を著しく損わない範囲で添加して
も差支えない。
また本発明のエチレン系重合体またはこれを含
む組成物は未架橋のまま用いてもよく、あるいは
必要ならば架橋処理を施して用いることができ
る。その架橋方法は通常の架橋方法が適用され
る。
(ヘ) 実施例
以下実施例を示す。
実施例 １〜５
窒素およびエチレンで充分に置換した内容積
3.8の撹拌機付き金属製オートクレーブ型反応
器に約1700ｇのエチレン、第１表に示した芳香族
化合物および所定量のｎ−ヘキサンを仕込み、更
に重合開始剤であるジ・ターシヤリーブチルパー
オキシドを注入し、重合温度170℃、重合圧力
1600Kg／cm2、重合時間60分間の重合を行ない、第
１表に示すような芳香族化合物に由来する単位を
含有する各種エチレン系重合体を調製した。
生成したポリマーの一部を加熱四塩化炭素に溶
解し、これを多量のアセトン中に投入して再沈
し、この操作を数回繰返して精製した後真空乾燥
した。
精製したポリマーを加熱圧縮により厚さ500μm
のシートに成形し、対照に同一厚さの芳香族化合
物を含まないエチレン重合体のシートを用いた補
償法による赤外分光分析によつて、各生成ポリマ
ー中の芳香族化合物に由来する単位の定量を行な
つた。
各生成ポリマー中に含まれる芳香族化合物に由
来する単位の定量は、主として1600cm-1付近の芳
香環に帰属される吸収の吸光度より行なつた。ま
た、各生成ポリマーのメルトインデツクスの測定
はJIS Ｋ−6760に準拠して行なつた。
各生成ポリマーの20℃および80℃におけるイン
パルス破壊強度を測定して、その結果を第１表に
示した。
なお、インパルス破壊強度の測定は以下の方法
で行なつた。試料は加熱圧縮成形により厚さ
50μmのシートとした。電極系には固定電極、い
わゆるマツケオン電極（第１図）を使用した。電
極系の基板４はポリメチルメタクリレート製でそ
の中央部には直径１／２インチの穴があいてい
る。電極は１／２インチのステンレス球１を用い
た。試料２は約８〜10mm角に切つたものを電極の
間にはさんだ。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、これを20℃および80℃の恒温槽に入れ
て測定を行なつた。破壊に用いた電圧波形は負極
性、１×40μSのインパルス波形で、波形をオシ
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点以上の平均値をとつた。
比較例 １〜３
実施例１と同様の重合条件で第１表に示すエチ
レン系重合体を調製してインパルス破壊強度を測
定し、その結果を第１表に示した。
(a) Industrial Application Field The present invention relates to an electrical insulating material having excellent breakdown strength against impact voltage. (b) Prior Art Various plastic materials have been used as electrical insulating materials for power cables and the like. In particular, olefin polymers have excellent properties such as electrical properties, mechanical properties, and chemical stability. Among them, low-density polyethylene produced by high-pressure radical polymerization is inexpensive, has low dielectric loss, has good processability, and can be crosslinked to greatly improve its heat resistance.Compared to ionic polymerization, low-density polyethylene is free from foreign substances such as catalyst residues. It is widely used for electric wires and power cables because it has many advantages such as less concern about tree phenomenon due to contamination. The current problem with such insulating materials for power cables is that as the transmission voltage increases with the anticipated increase in power transmission capacity, the thickness of the insulator must be increased to match the increased voltage. It is. That is, with current materials such as polyethylene, dielectric breakdown will occur if the insulating layer is not made very thick in response to high voltages. Various improvement methods have been proposed to address this problem. For example, several methods have been proposed in which styrene is graft-polymerized to polyethylene in order to improve the breakdown strength against impact voltage, especially in a high temperature range. One such method is disclosed in Japanese Patent Publication No. 54-18760, but this method has the problem that crosslinking of polyethylene is unavoidable and the impulse strength in the low temperature range is reduced. Unexamined Japanese Patent Publication 1987-
No. 80605 proposes a method of impregnating and polymerizing ethylene polymer particles with an aromatic vinyl monomer in an aqueous suspension, but this method has the disadvantage that the process is very complicated. Also, a method of blending aromatic polymers such as polystyrene with polyethylene or olefin polymers (Japanese Patent Publication No. 38-20717, JP-A-50-142651, JP-A No.
No. 52-54187) has been proposed, but it has the drawback of poor compatibility between polyethylene or olefin polymers and styrene polymers. A method of blending a block copolymer of styrene and conjugated dienes with polyethylene (Unexamined Japanese Patent Publication No. 1983-
41884) has also been proposed, but this method results in a decrease in heat resistance and extrusion processability. In addition, a method has been proposed in which polyethylene is impregnated with electrical insulating oil (Japanese Unexamined Patent Publication No. 49-33938). It has the disadvantage that it bleeds and the effect is impaired. (c) Problems to be Solved by the Invention As a result of intensive studies to solve the above-mentioned problems, the present invention has been developed to provide an electrical technology that does not have the above-mentioned drawbacks of the prior art and has increased breakdown strength against impact voltage. It provides an insulating material. (d) Means for solving the problem The gist of the present invention is to select from 2- to 3-ring aromatic compounds (excluding compounds a to e below) having one carbon-carbon double bond in one molecule. ethylene or a mixture of ethylene and other monomers in the presence of at least one monomer at a polymerization pressure of 500 to 4000 Kg/
cm 2 , an ethylene polymer obtained by high-pressure radical polymerization at a polymerization temperature of 50 to 400°C and containing 0.005 to 1 mol% of units derived from the aromatic compound as a polymer component. It is an electrically insulating material consisting of a combination. (a) (b) (c) (d) (e) [In the formula, R 1 is an alkylene group having 1 or 2 carbon atoms, R 2 and R 3 are hydrogen atoms, chlorine atoms, or linear or branched alkyl groups having 1 to 4 carbon atoms, and R 4 and R 5 are hydrogen atoms. each represents an atom or a methyl group] Various aromatic compounds having one carbon-carbon double bond and two to three benzene rings in one molecule can be preferably used. Representative compounds are illustrated below, but the present invention is not limited thereto. First, mention may be made of olefins having a fused or non-fused two-ring aromatic ring. These olefins include cyclic olefin derivatives such as cyclopentene and cyclohexene, and chain olefin derivatives. Examples of such olefins include compounds represented by the following general formulas () to (). general formula [In the formula, R 1 is an alkenylene group or a cycloalkenylene group having one unsaturated double bond. In addition, m and n are integers from 0 to 3, m R 2 and n R 3 are each the same or different, and are a hydrogen atom or an alkyl group] General formula [In the formula, R 4 is an alkenyl group or a cycloalkenyl group, and R 5 is an alkylene group or a cycloalkylene group. Also, m and n
is an integer from 0 to 3, m R 2 and n
Each R 3 is the same or different and is a hydrogen atom or an alkyl group] General formula Here, R 4 is an alkenyl group or a cycloalkenyl group. In addition, m and n are integers from 0 to 3, m R 2 and n R 3 are each the same or different, and are a hydrogen atom or an alkyl group] General formula [Here, R 4 is an alkenyl group or a cycloalkenyl group. In addition, m and n are integers from 0 to 3, and m R 2 and n R 3
are the same or different, and are a hydrogen atom or an alkyl group] The alkenylene group or cycloalkenylene group of R 1 in the above () is ethylene, propylene, butene, isobutene, pentene, methylpentene, hexene, cyclopentene, cyclohexene or It is a divalent substituent obtained by removing two hydrogen atoms from alkylcyclohexene, etc., and
Alkyl groups R2 and R3 include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and amyl groups. Specific compounds of formula () include stilbene, 4-methylstilbene, 1,2-diphenylpropene, 1,3-diphenylpropene, 1,4
-diphenylbutene-1, 1,4-diphenylbutene-2, 1,1-diphenylpropene-1,
2,3-diphenylpropene, 1,2-diphenylbutene-2, 1,3-diphenylbutene-1,
2,4-diphenyl-4-methylpentene-1,
Examples include 1,2-diphenylcyclohexene and phenylbenzylcyclohexene. These can be produced by acid-catalyzed dimerization or co-dimerization of styrene or styrenes such as α-methylstyrene and vinyltoluene. Further, 1,2-diphenylethylene and the like may be dehydrated by reacting benzaldehyde with benzylmagnesium bromide, and the same applies to 1,2-diphenylpropene. Furthermore, 1,1-diphenylethylene can be obtained by reacting diphenyl ketone with a Grignard reagent such as methylmagnesium iodide and dehydrating it. R 4 in the compound of formula () is vinyl, propenyl, isopropenyl, allyl, butenyl,
It is an alkenyl group or cycloalkenyl group such as cyclopentenyl and cyclohexenyl, and R 5
is a divalent substituent obtained by removing two hydrogen atoms from a chain saturated aliphatic hydrocarbon or a saturated alicyclic hydrocarbon such as cyclopentane, cyclohexane, and cycloheptane. Further, R 2 and R 3 which are alkyl groups are the same as R 2 and R 3 in formula (). Specific compounds of formula () include 1-phenyl-1-(4-vinylphenyl)ethane, 1-
(4-methylphenyl-1-(4-vinylphenyl)ethane, 1-phenyl-1-(4-isopropenylphenyl)ethane, phenyl-(4-vinylphenyl)methane, phenyl-(cyclohexenylphenyl)methane, etc. These can be synthesized by various synthetic chemical methods.For example, phenyl-(vinylphenyl)ethane is produced by reacting diphenylethane with acetyl chloride using a Friedel-Crafts catalyst to obtain phenyl-(acetylphenyl)ethane. , and then reduced with sodium borohydride etc. and then dehydrated. Phenyl-(isopropenyl phenyl) ethane etc. are obtained by reacting phenyl-(formylphenyl) ethane with a Grignard reagent such as methylmagnesium iodide, and then It can be obtained by dehydration. In addition, R 4 which is an alkenyl group or a cycloalkenyl group in formula () is the same as R 4 in formula (), and R 4 as an alkyl group
R 2 and R 3 are also the same as R 2 and R 3 in formula (). Specific compounds of the formula () include 2-isopropenylbiphenyl, 4-isopropenylbiphenyl, 2-isopropenyl-4'-isopropylbiphenyl, cyclohexenylbiphenyl, and cyclopentenylbiphenyl. Among these, for example, isopropenyl biphenyl is
It can be obtained by dehydrogenation of isopropyl biphenyl. Furthermore, R 4 as an alkenyl group or a cycloalkenyl group in formula () is also the same as R 4 in formula (), and R 2 and R 3 as an alkyl group are also the same as R 2 and R 3 in formula ().
Same as R3 . Specific compounds of this formula () include α-vinylnaphthalene, isopropenylnaphthalene, allylnaphthalene, and 1-cyclopent-2-enylnaphthalene. Among these, for example, vinylnaphthalene can be obtained by reacting formylnaphthalene with a Grignard reagent such as methylmagnesium iodide, followed by dehydration. Examples of other two-ring aromatic olefins include arylindenes, aralkylindenes, and acenaphthylenes. Examples of the three-ring aromatic olefin include those represented by the following general formulas () to (). general formula [In the formula, R 1 , R 2 and R 3 are hydrogen atoms or aliphatic hydrocarbon residues having 1 to 4 carbon atoms that may have an ethylenic double bond, and l, m
is an integer from 0 to 3, and n is an integer from 0 to 2. However, 1 R 1 , m R 2 and n
The total number of ethylenic double bonds that R 3 has is 1.] Specific examples of compounds represented by the general formula () include 1-vinylanthracene, 2-vinylanthracene, and 9-vinylanthracene. , 2-isopropenylanthracene, 9-propenyl-10-
Examples include propyl anthracene. general formula [In the formula, R 1 , R 2 and R 3 are hydrogen atoms or aliphatic hydrocarbon residues having 1 to 4 carbon atoms that may have an ethylenic double bond, and l, m
is an integer from 0 to 3, and n is an integer from 0 to 2. However, 1 R 1 , m R 2 and n
The total number of ethylenic double bonds that R 3 has is 1.] Specific examples of compounds represented by the general formula () include 2-vinylphenanthrene, 3-isopropenylphenanthrene, 3-isopropenylphenanthrene, Examples include vinylphenanthrene and 9-vinylphenanthrene. general formula [In the formula, R 1 is an ethylenic 2 having 1 to 4 carbon atoms
It is an aliphatic hydrocarbon residue that may have a heavy bond, and R 2 to R 4 are hydrogen atoms or carbon atoms with 1
It is an aliphatic hydrocarbon residue that may contain ~4 ethylenic double bonds. k is 0 or 1, and l, m, and n are each integers of 0 to 3. However, R 1 , l R 2 , m R 3 and n
The total number of R 4 ethylenic double bonds is 1. Examples of specific compounds represented by the general formula () include 1-phenyl-2-(1-naphthyl)ethylene,
1-phenyl-2-(2-naphthyl)ethylene,
1-phenyl-1-(1-naphthyl)ethylene,
1-phenyl-1-(2-naphthyl)ethylene,
1-phenyl-1-(1-naphthyl)propene,
1-phenyl-1-(2-naphthyl)propene,
1-phenyl-2-(2-naphthyl)propene,
Examples include 1-(1-naphthyl)-2-o-tolylethylene. general formula [In the formula, R 1 and R 2 are aliphatic hydrocarbon residues having 1 to 4 carbon atoms that may have an ethylenic double bond, and R 3 to R 5 are hydrogen atoms or hydrogen atoms having 1 to 4 carbon atoms. It is an aliphatic hydrocarbon residue that may have an ethylenic double bond. j and k
is 0 or 1, l, m and n are 0 to 3
is an integer. However, R 1 , R 2 , l R 3 , m
The total number of ethylenic double bonds of R 4 and n R 5 is 1] Examples of specific compounds represented by the above general formula () include 2-phenylstilbene, 4-phenylstilbene, enylstilbene, 1-phenyl-1-biphenylethylene, 4-benzylstilbene, 1-biphenyl-4-yl-1-p-tolylethylene, 1-
biphenyl-4-yl-2-phenylpropene,
1-phenyl-2-(4-benzylphenyl)propene, 1-phenyl-1-(benzylphenyl)
Ethylene, 1-tolyl-1-(benzylphenyl)
Examples include ethylene, 1-phenyl-1-(phenylethyl-phenyl)ethylene, and the like. general formula [In the formula, R 1 is an ethylenic 2 having 1 to 4 carbon atoms
It is an aliphatic hydrocarbon residue that may have a heavy bond, and R 2 to R 4 are hydrogen atoms or carbon atoms with 1 to 1 carbon atoms.
It is an aliphatic hydrocarbon residue that may have 4 ethylenic double bonds. Moreover, l, m and n are integers of 0 to 3. However, R 1 , l number of
R 2 , m R 3 and n R 4 ethylenic 2
The total number of double bonds is 1.] Specific examples of compounds represented by the above general formula () include 1,1,2-triphenylethylene, 1,1,2-triphenylpropene, 1,
1,3-triphenylbutene, 1,1-diphenyl-2-o-tolylethylene, 1,1-diphenyl-2-p-tolylethylene and 3,3,3-
Examples include triphenylpropene-1. The above-mentioned compounds are exemplified as those applicable to the production of the electrically insulating material of the present invention, and the present invention is not limited thereto. These aromatic olefins can be obtained by producing alcohol using various synthetic chemical techniques, such as the Grignard reaction, and then dehydrating the alcohol. For example, 1-phenyl-1-naphthylethylene is obtained by reacting a Grignard reagent from bromonaphthalene with acetophenone and dehydrating the resulting 1-phenyl-1-naphthylethanol. Moreover, vinyl anthracene can be obtained by reacting a Grignard reagent from bromoanthracene with acetaldehyde and dehydrating the obtained hydroxyethyl anthracene. Furthermore, the above-mentioned aromatic olefins can also be produced by dehydrogenating aromatic hydrocarbons that are saturated, ie, do not have ethylenic double bonds. That is, as a method using a dehydrogenation reaction, it is possible to produce a saturated aromatic hydrocarbon having three or more fused or non-fused aromatic rings by dehydrogenating it using an appropriate dehydrogenation catalyst. can. Note that diolefin can also be produced from monoolefin. During dehydrogenation, side reactions such as polymerization are suppressed, but if an aromatic hydrocarbon having three fused or non-fused aromatic rings is produced, side reactions such as decomposition reactions may occur. . The dehydrogenation catalyst is not particularly limited and any catalyst can be used. For example, Cr, Fe, Cu, K, Mg, Ca
Examples include one or a mixture of two or more metal oxides, such as noble metals such as Pt and Pd, and dehydrogenation catalysts in which these metal oxides or noble metals are supported on a carrier such as alumina. The temperature of the dehydrogenation reaction is 350-650℃, preferably
The temperature is 400-600℃. LHSV is 0.2-10, preferably 0.5-3.0. Further, during dehydrogenation, a gas such as water vapor, nitrogen, or hydrogen may be present in order to lower the partial pressure or to prevent carbon precipitation. Further, an appropriate diluent can be used as necessary. However, it is usually advantageous if the dehydrogenation rate is not increased so much because the raw material itself can act as a diluent. By the above dehydrogenation, vinyl anthracene is produced from ethyl anthracene, phenylnaphthyl ethylene is produced from phenylnaphthylethane, and phenyl stilbene is produced from phenyl biphenylethane. In addition to the above examples, examples of the three-ring aromatic olefin include diarylindenes, dialkylindenes, and terphenyls. Oxygen-containing derivatives having halogen substitutes such as chlorine and bromine, methoxy groups, carboxyl groups, carbonyl groups, ether bonds, ester bonds, phenolic hydroxyl groups, alcoholic hydroxyl groups, etc. as derivatives of the above-mentioned 2- to 3-ring aromatic olefins; Examples include derivatives having a sulfur atom and a nitrogen atom. In addition to the aromatic olefins and derivatives thereof of the above formulas () to (), they have one double bond such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, or vinyl esters. Based on biphenyl, naphthalene,
Aromatic compounds having two to three aromatic ring units or derivatives thereof such as diarylalkane, triarylalkane, triaryldialkane, anthracene, phenanthrene, arylnaphthalene, aralkylnaphthalene, and terphenyl can also be used. The various aromatic compounds mentioned above all have structures that can be included as polymer components in the polymer chain produced by high-pressure radical polymerization of ethylene or a mixture with other monomers containing ethylene as the main component. It has the following characteristics. Note that the compounds (a) to (e) above are excluded from the various compounds described above. The present inventor previously filed a patent application regarding an ethylene polymer using the compounds (a) to (e) above and an electrical insulating material made of the ethylene polymer.
59-207595~207598, 217924, 233950~
The present invention has been completed by discovering aromatic compounds that can improve dielectric strength in addition to these specific compounds (a) to (e), which have been filed as No. 233951. Polyethylene, which has traditionally been widely used as an insulating material for power cables, etc., decreases in its breakdown strength against impact voltage (impulse breakdown strength) when the degree of crystallinity decreases, and deteriorates workability when the degree of crystallinity increases. It has some drawbacks. It is generally known that when other components are introduced into the polyethylene chain, the degree of crystallinity decreases due to steric hindrance. However, the present inventors have discovered that when a specific ratio of units derived from a specific aromatic compound is contained in a polymer chain, there is a range in which the impulse rupture strength increases even if the degree of crystallinity decreases. I found it. The present invention is based on the unexpected finding that an improvement in impulse rupture strength can be achieved by introducing a very small amount of aromatic units into an ethylene polymer. This improvement effect is observed in a wide temperature range from low to high temperatures, and is particularly remarkable in the high temperature range. In the ethylene polymer of the present invention, the content of units derived from the above aromatic compound to be included as a polymer component is 0.005 to 1.0 mol%, preferably
It is 0.01-0.7 mol%. At less than 0.005 mol%, almost no improvement effect was observed, and at 1.0 mol%
If the unit exceeds 100%, the impulse rupture strength will not only be lower than in the case where units derived from the aromatic compound are not included, but also the consumption of high-pressure radical polymerization initiator will be large and a large amount of expensive aromatic compound will be used. It is uneconomical to use the ethylene polymer, and the chain transfer reaction becomes intense, resulting in a significant decrease in the molecular weight of the ethylene polymer, making it unsuitable as an electrical insulating material. The density of the ethylene polymer of the present invention is 0.890 to
A range of 0.950 g/cm 3 is preferred. In addition, the melt index (hereinafter abbreviated as MI) is preferably
0.05-50g/10 minutes, more preferably 0.1-20
g/10 minutes. The ethylene polymer of the present invention may contain other unsaturated monomers in addition to ethylene, such as propylene, butene, etc.
Examples include 1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1, vinyl acetate, ethyl acrylate, methacrylic acid or its ester, and mixtures thereof. The content of the unsaturated monomer in the ethylene polymer is preferably 0 to 3 mol%, particularly 1 mol% or less. The ethylene polymer of the present invention can be used in combination with an ethylene polymer that does not contain other aromatic units. Compositions containing other ethylene-based polymers are also preferred embodiments of the present invention, and when the aromatic unit content in the composition is within the above range, the impulse rupture strength of the composition is improved. Other ethylene polymers to be blended with the ethylene polymer of the present invention include ethylene homopolymer, ethylene and propylene, butene-1, pentene-1,
1, α- with 3 to 12 carbon atoms such as hexene-1, 4-methylpentene-1, octene-1, decene-1, etc.
Copolymers with olefins, copolymers of ethylene with polar group-containing monomers such as vinyl acetate, acrylic acid, ethyl acrylate, methacrylic acid, ethyl methacrylate, maleic acid, maleic anhydride,
Alternatively, examples thereof include polymers obtained by modifying the above-mentioned ethylene homopolymer or ethylene and α-olefin copolymer with unsaturated carboxylic acid or a derivative thereof such as acrylic acid or maleic acid, and mixtures thereof. The ethylene polymer of the present invention is produced by a radical polymerization method under high pressure. In other words, radical polymerization under high pressure means a polymerization pressure of 500
~4000 Kg/cm 2 , preferably 1000-3500 Kg/cm 2 , reaction temperature 50-400°C, preferably 100-350°C, in the presence of a free radical catalyst and a chain transfer agent, and if necessary auxiliaries. A method in which ethylene and aromatic compounds, and if desired, other monomers, are brought into contact and polymerized simultaneously or in stages in a mold or tubular reactor. When the aromatic compound is solid, it is supplied after being dissolved in an appropriate solvent. The free radical catalysts include customary initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, oxygen, and the like. Chain transfer agents include hydrogen, propylene, butene-1, C 1 to C 20 or higher saturated aliphatic hydrocarbons, and halogen-substituted hydrocarbons, such as
Methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C 1 ~
Saturated aliphatic alcohols of C 20 or more, such as methanol, ethanol, propanol and isopropanol, saturated aliphatic carbonyl compounds of C 1 to C 20 or more, such as acetone and methyl ethyl ketone, and other aromatic compounds such as toluene, Examples include compounds such as diethylbenzene and xylene. (E) Function and Effects of the Invention The ethylene polymer of the present invention produced as described above or the ethylene polymer composition obtained by blending the ethylene polymer with another ethylene polymer is as follows:
It has excellent dielectric strength as an electrical insulating material, and particularly has excellent breakdown strength against impact voltage in a high temperature range, so it is very useful as an insulating material for ultra-high voltage power cables. Further, the present invention is very superior in that it can be produced by a relatively simple process of high-pressure radical polymerization and does not require conventional complicated grafting and blending steps. In the present invention, olefin polymers (including copolymers), polyacrylonitrile, polyamide other than the other ethylene polymers may be used within the range that does not significantly impair the properties of the ethylene polymer or ethylene polymer composition. , polycarbonate,
Thermoplastic resins such as ABS resin, polystyrene, polyphenylene oxide, polyvinyl alcohol resin, vinyl chloride resin, vinylidene chloride resin, polyester resin, petroleum resin, coumaron-
Synthetic or natural rubber such as indene resin, ethylene-propylene copolymer rubber (EPR, EPDM, etc.), SBR, NBR, butadiene rubber, IIR, chloroprene rubber, isoprene rubber, styrene-butadiene-styrene block copolymer, etc. It can be used in combination with at least one of the following. On the other hand, in the present invention, organic/inorganic fillers,
Antioxidants, lubricants, various organic and inorganic pigments, UV inhibitors, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, antifoaming agents, flame retardants, crosslinking agents, flow improvers , weld strength improvers, nucleating agents, and other additives may be added to the extent that they do not significantly impair the effects of the present invention. Further, the ethylene polymer of the present invention or a composition containing the same may be used in an uncrosslinked state, or may be subjected to a crosslinking treatment if necessary. A normal crosslinking method is applied to the crosslinking method. (f) Examples Examples will be shown below. Examples 1-5 Internal volume fully substituted with nitrogen and ethylene
Approximately 1700 g of ethylene, the aromatic compounds shown in Table 1, and a predetermined amount of n-hexane were placed in a 3.8 metal autoclave reactor equipped with a stirrer, and di-tert-butyl peroxide as a polymerization initiator was added. Injection, polymerization temperature 170℃, polymerization pressure
Polymerization was carried out at 1600 Kg/cm 2 for 60 minutes to prepare various ethylene polymers containing units derived from aromatic compounds as shown in Table 1. A part of the produced polymer was dissolved in heated carbon tetrachloride and reprecipitated by pouring it into a large amount of acetone, and this operation was repeated several times to purify and then vacuum dry. The purified polymer is heated and compressed to a thickness of 500μm.
The number of units derived from aromatic compounds in each produced polymer was determined by infrared spectroscopic analysis using a compensation method using a sheet of ethylene polymer containing no aromatic compounds of the same thickness as a control. Quantification was performed. The amount of units derived from aromatic compounds contained in each produced polymer was determined mainly from the absorbance of absorption attributed to aromatic rings around 1600 cm -1 . Furthermore, the melt index of each produced polymer was measured in accordance with JIS K-6760. The impulse breaking strength of each produced polymer was measured at 20°C and 80°C, and the results are shown in Table 1. Incidentally, the impulse breaking strength was measured by the following method. The thickness of the sample is reduced by heating and compression molding.
It was made into a 50 μm sheet. A fixed electrode, a so-called Matskeon electrode (Fig. 1), was used as the electrode system. The electrode system substrate 4 is made of polymethyl methacrylate and has a hole with a diameter of 1/2 inch in its center. A 1/2 inch stainless steel bulb 1 was used as the electrode. Sample 2 was cut into approximately 8-10 mm squares and placed between the electrodes. 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 then placed in thermostats at 20°C and 80°C for measurements. The voltage waveform used for destruction was a negative polarity, 1 x 40 μS impulse waveform. The waveform was observed with an oscilloscope, and the data that broke at the wave front was used as data, and the average value of 20 points or more was taken. Comparative Examples 1 to 3 Ethylene polymers shown in Table 1 were prepared under the same polymerization conditions as in Example 1, and their impulse rupture strengths were measured, and the results are shown in Table 1.
【表】
評価結果
第１表から明らかなように実施例１〜５は本発
明のエチレン系重合体がエチレンホモポリマー
（比較例１）より耐破壊強度が、特に高温領域で
優れていることを示すものである。
一方、比較例２、３において、芳香族含量を本
発明の範囲外としたところ改良効果はみられなか
つた。[Table] Evaluation Results As is clear from Table 1, Examples 1 to 5 show that the ethylene polymer of the present invention has superior fracture resistance, especially in the high temperature range, compared to the ethylene homopolymer (Comparative Example 1). It shows. On the other hand, in Comparative Examples 2 and 3, no improvement effect was observed when the aromatic content was set outside the range of the present invention.
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、３…エポキシ樹
脂、４…ポリメチルメタクリレート製基板。
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, 3... Epoxy resin, 4... Polymethyl methacrylate substrate.
Claims (1)
２〜３環芳香族化合物であつて、一般式 (a) (b) (c) (d) (e) 〔式中、R1は炭素数が１または２のアルキ
レン基、R2，R3は水素原子、塩素原子または
炭素数１〜４の直鎖もしくは分岐のアルキル
基、R4，R5は水素原子またはメチル基をそれ
ぞれ表わす〕 にて示される化合物を除いた該２〜３環芳香族化
合物から選ばれた少なくとも１種の存在下、エチ
レンもしくはエチレンと他の単量体との混合物
を、重合圧力500〜4000Kg／cm2、重合温度50〜400
℃の条件下にて高圧ラジカル重合して得られた、
重合体成分として該芳香族化合物に由来する単位
を0.005〜１モル％含むことを特徴とするエチレ
ン系重合体から成る電気絶縁材料。[Scope of Claims] 1. A 2- to 3-ring aromatic compound having one carbon-carbon double bond in one molecule, which has the general formula (a) (b) (c) (d) (e) [In the formula, R 1 is an alkylene group having 1 or 2 carbon atoms, R 2 and R 3 are hydrogen atoms, chlorine atoms, or linear or branched alkyl groups having 1 to 4 carbon atoms, and R 4 and R 5 are hydrogen atoms. ethylene or a mixture of ethylene and other monomers is polymerized in the presence of at least one selected from the two- to three-ring aromatic compounds excluding the compounds represented by [representing atoms or methyl groups, respectively]. Pressure 500~4000Kg/ cm2 , polymerization temperature 50~400
Obtained by high-pressure radical polymerization under conditions of ℃,
An electrical insulating material made of an ethylene polymer, characterized in that it contains 0.005 to 1 mol% of units derived from the aromatic compound as a polymer component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4605985A JPS61206110A (en) | 1985-03-08 | 1985-03-08 | Insulating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4605985A JPS61206110A (en) | 1985-03-08 | 1985-03-08 | Insulating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61206110A JPS61206110A (en) | 1986-09-12 |
| JPH0552606B2 true JPH0552606B2 (en) | 1993-08-05 |
Family
ID=12736438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4605985A Granted JPS61206110A (en) | 1985-03-08 | 1985-03-08 | Insulating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61206110A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191803A (en) * | 1984-10-09 | 1986-05-09 | 日本石油化学株式会社 | Electric insulator |
-
1985
- 1985-03-08 JP JP4605985A patent/JPS61206110A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61206110A (en) | 1986-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4994539A (en) | Method for improving impulse destructive stength of electrical insulating materials | |
| US4871819A (en) | Ethylene copolymer and process for the production thereof | |
| EP0197303B1 (en) | Electrical insulating materials | |
| JPH0552606B2 (en) | ||
| JPH0552608B2 (en) | ||
| EP0180982B1 (en) | Ethylene copolymers | |
| US4736007A (en) | Novel ethylene copolymers | |
| JPS61206108A (en) | Insulating material | |
| EP0180797B1 (en) | Method for improving impulse breakdown strength of electrical insulating materials | |
| TW552273B (en) | Thermal stability of alpha-substituted acrylate graft copolymers | |
| JPS6345705A (en) | Electrically insulating material | |
| JPS61206111A (en) | Insulating material | |
| JPH0582004B2 (en) | ||
| JPH0552605B2 (en) | ||
| JPS61110907A (en) | Electric material | |
| JPH0641492B2 (en) | Novel ethylene copolymer | |
| JPS60144307A (en) | Curable impregnant composition | |
| JPS6210112A (en) | Ethylene copolymer and its production | |
| JPS6196604A (en) | Electric insulator | |
| JPS5989345A (en) | Electrical insulating composition | |
| JPH01117202A (en) | Radiation-resistant electrical wire and cable | |
| JPS6210113A (en) | Ethylene copolymer and its production | |
| JPH0481605B2 (en) | ||
| JPS6210117A (en) | Ethylene copolymer and its production | |
| JPH0481606B2 (en) |