JP2010222574A - Method for producing ethylene-alpha-olefin-nonconjugated polyene-based copolymer rubber composition - Google Patents
Method for producing ethylene-alpha-olefin-nonconjugated polyene-based copolymer rubber composition Download PDFInfo
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- JP2010222574A JP2010222574A JP2010039979A JP2010039979A JP2010222574A JP 2010222574 A JP2010222574 A JP 2010222574A JP 2010039979 A JP2010039979 A JP 2010039979A JP 2010039979 A JP2010039979 A JP 2010039979A JP 2010222574 A JP2010222574 A JP 2010222574A
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- Japan
- Prior art keywords
- olefin
- ethylene
- copolymer rubber
- polymerization
- general formula
- 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.)
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 118
- 229920001577 copolymer Polymers 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 150000004291 polyenes Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 88
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000005977 Ethylene Substances 0.000 claims abstract description 39
- 239000004711 α-olefin Substances 0.000 claims abstract description 34
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 24
- 125000005843 halogen group Chemical group 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 22
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- 239000011630 iodine Substances 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 9
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229920001821 foam rubber Polymers 0.000 abstract description 16
- -1 aluminum compound Chemical class 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 description 43
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000004073 vulcanization Methods 0.000 description 13
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 238000005187 foaming Methods 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- FZUNCODNAAEALR-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;1,1,3-trimethylcyclohexane Chemical compound CC1CCCC(C)(C)C1.CC(C)(C)OOC(C)(C)C FZUNCODNAAEALR-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 231100000987 absorbed dose Toxicity 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 2
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 description 1
- YHHHHJCAVQSFMJ-FNORWQNLSA-N (3e)-deca-1,3-diene Chemical compound CCCCCC\C=C\C=C YHHHHJCAVQSFMJ-FNORWQNLSA-N 0.000 description 1
- ZTJHDEXGCKAXRZ-FNORWQNLSA-N (3e)-octa-1,3,7-triene Chemical compound C=CCC\C=C\C=C ZTJHDEXGCKAXRZ-FNORWQNLSA-N 0.000 description 1
- HFVZWWUGHWNHFL-FMIVXFBMSA-N (4e)-5,9-dimethyldeca-1,4,8-triene Chemical compound CC(C)=CCC\C(C)=C\CC=C HFVZWWUGHWNHFL-FMIVXFBMSA-N 0.000 description 1
- TVEFFNLPYIEDLS-VQHVLOKHSA-N (4e)-deca-1,4,9-triene Chemical compound C=CCCC\C=C\CC=C TVEFFNLPYIEDLS-VQHVLOKHSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
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- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- JSCFNQDWXBNVBP-UHFFFAOYSA-N 1,2-diphenylguanidine;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 JSCFNQDWXBNVBP-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
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- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 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
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- VMSRVIHUFHQIAL-UHFFFAOYSA-M sodium;n,n-dimethylcarbamodithioate Chemical compound [Na+].CN(C)C([S-])=S VMSRVIHUFHQIAL-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 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
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- PZKZVLYBWITYEF-UHFFFAOYSA-L zinc;n,n-diethylcarbamothioate Chemical compound [Zn+2].CCN(CC)C([O-])=S.CCN(CC)C([O-])=S PZKZVLYBWITYEF-UHFFFAOYSA-L 0.000 description 1
- LAGTXXPOZSLGSF-UHFFFAOYSA-L zinc;n-butyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCCCN(C([S-])=S)C1=CC=CC=C1.CCCCN(C([S-])=S)C1=CC=CC=C1 LAGTXXPOZSLGSF-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
本発明は、エチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物の製造方法に関するものである。 The present invention relates to a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition.
自動車には、ウェザーストリップ、ドアーグラスランチャンネルなど、車体開口部周縁とドアやトランクリッド等の開口部開閉部材との間をシールして、外からの雨、風、音を防ぐシール材が用いられている。該シール材には、エチレン−α−オレフィン−非共役ジエン系共重合体ゴムからなるゴム発泡体が、広く用いられている。 For automobiles, sealing materials are used to prevent rain, wind, and sound from the outside, such as weatherstrips and doorgrass run channels, that seal between the periphery of the vehicle body opening and the opening and closing members such as doors and trunk lids. ing. A rubber foam made of ethylene-α-olefin-nonconjugated diene copolymer rubber is widely used as the sealing material.
例えば、特許文献1には、結晶性ポリプロピレン樹脂が配合された特定のエチレン−プロピレン−非共役ジエン共重合体ゴムを加硫発泡させたゴム発泡体が提案されている。また、特許文献2には、低エチレン単位量かつ低ヨウ素価のエチレン−プロピレン−非共役ジエン共重合体ゴムと高エチレン単位量かつ高ヨウ素価のエチレン−1−ブテン−非共役ジエン共重合体ゴムとを溶融混合した組成物を、加硫発泡させたゴム発泡体が提案されている。 For example, Patent Document 1 proposes a rubber foam obtained by vulcanizing and foaming a specific ethylene-propylene-nonconjugated diene copolymer rubber blended with a crystalline polypropylene resin. Patent Document 2 discloses a low ethylene unit amount and low iodine number ethylene-propylene-nonconjugated diene copolymer rubber and a high ethylene unit amount and high iodine number ethylene-1-butene-nonconjugated diene copolymer. A rubber foam obtained by vulcanizing and foaming a composition obtained by melting and mixing rubber has been proposed.
しかしながら、従来のエチレン−プロピレン−非共役ジエン共重合体ゴムからなる発泡体は、吸水率が高くなることがあり、雨水などのシール性には、未だ十分満足のいくものではなかった。
かかる状況のもと、本発明が解決しようとする課題は、低吸水性に優れるゴム発泡体が得られる共重合体ゴム組成物の製造方法を提供することにある。
However, the foam made of the conventional ethylene-propylene-nonconjugated diene copolymer rubber may have a high water absorption rate, and the sealing properties such as rainwater have not been sufficiently satisfactory.
Under such circumstances, a problem to be solved by the present invention is to provide a method for producing a copolymer rubber composition from which a rubber foam excellent in low water absorption can be obtained.
本発明は、2つ以上の反応槽が直列に連結した重合反応装置を用いて、連続溶液重合でエチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物を製造する方法であって、下記重合工程(A)および重合工程(B)を有するエチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物の製造方法にかかるものである。
重合工程(A):
下記一般式(1)で表されるバナジウム化合物と下記一般式(2)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒の存在下、エチレンとα−オレフィンと非共役ポリエンとを共重合する工程
一般式(1)
VO(OR)mX3-m(式中、Rは炭素原子数1〜8の直鎖状炭化水素基を表し、Xはハロゲン原子を表し、mは0≦m≦3を充足する数を表す。)
一般式(2)
R”jAlX”3-j(式中、R”は炭化水素基を表し、X”はハロゲン原子を表し、jは0<j≦3を充足する数を表す。)
重合工程(B):
下記一般式(3)で表されるバナジウム化合物と下記一般式(4)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒の存在下、エチレンとα−オレフィンとを共重合、あるいは、エチレンとα−オレフィンと非共役ポリエンとを共重合する工程
一般式(3)
VO(OR’)nX’3-n(式中、R’は炭素原子数3〜8の第2級または第3級炭化水素基を表し、X’はハロゲン原子を表し、nは0<n≦3を充足する数を表す。)
一般式(4)
R'''kAlX'''3-k(式中、R'''は炭化水素基を表し、X'''はハロゲン原子を表し、kは0<k≦3を充足する数を表す。)
The present invention is a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition by continuous solution polymerization using a polymerization reactor in which two or more reaction vessels are connected in series, The present invention relates to a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition having the following polymerization step (A) and polymerization step (B).
Polymerization step (A):
In the presence of a polymerization catalyst comprising a vanadium compound represented by the following general formula (1) and an organoaluminum compound represented by the following general formula (2) as a polymerization catalyst component, ethylene, an α-olefin and a non-conjugated polyene are produced. Step of copolymerization General formula (1)
VO (OR) m X 3-m (wherein R represents a linear hydrocarbon group having 1 to 8 carbon atoms, X represents a halogen atom, and m represents a number satisfying 0 ≦ m ≦ 3) To express.)
General formula (2)
R ″ j AlX ″ 3-j (wherein R ″ represents a hydrocarbon group, X ″ represents a halogen atom, and j represents a number satisfying 0 <j ≦ 3).
Polymerization step (B):
In the presence of a polymerization catalyst comprising a vanadium compound represented by the following general formula (3) and an organoaluminum compound represented by the following general formula (4) as a polymerization catalyst component, ethylene and an α-olefin are copolymerized, or Step of copolymerizing ethylene, α-olefin and non-conjugated polyene General formula (3)
VO (OR ′) n X ′ 3-n (wherein R ′ represents a secondary or tertiary hydrocarbon group having 3 to 8 carbon atoms, X ′ represents a halogen atom, and n is 0 < It represents the number that satisfies n ≦ 3.)
General formula (4)
R ′ ″ k AlX ′ ″ 3-k (wherein R ′ ″ represents a hydrocarbon group, X ′ ″ represents a halogen atom, and k represents a number satisfying 0 <k ≦ 3) .)
本発明により、低吸水性に優れるゴム発泡体が得られる共重合体ゴム組成物の製造方法を提供することができる。 According to the present invention, it is possible to provide a method for producing a copolymer rubber composition from which a rubber foam excellent in low water absorption can be obtained.
本発明は、2つ以上の反応槽が直列に連結した重合反応装置を用いて、連続溶液重合でエチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物を製造する方法であり、下記重合工程(A)および重合工程(B)を有する。 The present invention is a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition by continuous solution polymerization using a polymerization reactor in which two or more reaction vessels are connected in series. It has a polymerization step (A) and a polymerization step (B).
重合工程(A):
下記一般式(1)で表されるバナジウム化合物と下記一般式(2)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒の存在下、エチレンとα−オレフィンと非共役ポリエンとを共重合する工程
一般式(1)
VO(OR)mX3-m(式中、Rは炭素原子数1〜8の直鎖状炭化水素基を表し、Xはハロゲン原子を表し、mは0≦m≦3を充足する数を表す。)
一般式(2)
R”jAlX”3-j(式中、R”は炭化水素基を表し、X”はハロゲン原子を表し、jは0<j≦3を充足する数を表す。)
Polymerization step (A):
In the presence of a polymerization catalyst comprising a vanadium compound represented by the following general formula (1) and an organoaluminum compound represented by the following general formula (2) as a polymerization catalyst component, ethylene, an α-olefin and a non-conjugated polyene are produced. Step of copolymerization General formula (1)
VO (OR) m X 3-m (wherein R represents a linear hydrocarbon group having 1 to 8 carbon atoms, X represents a halogen atom, and m represents a number satisfying 0 ≦ m ≦ 3) To express.)
General formula (2)
R ″ j AlX ″ 3-j (wherein R ″ represents a hydrocarbon group, X ″ represents a halogen atom, and j represents a number satisfying 0 <j ≦ 3).
重合工程(B):
下記一般式(3)で表されるバナジウム化合物と下記一般式(4)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒の存在下、エチレンとα−オレフィンとを共重合、あるいは、エチレンとα−オレフィンと非共役ポリエンとを共重合する工程
一般式(3)
VO(OR’)nX’3-n(式中、R’は炭素原子数3〜8の第2級または第3級炭化水素基を表し、X’はハロゲン原子を表し、nは0<n≦3を充足する数を表す。)
一般式(4)
R'''kAlX'''3-k(式中、R'''は炭化水素基を表し、X'''はハロゲン原子を表し、kは0<k≦3を充足する数を表す。)
Polymerization step (B):
In the presence of a polymerization catalyst comprising a vanadium compound represented by the following general formula (3) and an organoaluminum compound represented by the following general formula (4) as a polymerization catalyst component, ethylene and an α-olefin are copolymerized, or Step of copolymerizing ethylene, α-olefin and non-conjugated polyene General formula (3)
VO (OR ′) n X ′ 3-n (wherein R ′ represents a secondary or tertiary hydrocarbon group having 3 to 8 carbon atoms, X ′ represents a halogen atom, and n is 0 < It represents the number that satisfies n ≦ 3.)
General formula (4)
R ′ ″ k AlX ′ ″ 3-k (wherein R ′ ″ represents a hydrocarbon group, X ′ ″ represents a halogen atom, and k represents a number satisfying 0 <k ≦ 3) .)
α−オレフィンとしては、炭素原子数3〜20のα−オレフィンが好ましく、プロピレン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン等の直鎖状α−オレフィン;3−メチル−1−ブテン、3−メチル−1−ペンテン、4−メチル−1−ペンテン等の分岐状α−オレフィンがあげられる。これらは、単独で使用されてもよく、二種以上を併用されてもよい。α−オレフィンとしては、好ましくは、プロピレン、1−ブテンであり、より好ましくはプロピレンである。 The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. Linear α-olefins; branched α-olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and the like. These may be used alone or in combination of two or more. The α-olefin is preferably propylene or 1-butene, more preferably propylene.
非共役ポリエンとしては、たとえば、1,4−ヘキサジエン、1,6−オクタジエン、2−メチル−1,5−ヘキサジエン、6−メチル−1,5−ヘプタジエン、7−メチル−1,6−オクタジエン等の鎖状非共役ジエン;シクロヘキサジエン、ジシクロペンタジエン、メチルテトラインデン、5−ビニル−2−ノルボルネン、5−(2−プロペニル)−2−ノルボルネン、5−(3−ブテニル)−2−ノルボルネン、5−(4−ペンテニル)−2−ノルボルネン、5−(5−ヘキセニル)−2−ノルボルネン、5−(5−ヘプテニル)−2−ノルボルネン、5−(7−オクテニル)−2−ノルボルネン、5−メチレン−2−ノルボルネン、5−エチリデン−2−ノルボルネン、6−クロロメチル−5−イソプロペニル−2−ノルボルネン等の環状非共役ジエン;2,3−ジイソプロピリデン−5−ノルボルネン、2−エチリデン−3−イソプロピリデン−5−ノルボルネン、2−プロペニル−2,2−ノルボルナジエン、1,3,7−オクタトリエン、1,4,9−デカトリエン、6,10−ジメチル−1,5,9−ウンデカトリエン、5,9−ジメチル−1,4,8−デカトリエン、4−エチリデン−8−メチル−1,7−ノナジエン、13−エチル−9−メチル−1,9,12−ペンタデカトリエン、8,14,16−トリメチル−1,7,14−ヘキサデカトリエン、4−エチリデン−12−メチル−1,11−ペンタデカジエン等のトリエンがあげられる。これらは、単独で使用されてもよく、二種以上を併用されてもよい。非共役ポリエンとしては、5−エチリデン−2−ノルボルネン、ジシクロペンタジエンおよび5−ビニル−2−ノルボルネンからなる非共役ポリエン群から選ばれる少なくとも1種の化合物が好ましい。 Examples of the non-conjugated polyene include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, and the like. A chain non-conjugated diene: cyclohexadiene, dicyclopentadiene, methyltetraindene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- Methylene-2-norbornene, 5-ethylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, etc. Cyclic non-conjugated dienes; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 1,3,7-octatriene, 1 , 4,9-decatriene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 8,14,16-trimethyl-1,7,14-hexadecatriene, 4-ethylidene-12-methyl-1,11-penta Examples include trienes such as decadiene. These may be used alone or in combination of two or more. The nonconjugated polyene is preferably at least one compound selected from the group of nonconjugated polyenes consisting of 5-ethylidene-2-norbornene, dicyclopentadiene and 5-vinyl-2-norbornene.
重合工程(A)で用いられる重合触媒は、一般式(1)で表されるバナジウム化合物と一般式(2)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒である。
一般式(1)
VO(OR)mX3-m(式中、Rは炭素原子数1〜8の直鎖状炭化水素基を表し、Xはハロゲン原子を表し、mは0≦m≦3を充足する数を表す。)
一般式(2)
R”jAlX”3-j(式中、R”は炭化水素基を表し、X”はハロゲン原子を表し、jは0<j≦3を充足する数を表す。)
The polymerization catalyst used in the polymerization step (A) is a polymerization catalyst having a vanadium compound represented by the general formula (1) and an organoaluminum compound represented by the general formula (2) as polymerization catalyst components.
General formula (1)
VO (OR) m X 3-m (wherein R represents a linear hydrocarbon group having 1 to 8 carbon atoms, X represents a halogen atom, and m represents a number satisfying 0 ≦ m ≦ 3) To express.)
General formula (2)
R ″ j AlX ″ 3-j (wherein R ″ represents a hydrocarbon group, X ″ represents a halogen atom, and j represents a number satisfying 0 <j ≦ 3).
一般式(1)において、Rは炭素原子数1〜8の直鎖状炭化水素基を表し、例えば、メチル基、エチル基、n−プロピル基、n−ブチル基、n−ペンチル基、n−ヘキシル基などの炭素原子数1〜8の直鎖状アルキル基をあげることができる。好ましくは、炭素原子数1〜3の直鎖状アルキル基である。Xはハロゲン原子を表し、塩素原子などをあげることができる。また、mは0≦m≦3を充足する数を表し、好ましくは0≦m≦2を充足する数である。 In the general formula (1), R represents a linear hydrocarbon group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- Examples thereof include straight-chain alkyl groups having 1 to 8 carbon atoms such as hexyl group. Preferably, it is a linear alkyl group having 1 to 3 carbon atoms. X represents a halogen atom, and examples thereof include a chlorine atom. M represents a number satisfying 0 ≦ m ≦ 3, and preferably a number satisfying 0 ≦ m ≦ 2.
一般式(1)で表されるバナジウム化合物としては、VOCl3、VO(OCH3)Cl2、VO(OC2H5)Cl2、VO(O(n-C3H7))Cl2、VO(O(n-C4H9))Cl2、VO(O(n-C5H11))Cl2、VO(O(n-C6H13))Cl2、VO(O(n-C7H15))Cl2、VO(O(n-C8H17))Cl2、VO(OCH3)0.5Cl2.5、VO(OC2H5)0.5Cl2.5、VO(O(n-C3H7))0.5Cl2.5、VO(O(n-C4H9))0.5Cl2.5、VO(O(n-C5H11))0.5Cl2.5、VO(O(n-C6H13))0.5Cl2.5、VO(O(n-C7H15))0.5Cl2.5、VO(O(n-C8H17))0.5Cl2.5、VO(OCH3)1.5Cl0.5、VO(OC2H5)1.5Cl0.5、VO(O(n-C3H7))1.5Cl0.5、VO(O(n-C4H9))1.5Cl0.5、VO(O(n-C5H11))1.5Cl0.5、VO(O(n-C6H13))1.5Cl0.5、VO(O(n-C7H15))1.5Cl0.5、VO(O(n-C8H17))1.5Cl0.5、VO(OCH3)0.8Cl2.2、VO(OC2H5)0.8Cl2.2、VO(O(n-C3H7))0.8Cl2.2、VO(O(n-C4H9))0.8Cl2.2、VO(O(n-C5H11))0.8Cl2.2、VO(O(n-C6H13))0.8Cl2.2、VO(O(n-C7H15))0.8Cl2.2、VO(O(n-C8H17))0.8Cl2.2等をあげることができる。好ましくは、VOCl3、VO(OC2H5)Cl2、VO(OC2H5)0.5Cl2.5、VO(OC2H5)1.5Cl0.5、VO(OC2H5)0.8Cl2.2である。 Examples of the vanadium compound represented by the general formula (1) include VOCl 3 , VO (OCH 3 ) Cl 2 , VO (OC 2 H 5 ) Cl 2 , VO (O (n—C 3 H 7 )) Cl 2 , VO (O (n-C 4 H 9)) Cl 2, VO (O (n-C 5 H 11)) Cl 2, VO (O (n-C 6 H 13)) Cl 2, VO (O (n -C 7 H 15)) Cl 2 , VO (O (n-C 8 H 17)) Cl 2, VO (OCH 3) 0.5 Cl 2.5, VO (OC 2 H 5) 0.5 Cl 2.5, VO (O (n -C 3 H 7)) 0.5 Cl 2.5, VO (O (n-C 4 H 9)) 0.5 Cl 2.5, VO (O (n-C 5 H 11)) 0.5 Cl 2.5, VO (O (n-C 6 H 13)) 0.5 Cl 2.5 , VO (O (n-C 7 H 15)) 0.5 Cl 2.5, VO (O (n-C 8 H 17)) 0.5 Cl 2.5, VO (OCH 3) 1.5 Cl 0.5, VO (OC 2 H 5 ) 1.5 Cl 0.5 , VO (O (n—C 3 H 7 )) 1.5 C l 0.5 , VO (O (n—C 4 H 9 )) 1.5 Cl 0.5 , VO (O (n—C 5 H 11 )) 1.5 Cl 0.5 , VO (O (n—C 6 H 13 )) 1.5 Cl 0.5 , VO (O (n-C 7 H 15)) 1.5 Cl 0.5, VO (O (n-C 8 H 17)) 1.5 Cl 0.5, VO (OCH 3) 0.8 Cl 2.2, VO (OC 2 H 5) 0.8 Cl 2.2 , VO (O (n—C 3 H 7 )) 0.8 Cl 2.2 , VO (O (n—C 4 H 9 )) 0.8 Cl 2.2 , VO (O (n—C 5 H 11 )) 0.8 Cl 2.2 , VO (O (n-C 6 H 13)) 0.8 Cl 2.2, VO (O (n-C 7 H 15)) 0.8 Cl 2.2, the VO (O (n-C 8 H 17)) 0.8 Cl 2.2 , etc. I can give you. Preferably, VOCl 3 , VO (OC 2 H 5 ) Cl 2 , VO (OC 2 H 5 ) 0.5 Cl 2.5 , VO (OC 2 H 5 ) 1.5 Cl 0.5 , VO (OC 2 H 5 ) 0.8 Cl 2.2 .
一般式(1)で表されるバナジウム化合物において、mが0を超える化合物は、VOX3とROHとを所定のモル比で反応させる方法により得られる。例えば、VOCl3とC2H5OHとの反応は、次式で示される。
VOCl3 + m・C2H5OH → VO(OC2H5)mCl3-m + m・HCl
In the vanadium compound represented by the general formula (1), a compound in which m exceeds 0 is obtained by a method in which VOX 3 and ROH are reacted at a predetermined molar ratio. For example, the reaction between VOCl 3 and C 2 H 5 OH is represented by the following formula.
VOCl 3 + m · C 2 H 5 OH → VO (OC 2 H 5 ) m Cl 3-m + m · HCl
一般式(2)において、R”は炭化水素基を表し、例えば、メチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、iso−ブチル基、ペンチル基、ヘキシル基などの炭素原子数1〜10のアルキル基をあげることができる。X”はハロゲン原子を表し、塩素原子などをあげることができる。また、jは0<j≦3を充足する数を表し、好ましくは1≦m≦2を充足する数である。 In the general formula (2), R ″ represents a hydrocarbon group, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a pentyl group, a hexyl group, etc. And an alkyl group having 1 to 10 carbon atoms, X ″ represents a halogen atom, such as a chlorine atom. J represents a number satisfying 0 <j ≦ 3, and preferably a number satisfying 1 ≦ m ≦ 2.
一般式(2)で表される有機アルミニウム化合物としては、(C2H5)2AlCl、(n-C4H9)2AlCl、(iso-C4H9)2AlCl、(n-C6H13)2AlCl、(n-C2H5)1.5AlCl1.5、(n-C4H9)1.5AlCl1.5、(iso-C4H9)1.5AlCl1.5、(n-C6H13)1.5AlCl1.5、C2H5AlCl2、(n-C4H9)AlCl2、(iso-C4H9)AlCl2、(n-C6H13)AlCl2等が例示できる。好ましくは、(C2H5)2AlCl、(n-C2H5)1.5AlCl1.5である。 Examples of the organoaluminum compound represented by the general formula (2) include (C 2 H 5 ) 2 AlCl, (n-C 4 H 9 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, (n-C 6 H 13 ) 2 AlCl, (n-C 2 H 5 ) 1.5 AlCl 1.5 , (n-C 4 H 9 ) 1.5 AlCl 1.5 , (iso-C 4 H 9 ) 1.5 AlCl 1.5 , (n-C 6 H 13 ) 1.5 AlCl 1.5 , C 2 H 5 AlCl 2 , (n—C 4 H 9 ) AlCl 2 , (iso-C 4 H 9 ) AlCl 2 , (n—C 6 H 13 ) AlCl 2 and the like can be exemplified. Preferred are (C 2 H 5 ) 2 AlCl, (n—C 2 H 5 ) 1.5 AlCl 1.5 .
上記有機アルミニウム化合物の使用量と上記バナジウム化合物の使用量のモル比(有機アルミニウム化合物のモル/バナジウム化合物のモル)は、好ましくは、2.5〜50である。 The molar ratio of the amount of the organoaluminum compound used to the amount of the vanadium compound used (mol of organoaluminum compound / mol of vanadium compound) is preferably 2.5 to 50.
重合溶媒としては、プロパン、ブタン、イソブタン、ペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン等の脂環族炭化水素等の不活性溶媒を用いることができる。 As the polymerization solvent, inert solvents such as aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane; and alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used.
重合温度は、通常、−20〜200℃であり、好ましくは0〜150℃であり、より好ましくは20〜120℃である。また、重合圧力は、通常、0.1〜10MPaであり、好ましくは0.1〜5MPaであり、より好ましくは0.1〜3MPaである。 The polymerization temperature is usually from -20 to 200 ° C, preferably from 0 to 150 ° C, more preferably from 20 to 120 ° C. The polymerization pressure is usually 0.1 to 10 MPa, preferably 0.1 to 5 MPa, and more preferably 0.1 to 3 MPa.
重合工程(A)においては、製造される共重合体の分子量を調節するために、水素等の分子量調節剤を用いてもよい。 In the polymerization step (A), a molecular weight regulator such as hydrogen may be used to adjust the molecular weight of the produced copolymer.
重合工程(A)で製造される共重合体は、エチレン−α−オレフィン−非共役ポリエン共重合体ゴムである。例えば、エチレン−プロピレン−5−エチリデン−2−ノルボルネン共重合体ゴム、エチレン−プロピレン−ジシクロペンタジエン共重合体ゴム、エチレン−プロピレン−5−ビニル−2−ノルボルネン共重合体ゴム、エチレン−1−ブテン−5−エチリデン−2−ノルボルネン共重合体ゴム、エチレン−1−ブテン−ジシクロペンタジエン共重合体ゴム、エチレン−1−ブテン−5−ビニル−2−ノルボルネン共重合体ゴムをあげることができる。 The copolymer produced in the polymerization step (A) is an ethylene-α-olefin-nonconjugated polyene copolymer rubber. For example, ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, ethylene-propylene-5-vinyl-2-norbornene copolymer rubber, ethylene-1- Examples include butene-5-ethylidene-2-norbornene copolymer rubber, ethylene-1-butene-dicyclopentadiene copolymer rubber, and ethylene-1-butene-5-vinyl-2-norbornene copolymer rubber. .
重合工程(A)で製造される共重合体ゴム(共重合体ゴム(A))のエチレンに基づく単量体単位(エチレン単位)の含有量は、好ましくは、40モル%以上70モル%以下であり、より好ましくは、45モル%以上70モル%以下であり、更に好ましくは、50モル%以上70モル%以下であり、α−オレフィンに基づく単量体単位(α−オレフィン単位)の含有量は、好ましくは、60モル%以下30モル%以上であり、より好ましくは、55モル%以下30モル%以上であり、更に好ましくは、50モル%以下30モル%以上である。ただし、エチレンに基づく単量体単位とα−オレフィンに基づく単量体単位との合計を100モル%とする。 The content of the monomer unit (ethylene unit) based on ethylene in the copolymer rubber (copolymer rubber (A)) produced in the polymerization step (A) is preferably 40 mol% or more and 70 mol% or less. More preferably, it is 45 mol% or more and 70 mol% or less, More preferably, it is 50 mol% or more and 70 mol% or less, and contains monomer units (α-olefin units) based on α-olefins The amount is preferably 60 mol% or less and 30 mol% or more, more preferably 55 mol% or less and 30 mol% or more, and further preferably 50 mol% or less and 30 mol% or more. However, the total of the monomer unit based on ethylene and the monomer unit based on α-olefin is 100 mol%.
共重合体ゴム(A)のヨウ素価(g/100gポリマー)は、好ましくは1以上50以下であり、より好ましくは5以上45以下である。 The iodine value (g / 100 g polymer) of the copolymer rubber (A) is preferably 1 or more and 50 or less, more preferably 5 or more and 45 or less.
共重合体ゴム(A)の極限粘度[η]は、好ましくは0.5dl/g以上10dl/g以下であり、より好ましくは1dl/g以上8dl/g以下であり、更に好ましくは1.5dl/g以上5dl/g以下である。該極限粘度[η]は、テトラリン中、135℃で測定される。 The intrinsic viscosity [η] of the copolymer rubber (A) is preferably 0.5 dl / g or more and 10 dl / g or less, more preferably 1 dl / g or more and 8 dl / g or less, further preferably 1.5 dl. / G or more and 5 dl / g or less. The intrinsic viscosity [η] is measured at 135 ° C. in tetralin.
重合工程(B)で用いられる重合触媒は、一般式(3)で表されるバナジウム化合物と一般式(4)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒である。
一般式(3)
VO(OR’)nX’3-n(式中、R’は炭素原子数3〜8の第2級または第3級炭化水素基を表し、X’はハロゲン原子を表し、nは0<n≦3を充足する数を表す。)
一般式(4)
R'''kAlX'''3-k(式中、R'''は炭化水素基を表し、X'''はハロゲン原子を表し、kは0<k≦3を充足する数を表す。)
The polymerization catalyst used in the polymerization step (B) is a polymerization catalyst having a vanadium compound represented by the general formula (3) and an organoaluminum compound represented by the general formula (4) as polymerization catalyst components.
General formula (3)
VO (OR ′) n X ′ 3-n (wherein R ′ represents a secondary or tertiary hydrocarbon group having 3 to 8 carbon atoms, X ′ represents a halogen atom, and n is 0 < It represents the number that satisfies n ≦ 3.)
General formula (4)
R ′ ″ k AlX ′ ″ 3-k (wherein R ′ ″ represents a hydrocarbon group, X ′ ″ represents a halogen atom, and k represents a number satisfying 0 <k ≦ 3) .)
一般式(3)において、R’は炭素原子数3〜8の第2級または第3級炭化水素基を表し、例えば、iso−プロピル基、sec−ブチル基、tert−ブチル基などの炭素原子数3〜8の第2級または第3級アルキル基をあげることができる。好ましくは、炭素原子数3〜4の第2級または第3級アルキル基である。X’はハロゲン原子を表し、塩素原子などをあげることができる。また、nは0<n≦3を充足する数を表し、好ましくは0.5<n≦2を充足する数である。 In the general formula (3), R ′ represents a secondary or tertiary hydrocarbon group having 3 to 8 carbon atoms, for example, a carbon atom such as an iso-propyl group, a sec-butyl group, or a tert-butyl group. Examples thereof include secondary or tertiary alkyl groups of 3 to 8. Preferably, it is a secondary or tertiary alkyl group having 3 to 4 carbon atoms. X ′ represents a halogen atom, and examples thereof include a chlorine atom. N represents a number satisfying 0 <n ≦ 3, and preferably 0.5 <n ≦ 2.
一般式(3)で表されるバナジウム化合物としては、VO(O(iso-C3H7))Cl2、VO(O(iso-C3H7))0.5Cl2.5、VO(O(iso-C3H7))1.5Cl0.5、VO(O(iso-C3H7))0.8Cl2.2等をあげることができる。好ましくは、VO(O(iso-C3H7))0.8Cl2.2である。 Examples of the vanadium compound represented by the general formula (3) include VO (O (iso-C 3 H 7 )) Cl 2 , VO (O (iso-C 3 H 7 )) 0.5 Cl 2.5 , VO (O (iso -C 3 H 7 )) 1.5 Cl 0.5 , VO (O (iso-C 3 H 7 )) 0.8 Cl 2.2 and the like. Preferably, VO (O (iso-C 3 H 7)) is 0.8 Cl 2.2.
一般式(3)で表されるバナジウム化合物は、VOX’3とR’OHとを所定のモル比で反応させる方法により得られる。例えば、VOCl3とiso-C3H7OHとの反応は、次式で示される。
VOCl3 + n・iso-C3H7OH
→ VO(O(iso-C3H7)nCl3-n + n・HCl
The vanadium compound represented by the general formula (3) is obtained by a method in which VOX ′ 3 and R′OH are reacted at a predetermined molar ratio. For example, the reaction between VOCl 3 and iso-C 3 H 7 OH is represented by the following formula.
VOCl 3 + n · iso-C 3 H 7 OH
→ VO (O (iso-C 3 H 7) n Cl 3-n + n · HCl
一般式(4)において、R'''は炭化水素基を表し、例えば、メチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、iso−ブチル基、ペンチル基、ヘキシル基などの炭素原子数1〜10のアルキル基をあげることができる。X'''はハロゲン原子を表し、塩素原子などをあげることができる。また、kは0<k≦3を充足する数を表し、好ましくは1≦k≦2を充足する数である。 In the general formula (4), R ′ ″ represents a hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, pentyl group, hexyl. Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a group. X ″ ′ represents a halogen atom, and examples thereof include a chlorine atom. K represents a number satisfying 0 <k ≦ 3, and preferably a number satisfying 1 ≦ k ≦ 2.
一般式(4)で表される有機アルミニウム化合物としては、(C2H5)2AlCl、(n-C4H9)2AlCl、(iso-C4H9)2AlCl、(n-C6H13)2AlCl、(n-C2H5)1.5AlCl1.5、(n-C4H9)1.5AlCl1.5、(iso-C4H9)1.5AlCl1.5、(n-C6H13)1.5AlCl1.5、C2H5AlCl2、(n-C4H9)AlCl2、(iso-C4H9)AlCl2、(n-C6H13)AlCl2等が例示できる。好ましくは、(C2H5)2AlCl、C2H5AlCl2である。 Examples of the organoaluminum compound represented by the general formula (4) include (C 2 H 5 ) 2 AlCl, (n-C 4 H 9 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, (n-C 6 H 13 ) 2 AlCl, (n-C 2 H 5 ) 1.5 AlCl 1.5 , (n-C 4 H 9 ) 1.5 AlCl 1.5 , (iso-C 4 H 9 ) 1.5 AlCl 1.5 , (n-C 6 H 13 ) 1.5 AlCl 1.5 , C 2 H 5 AlCl 2 , (n—C 4 H 9 ) AlCl 2 , (iso-C 4 H 9 ) AlCl 2 , (n—C 6 H 13 ) AlCl 2 and the like can be exemplified. Preferred are (C 2 H 5 ) 2 AlCl and C 2 H 5 AlCl 2 .
上記有機アルミニウム化合物の使用量と上記バナジウム化合物の使用量のモル比(有機アルミニウム化合物のモル/バナジウム化合物のモル)は、好ましくは、2.5〜50である。 The molar ratio of the amount of the organoaluminum compound used to the amount of the vanadium compound used (mol of organoaluminum compound / mol of vanadium compound) is preferably 2.5 to 50.
重合溶媒としては、プロパン、ブタン、イソブタン、ペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン等の脂環族炭化水素等の不活性溶媒を用いることができる。 As the polymerization solvent, inert solvents such as aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane; and alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used.
重合温度は、通常、−20〜200℃であり、好ましくは0〜150℃であり、より好ましくは20〜120℃である。また、重合圧力は、通常、0.1〜10MPaであり、好ましくは0.1〜5MPaであり、より好ましくは0.1〜3MPaである。 The polymerization temperature is usually from -20 to 200 ° C, preferably from 0 to 150 ° C, more preferably from 20 to 120 ° C. The polymerization pressure is usually 0.1 to 10 MPa, preferably 0.1 to 5 MPa, and more preferably 0.1 to 3 MPa.
重合工程(B)においては、製造される共重合体の分子量を調節するために、水素等の分子量調節剤を用いてもよい。 In the polymerization step (B), a molecular weight regulator such as hydrogen may be used to adjust the molecular weight of the produced copolymer.
重合工程(B)で製造される共重合体は、エチレン−α−オレフィン系共重合体ゴムであり、エチレン−α−オレフィン共重合体ゴム、エチレン−α−オレフィン−非共役ポリエン共重合体ゴムをあげることができる。エチレン−α−オレフィン共重合体ゴムとしては、例えば、エチレン−プロピレン共重合体ゴム、エチレン−1−ブテン共重合体ゴム、エチレン−1−ヘキセン共重合体ゴム、エチレン−1−オクテン共重合体ゴム、エチレン−プロピレン−1−ブテン共重合体ゴム、エチレン−プロピレン−1−ヘキセン共重合体ゴムをあげることができる。エチレン−α−オレフィン−非共役ポリエン共重合体ゴムとしては、例えば、エチレン−プロピレン−5−エチリデン−2−ノルボルネン共重合体ゴム、エチレン−プロピレン−ジシクロペンタジエン共重合体ゴム、エチレン−プロピレン−5−ビニル−2−ノルボルネン共重合体ゴム、エチレン−1−ブテン−5−エチリデン−2−ノルボルネン共重合体ゴム、エチレン−1−ブテン−ジシクロペンタジエン共重合体ゴム、エチレン−1−ブテン−5−ビニル−2−ノルボルネン共重合体ゴムをあげることができる。 The copolymer produced in the polymerization step (B) is an ethylene-α-olefin copolymer rubber, an ethylene-α-olefin copolymer rubber, an ethylene-α-olefin-nonconjugated polyene copolymer rubber. Can give. Examples of the ethylene-α-olefin copolymer rubber include ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer. Examples thereof include rubber, ethylene-propylene-1-butene copolymer rubber, and ethylene-propylene-1-hexene copolymer rubber. Examples of the ethylene-α-olefin-nonconjugated polyene copolymer rubber include ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, and ethylene-propylene- 5-vinyl-2-norbornene copolymer rubber, ethylene-1-butene-5-ethylidene-2-norbornene copolymer rubber, ethylene-1-butene-dicyclopentadiene copolymer rubber, ethylene-1-butene- Examples thereof include 5-vinyl-2-norbornene copolymer rubber.
重合工程(B)で製造される共重合体ゴム(共重合体ゴム(B))のエチレンに基づく単量体単位(エチレン単位)の含有量は、好ましくは、70モル%を超え95モル%以下であり、より好ましくは、73モル%以上92モル%以下であり、更に好ましくは、75モル%以上90モル%以下であり、α−オレフィンに基づく単量体単位(α−オレフィン単位)の含有量は、好ましくは、30モル%未満5モル%以上であり、より好ましくは、27モル%以下8モル%以上であり、更に好ましくは、25モル%以下10モル%以上である。ただし、エチレンに基づく単量体単位とα−オレフィンに基づく単量体単位との合計を100モル%とする。 The content of monomer units (ethylene units) based on ethylene in the copolymer rubber (copolymer rubber (B)) produced in the polymerization step (B) is preferably more than 70 mol% and 95 mol% Or less, more preferably 73 mol% or more and 92 mol% or less, still more preferably 75 mol% or more and 90 mol% or less, and the monomer unit based on α-olefin (α-olefin unit). The content is preferably less than 30 mol% and 5 mol% or more, more preferably 27 mol% or less and 8 mol% or more, and further preferably 25 mol% or less and 10 mol% or more. However, the total of the monomer unit based on ethylene and the monomer unit based on α-olefin is 100 mol%.
共重合体ゴム(B)のヨウ素価(g/100gポリマー)は、好ましくは0以上50以下であり、より好ましくは5以上45以下である。 The iodine value (g / 100 g polymer) of the copolymer rubber (B) is preferably 0 or more and 50 or less, and more preferably 5 or more and 45 or less.
共重合体ゴム(B)の極限粘度[η]は、好ましくは0.5dl/g以上10dl/g以下であり、より好ましくは1dl/g以上8dl/g以下であり、更に好ましくは1.5dl/g以上5dl/g以下である。該極限粘度[η]は、テトラリン中、135℃で測定される。 The intrinsic viscosity [η] of the copolymer rubber (B) is preferably 0.5 dl / g or more and 10 dl / g or less, more preferably 1 dl / g or more and 8 dl / g or less, further preferably 1.5 dl. / G or more and 5 dl / g or less. The intrinsic viscosity [η] is measured at 135 ° C. in tetralin.
共重合体ゴム(A)の量と共重合体ゴム(B)の量との合計を100重量%として、共重合体ゴム(A)の量は、好ましくは、40重量%以上90重量%以下であり、より好ましくは、45重量%以上85重量%以下であり、更に好ましくは、50重量%以上80重量%以下であり、共重合体ゴム(B)の量は、好ましくは、60重量%以下10重量%以上であり、より好ましくは、55重量%以下15重量%以上であり、更に好ましくは、50重量%以下20重量%以上である。 The total amount of the copolymer rubber (A) and the copolymer rubber (B) is 100% by weight, and the amount of the copolymer rubber (A) is preferably 40% by weight or more and 90% by weight or less. More preferably, it is 45% by weight or more and 85% by weight or less, more preferably 50% by weight or more and 80% by weight or less, and the amount of the copolymer rubber (B) is preferably 60% by weight. The content is 10% by weight or more, more preferably 55% by weight or less and 15% by weight or more, and further preferably 50% by weight or less and 20% by weight or more.
共重合体ゴム組成物中の共重合体ゴム(A)および共重合体ゴム(B)から構成されるゴム成分の極限粘度[η]は、好ましくは0.5dl/g以上10dl/g以下であり、より好ましくは1dl/g以上8dl/g以下であり、更に好ましくは1.5dl/g以上5dl/g以下である。該極限粘度[η]は、テトラリン中、135℃で測定される。 The intrinsic viscosity [η] of the rubber component composed of the copolymer rubber (A) and the copolymer rubber (B) in the copolymer rubber composition is preferably 0.5 dl / g or more and 10 dl / g or less. More preferably, it is 1 dl / g or more and 8 dl / g or less, More preferably, it is 1.5 dl / g or more and 5 dl / g or less. The intrinsic viscosity [η] is measured at 135 ° C. in tetralin.
本発明では、2つ以上の反応槽が直列に連結した重合反応装置を用いて、連続溶液重合でエチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物を製造する。2つの反応槽が直列に連結した重合反応装置を用いた製造方法としては、例えば、エチレン、α−オレフィン、非共役ポリエン、重合溶媒および重合触媒を第1反応槽に供給し、重合工程(A)あるいは重合工程(B)のいずれかを第1反応槽で行い、第1反応槽から抜き出された重合溶液、エチレン、α−オレフィン、非共役ポリエン、重合溶媒および重合触媒を第2反応槽に供給し、他方の重合工程を第2反応槽で行う方法があげられる。 In the present invention, an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition is produced by continuous solution polymerization using a polymerization reaction apparatus in which two or more reaction vessels are connected in series. As a production method using a polymerization reaction apparatus in which two reaction vessels are connected in series, for example, ethylene, α-olefin, non-conjugated polyene, a polymerization solvent and a polymerization catalyst are supplied to the first reaction vessel, and a polymerization step (A ) Or polymerization step (B) in the first reaction tank, and the polymerization solution, ethylene, α-olefin, non-conjugated polyene, polymerization solvent and polymerization catalyst extracted from the first reaction tank are used in the second reaction tank. And the other polymerization step is carried out in the second reaction vessel.
共重合体ゴム組成物は、添加剤、例えば、加硫剤、加硫助剤、加硫促進剤、軟化剤、補強剤、発泡剤、発泡助剤、安定剤、消泡剤を含有していてもよい。 The copolymer rubber composition contains additives such as a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a softening agent, a reinforcing agent, a foaming agent, a foaming aid, a stabilizer, and an antifoaming agent. May be.
加硫剤としては、硫黄、硫黄系化合物及び有機過酸化物などを用いることができる。硫黄としては、粉末硫黄、沈降硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄などを用いることができる。硫黄および硫黄系化合物の使用量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.01〜10重量部であり、より好ましくは0.1〜5重量部である。 As the vulcanizing agent, sulfur, a sulfur compound, an organic peroxide, or the like can be used. As sulfur, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used. The amount of sulfur and sulfur-based compound used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition. .
有機過酸化物としては、ジクミルペルオキシド、2,5−ジメチル−2,5−ジ(第三ブチルペルオキシ)ヘキサン、2,5−ジメチル−2,5−ジ(ベンゾイルペルオキシ)ヘキサン、2,5−ジメチル−2,5−(第三ブチルペルオキシ)ヘキシン−3、ジ第三ブチルペルオキシド、ジ第三ブチルペルオキシド−3,3,5−トリメチルシクロヘキサン、および第三ブチルヒドロペルオキシドなどをあげることができる。好ましくは、ジクミルペルオキシド、ジ第三ブチルペルオキシド、ジ第三ブチルペルオキシド−3,3,5−トリメチルシクロヘキサンであり、より好ましくは、ジ第三ブチルペルオキシド−3,3,5−トリメチルシクロヘキサンである。有機過酸化物の使用量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.1〜15重量部であり、より好ましくは1〜8重量部である。 Examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5- (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and tert-butyl hydroperoxide . Preferred is dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and more preferred is di-tert-butyl peroxide-3,3,5-trimethylcyclohexane. . The amount of the organic peroxide used is preferably 0.1 to 15 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
硫黄または硫黄系化合物に対する加硫助剤としては、酸化マグネシウム、酸化亜鉛などの金属酸化物をあげることができる。好ましくは、酸化亜鉛である。該加硫助剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは1〜20重量部である。 Examples of vulcanization aids for sulfur or sulfur compounds include metal oxides such as magnesium oxide and zinc oxide. Zinc oxide is preferable. The compounding amount of the vulcanization aid is preferably 1 to 20 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
有機過酸化物に対する加硫助剤としては、トリアリルイソシアヌレート、N,N’−m−フェニレンビスマレイミド、メタクリル酸、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、n−ブチルメタクリレート、i−ブチルメタクリレート、sec−ブチルメタクリレート、t−ブチルメタクリレート、2−エチルヘキシルメタクリレート、シクロヘキシルメタクリレート、イソデシルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、ステアリルメタクリレート、2−ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、2−エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、アリルメタクリレート、グリシジルメタクリレート、ベンジルメタクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、メタアクリロキシエチルホスフェート、1,4−ブタンジオールジアクリレート、エチレングリコールジメタクリレート、1,3−ブチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、1,6−ヘキサンジオールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、ジプロピレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート、トリメチロールエタントリメタクリレート、トリメチロールプロパントリメタクリレート、アリルグリシジルエーテル、N−メチロールメタクリルアミド、2,2−ビス(4−メタクリロキシポリエトキシフェニル)プロパン、メタクリル酸アルミニウム、メタクリル亜鉛、メタクリル酸カルシウム、メタクリル酸マグネシウム、3−クロロ−2−ヒドロキシプロピルメタクリレート等をあげることができる。該架橋助剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.05〜15重量部であり、より好ましくは0.1〜8重量部である。 As vulcanization aids for organic peroxides, triallyl isocyanurate, N, N′-m-phenylenebismaleimide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i- Butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, Polypropylene glycol monomethacrylate, 2-ethoxyethyl methacrylate Chryrate, tetrahydrofurfuryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacryloxyethyl phosphate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene Glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate Les Trimethylolpropane trimethacrylate, allyl glycidyl ether, N-methylol methacrylamide, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, aluminum methacrylate, zinc methacrylate, calcium methacrylate, magnesium methacrylate, 3 -Chloro-2-hydroxypropyl methacrylate and the like can be mentioned. The blending amount of the crosslinking aid is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
加硫促進剤としては、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ジペンタメチレンチウラムモノスルフィド、ジペンタメチレンチウラムジスルフィド、ジペンタメチレンチウラムテトラスルフィド、N,N’−ジメチル−N,N’−ジフェニルチウラムジスルフィド、N,N’−ジオクタデシル−N,N’−ジイソプロピルチウラムジスルフィド、N−シクロヘキシル−2−ベンゾチアゾール−スルフエンアミド、N−オキシジエチレン−2−ベンゾチアゾール−スルフエンアミド、N,N−ジイソプロピル−2−ベンゾチアゾールスルフエンアミド、2−メルカプトベンゾチアゾール、2−(2,4−ジニトロフエニル)メルカプトベンゾチアゾール、2−(2,6−ジエチル−4−モルホリノチオ)ベンゾチアゾール、ジベンゾチアジル−ジスルフイド、ジフエニルグアニジン、トリフエニルグアニジン、ジオルソトリルグアニジン、オルソトリル−バイ−グアナイド、ジフエニルグアニジン−フタレート、アセトアルデヒド−アニリン反応物、ブチルアルデヒド−アニリン縮合物、ヘキサメチレンテトラミン、アセトアルデヒドアンモニア、2−メルカプトイミダゾリン、チオカルバニリド、ジエチルチオユリア、ジブチルチオユリア、トリメチルチオユリア、ジオルソトリルチオユリア、ジメチルジチオカルバミン酸亜鉛、ジエチルチオカルバミン酸亜鉛、ジ−n−ブチルジチオカルバミン酸亜鉛、エチルフエニルジチオカルバミン酸亜鉛、ブチルフエニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸ナトリウム、ジメチルジチオカルバミン酸セレン、ジエチルジチオカルバミン酸テルル、ジブチルキサントゲン酸亜鉛、エチレンチオウレアなどをあげることができる。加硫促進剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.05〜20重量部であり、より好ましくは0.1〜8重量部である。 Examples of the vulcanization accelerator include tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram tetrasulfide, N, N′-dimethyl-N, N′-diphenylthiuram disulfide, N, N′-dioctadecyl-N, N′-diisopropylthiuram disulfide, N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N -Diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6- Ethyl-4-morpholinothio) benzothiazole, dibenzothiazyl-disulfide, diphenylguanidine, triphenylguanidine, diorthotolylguanidine, orthotolyl-by-guanide, diphenylguanidine-phthalate, acetaldehyde-aniline reactant, butyraldehyde- Aniline condensate, hexamethylenetetramine, acetaldehyde ammonia, 2-mercaptoimidazoline, thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diortholylthiourea, zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, di-n -Zinc butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyldithiocarbamate Sodium vammin acid, dimethyl dithiocarbamate selenium include diethyl dithiocarbamate tellurium, dibutyl xanthate zinc, and ethylene thiourea. The amount of the vulcanization accelerator is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
軟化剤としては、プロセスオイル、潤滑油、パラフィン、流動パラフィン、石油アスファルト、ワセリンなどの石油系軟化剤;コールタール、コールタールピッチなどのコールタール系軟化剤;ヒマシ油、アマニ油、ナタネ油、ヤシ油などの脂肪油系軟化剤;トール油、サブ、蜜ロウ、カルナウバロウ、ラノリンなどのロウ類、リシノール酸、パルミチン酸、ステアリン酸バリウム、ステアリン酸カルシウム、ラウリン酸亜鉛などの脂肪酸及び脂肪酸塩;石油樹脂、アタクチックポリプロピレン、クマロンインデン樹脂などの合成高分子物質などがあげられる。軟化剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは1〜300重量部であり、より好ましくは20〜250重量部であり、更に好ましくは50〜200重量部である。 As softeners, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil softeners such as coconut oil; waxes such as tall oil, sub, beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer substances such as resins, atactic polypropylene, and coumarone indene resins. The compounding amount of the softening agent is preferably 1 to 300 parts by weight, more preferably 20 to 250 parts by weight, still more preferably 50 to 200 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition. Parts by weight.
補強剤としては、カーボンブラック、シリカ、炭酸カルシウム、微粉タルク、微粉ケイ酸アルミニウムなどがあげられる。カーボンブラックとしては、SRF、GPF、FEF、MAF、HAF、ISAF、SAF、FT、MTなどがあげられ、これらのカーボンブラックは、シランカップリング剤などで表面処理されていてもよい。補強剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは1〜300重量部であり、より好ましくは20〜250重量部であり、更に好ましくは50〜200重量部である。 Examples of the reinforcing agent include carbon black, silica, calcium carbonate, fine powder talc, fine powder aluminum silicate and the like. Examples of the carbon black include SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. These carbon blacks may be surface-treated with a silane coupling agent or the like. The compounding amount of the reinforcing agent is preferably 1 to 300 parts by weight, more preferably 20 to 250 parts by weight, and still more preferably 50 to 200 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition. Parts by weight.
発泡剤としては、重炭酸ナトリウム、炭酸ナトリウム、重炭酸アンモニウム、炭酸アンモニウム、亜硝酸アンモニウム等の無機発泡剤;N,N’−ジメチル−N,N’−ジニトロソテレフタルアミド、N,N’−ジニトロソペンタメチレンテトラミン等のニトロソ化合物;アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾビスシクロヘキシルニトリル、アゾジアミノベンゼン、バリウムアゾジカルボキシレート等のアゾ化合物;ベンゼンスルホニルヒドラジド、トルエンスルホニルヒドラジド、P,P’−オキシビス(ベンゼンスルホニルヒドラジド)、ジフェニルスルホン−3,3’−ジスルホニルヒドラジド等のスルホニルヒドラジド化合物;カルシウムアジド、4,4’−ジフェニルジスルホニルアジド、P−トルエンスルホニルアジド等のアジド化合物などをあげることができる。発泡剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.01〜15重量部であり、より好ましくは0.05〜8重量部である。 Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthalamide, N, N′-di Nitroso compounds such as nitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azobiscyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, P, P Sulfonyl hydrazide compounds such as' -oxybis (benzenesulfonylhydrazide) and diphenylsulfone-3,3'-disulfonylhydrazide; calcium azide, 4,4'-diphenyldisulfonylazide, P-toluenesulfur Such as azide compounds such as Niruajido can be mentioned. The blending amount of the foaming agent is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
発泡助剤としては、サリチル酸、フタル酸、ステアリン酸、しゅう酸等の有機酸;尿素またはその誘導体などをあげることができる。発泡助剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.01〜15重量部であり、より好ましくは0.05〜8重量部である。 Examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid; urea or derivatives thereof. The blending amount of the foaming aid is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
安定剤としては、アミン系老化防止剤、ヒンダードフェノール系老化防止剤、イオウ系老化防止剤などをあげることができる。安定剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.01〜15重量部であり、より好ましくは0.05〜8重量部である。 Examples of the stabilizer include amine-based anti-aging agents, hindered phenol-based anti-aging agents, and sulfur-based anti-aging agents. The amount of the stabilizer is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
消泡剤としては、酸化カルシウムをあげることができる。消泡剤の配合量は、共重合体ゴム組成物中のゴム成分を100重量部として、好ましくは0.05〜20重量部であり、より好ましくは0.1〜8重量部である。 An example of an antifoaming agent is calcium oxide. The blending amount of the antifoaming agent is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the rubber component in the copolymer rubber composition.
共重合体ゴム組成物は、必要に応じて、樹脂を含有していてもよい。樹脂としては、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブテン、ポリ−4−メチル−ペンテン−1、ポリスチレン、ポリエステル、ポリアミド、ポリフェニレンエーテルなどがあげられる。ポリエチレン系樹脂としては、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン等をあげることができる。 The copolymer rubber composition may contain a resin as necessary. Examples of the resin include polyethylene resin, polypropylene resin, polybutene, poly-4-methyl-pentene-1, polystyrene, polyester, polyamide, polyphenylene ether, and the like. Examples of the polyethylene resin include high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene.
共重合体ゴム組成物への上記添加剤等の配合方法としては、公知のゴム配合物の調製方法を用いることができる。例えば、バンバリーミキサー、ニーダー、インターミックスなどのインターナルミキサーを用いて、軟化剤、補強剤、安定剤などと共重合体ゴムとを、80〜170℃の温度で3〜10分間混練し、次いで、オープンロールなどのロ−ル類あるいはニーダーを用いて、温度40〜80℃で必要に応じて加硫剤、加硫促進剤、加硫助剤などを加えて、5〜30分間混練することにより調製することができる。このようにして通常リボン状又はシート状の組成物(配合ゴム)が得られる。上記のインターナルミキサーでの混練温度が加硫剤や発泡剤の分解温度よりも低い場合には、加硫剤、発泡剤などを同時に混練することもできる。 As a method for blending the above-mentioned additives into the copolymer rubber composition, a known method for preparing a rubber blend can be used. For example, using an internal mixer such as a Banbury mixer, a kneader, or an intermix, a softener, a reinforcing agent, a stabilizer, and the like and a copolymer rubber are kneaded at a temperature of 80 to 170 ° C. for 3 to 10 minutes, Using a roll such as an open roll or a kneader, knead for 5 to 30 minutes by adding a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, etc. as necessary at a temperature of 40 to 80 ° C. Can be prepared. Thus, a ribbon-like or sheet-like composition (blended rubber) is usually obtained. When the kneading temperature in the internal mixer is lower than the decomposition temperature of the vulcanizing agent or the blowing agent, the vulcanizing agent, the blowing agent, etc. can be kneaded at the same time.
共重合体ゴム組成物は、好適には、加硫発泡成形により、ゴム発泡体に成形されて、自動車用シール材(ウェザーストリップ、ドアーグラスランチャンネルなど)、窓枠、ラジエータホース、ブレーキ部品、ワイパーブレードなどの自動車工業部品;ゴムロール、ベルト、パッキン、ホースなどの工業用ゴム製品;アノードキャップ、グロメットなどの電気絶縁材;建築用ガスケット、土木用シートなどの土木建材用品;ゴム引布;断熱材;クッション材などに用いられる。 The copolymer rubber composition is preferably molded into a rubber foam by vulcanization foam molding, and is used as a sealing material for automobiles (weather strip, door glass run channel, etc.), window frame, radiator hose, brake parts, wiper. Automotive industrial parts such as blades; industrial rubber products such as rubber rolls, belts, packings and hoses; electrical insulation materials such as anode caps and grommets; civil engineering materials such as construction gaskets and civil engineering sheets; Used for cushioning materials.
加硫発泡成形によりゴム発泡体を製造する方法としては、架橋剤、発泡剤等の添加剤を配合したゴム組成物を、公知の成形機(例えば、押出成形機、カレンダーロール成形機、プレス成形機、インジェクション成形機、トランスファー成形機など)によって、所望形状を有する成形体に成形し、該成形と同時に又は該成形の後に、成形体を加熱して、成形体を加硫および発泡する方法;発泡剤等の添加剤を配合したゴム組成物を、上記公知の成形機によって、所望形状を有する成形体に成形し、該成形と同時に又は該成形の後に、成形体を加熱して成形体を発泡し、次に、成形体に電子線を照射して成形体を加硫する方法などがあげられる。 As a method for producing a rubber foam by vulcanization foam molding, a rubber composition containing additives such as a cross-linking agent and a foaming agent is used as a known molding machine (for example, an extrusion molding machine, a calender roll molding machine, a press molding). A molded body having a desired shape by a molding machine, an injection molding machine, a transfer molding machine, etc., and a molded body is heated simultaneously with or after the molding to vulcanize and foam the molded body; A rubber composition containing an additive such as a foaming agent is molded into a molded body having a desired shape by the known molding machine, and the molded body is heated simultaneously with or after the molding to form the molded body. Examples of the method include foaming, and then irradiating the molded body with an electron beam to vulcanize the molded body.
加熱により加硫発泡あるいは発泡する方法においては、熱空気、ガラスビーズ流動床、UHF(極超短波電磁波)、スチーム、LCM(熱溶融塩槽)などの加熱手段を有する加熱槽;金型を用いることができる。加熱温度は、好ましくは150〜270℃であり、加熱時間は、好ましくは1〜30分間である。 In the method of vulcanization foaming or foaming by heating, a heating tank having heating means such as hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, LCM (hot molten salt tank); Can do. The heating temperature is preferably 150 to 270 ° C., and the heating time is preferably 1 to 30 minutes.
電子線照射により加硫する方法においては、電子線のエネルギーは、好ましくは0.1〜10MeVであり、より好ましくは0.3〜2MeVである。また、吸収線量が0.5〜35Mradとなるように照射することが好ましく、吸収線量が0.5〜10Mradとなるように照射することがより好ましい。 In the method of vulcanizing by electron beam irradiation, the energy of the electron beam is preferably 0.1 to 10 MeV, more preferably 0.3 to 2 MeV. Moreover, it is preferable to irradiate so that an absorbed dose may be 0.5-35 Mrad, and it is more preferable to irradiate so that an absorbed dose may be 0.5-10 Mrad.
以下、実施例及び比較例によって本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[測定・評価方法]
(1)エチレン単位量およびプロピレン単位量
共重合体ゴムおよび共重合体ゴム組成物をホットプレス機により厚み約0.1mmのフィルムに成形し、赤外分光光度計(日本分光工業社製 IR−810)により該フィルムの赤外吸収スペクトルを測定した。該赤外吸収スペクトルから、文献(赤外吸収スペクトルによるポリエチレンのキャラクタリゼーション 高山、宇佐美 等著 又は Die Makromolekulare Chemie,177,461(1976)Mc Rae,M.A.,MadamS,W.F.等著)記載の方法に従って、エチレン単位量およびプロピレン単位量を求めた。
[Measurement and evaluation method]
(1) Ethylene unit amount and propylene unit amount A copolymer rubber and a copolymer rubber composition were formed into a film having a thickness of about 0.1 mm by a hot press machine, and an infrared spectrophotometer (IR-manufactured by JASCO) 810), the infrared absorption spectrum of the film was measured. From the infrared absorption spectrum, literature (characterizing polyethylene by infrared absorption spectrum, Takayama, Usami et al. Or Die Makromolekulare Chemie, 177, 461 (1976) Mc Rae, MA, Madam S, WF, etc. ) According to the method described, the ethylene unit amount and the propylene unit amount were determined.
(2)ヨウ素価
共重合体ゴムおよび共重合体ゴム組成物をホットプレス機により厚み約0.5mmのフィルムに成形した。赤外分光光度計により該フィルムの5−エチリデン−2−ノルボルネン由来のピーク(1688cm-1の吸収ピーク)の強度を測定した。該ピーク強度から二重結合のモル含量を求め、該モル含量からヨウ素価を算出した。
(2) Iodine value The copolymer rubber and the copolymer rubber composition were formed into a film having a thickness of about 0.5 mm by a hot press machine. The intensity of the peak derived from 5-ethylidene-2-norbornene (absorption peak at 1688 cm −1 ) of the film was measured by an infrared spectrophotometer. The molar content of the double bond was determined from the peak intensity, and the iodine value was calculated from the molar content.
(3)分子量分布
ゲル・パーミエイション・クロマトグラフ(GPC)法によって、下記の条件(1)〜(9)で、z平均分子量(Mz)と数平均分子量(Mn)を測定し、分子量分布(Mz/Mn)を求めた。
(1)装置:Waters製150C
(2)分離カラム:昭和電工社製Shodex Packed ColumnA−80M
(3)測定温度:140℃
(4)キャリア:オルトジクロロベンゼン
(5)流量:1.0mL/分
(6)試料濃度:約1mg/1mL
(7)試料注入量:400μL
(8)検出器:示差屈折
(9)分子量標準物質:標準ポリスチレン
(3) Molecular weight distribution By gel permeation chromatograph (GPC) method, under the following conditions (1) to (9), z average molecular weight (Mz) and number average molecular weight (Mn) are measured, and molecular weight distribution. (Mz / Mn) was determined.
(1) Equipment: Waters 150C
(2) Separation column: Shodex Packed Column A-80M manufactured by Showa Denko KK
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Sample concentration: about 1mg / 1mL
(7) Sample injection amount: 400 μL
(8) Detector: Differential refraction
(9) Molecular weight reference material: Standard polystyrene
(4)極限粘度
ウベローデ型粘度計を用い、135℃のテトラリン溶液中で測定した。
(4) Intrinsic viscosity The intrinsic viscosity was measured in a 135 ° C. tetralin solution using an Ubbelohde viscometer.
(5)密度
23℃の雰囲気において、長さ50mmに調製したゴム発泡体の空気中での重量と水中に浸漬したときの浮力を測定した。浮力からゴム発泡体の容積を求め、重量/容積により密度を算出した。
(5) Density In an atmosphere at 23 ° C., the weight of the rubber foam prepared to a length of 50 mm in air and the buoyancy when immersed in water were measured. The volume of the rubber foam was determined from the buoyancy, and the density was calculated from the weight / volume.
(6)吸水率
長さ50mmに調製したゴム発泡体をASTM D1667に従って測定した。
(6) Water absorption The rubber foam prepared to a length of 50 mm was measured according to ASTM D1667.
実施例1
(共重合体ゴム組成物の調製)
攪拌機を備えたステンレススチール製の第1重合槽に、単位時間・単位重合槽容積あたり、ヘキサンを754g/(hr・L)、エチレン、プロピレンを各々34.4g/(hr・L)、90.5g/(hr・L)の速度で供給した。VOCl3、エタノールを各々59.5mg/(hr・L)、28.6mg/(hr・L)の速度(VOCl3/エタノール=1/1.8(モル比))で、ラインミキサーで混合・攪拌した後に、該重合槽に供給した。また、エチルアルミニウムセスキクロライド(EASC)、水素を各々339.3mg/(hr・L)、0.04NL/(hr・L)の速度で該重合槽に供給した。更に5−エチリデン−2−ノルボルネンを毎時10.05g/(hr・L)の速度で該重合槽に供給した。該重合槽の温度を40℃に保った。該重合槽で、単位時間・単位重合槽容積あたり、43g/(hr・L)の共重合体ゴムが生成した。該共重合体ゴムのエチレン単位量/プロピレン単位量(モル比)は0.65/0.35であり、ヨウ素価は30.9(g/100gポリマー)であった。
Example 1
(Preparation of copolymer rubber composition)
In a first polymerization tank made of stainless steel equipped with a stirrer, 754 g / (hr · L) of hexane, 34.4 g / (hr · L) of ethylene and propylene, and 90. It was supplied at a rate of 5 g / (hr · L). VOCl 3 and ethanol were mixed at a rate of 59.5 mg / (hr · L) and 28.6 mg / (hr · L) (VOCl 3 /ethanol=1/1.8 (molar ratio)) with a line mixer. After stirring, it was supplied to the polymerization tank. Further, ethylaluminum sesquichloride (EASC) and hydrogen were supplied to the polymerization tank at rates of 339.3 mg / (hr · L) and 0.04 NL / (hr · L), respectively. Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 10.05 g / (hr · L) per hour. The temperature of the polymerization tank was kept at 40 ° C. In the polymerization tank, 43 g / (hr · L) of copolymer rubber was produced per unit time / unit polymerization tank volume. The copolymer rubber had an ethylene unit amount / propylene unit amount (molar ratio) of 0.65 / 0.35 and an iodine value of 30.9 (g / 100 g polymer).
第1重合槽と同容積の攪拌機を備えたステンレススチール製の第2重合槽に、第1重合槽から抜き出された重合溶液をフィードした。単位時間・単位重合槽容積あたり、ヘキサンを345g/(hr・L)、エチレンを29.4g/(hr・L)の速度で供給した。VO(O(iso−C3H7))0.8Cl2.2を26.7mg/(hr・L)の速度で第2重合槽に供給した。また、エチルアルミニウムセスキクロライド(EASC)、水素を各々339.3mg/(hr・L)、0.12NL/(hr・L)の速度で該重合槽に供給した。更に5−エチリデン−2−ノルボルネンを毎時0.15g/(hr・L)の速度で該重合槽に供給した。該重合槽の温度を60℃に保った。
第2重合槽から抜き出された重合溶液を分析した結果、共重合体ゴム組成物(以下、EPDM−Aと記す。)の生成量は、単位時間・単位重合槽容積あたり、64g/(hr・L)であり、該共重合体ゴム組成物のエチレン単位量/プロピレン単位量(モル比)は0.73/0.27であり、ヨウ素価は24.8(g/100gポリマー)であり、極限粘度は2.2dl/g、分子量分布は3.6であった。
第2重合槽では、単位時間・単位重合槽容積あたり、21g/(hr・L)の共重合体ゴムが生成し、該共重合体ゴムのエチレン単位量/プロピレン単位量(モル比)は0.88/0.12であり、ヨウ素価は11.9(g/100gポリマー)であることがわかった。
The polymerization solution extracted from the first polymerization tank was fed into a second polymerization tank made of stainless steel equipped with a stirrer having the same volume as the first polymerization tank. Hexane was supplied at a rate of 345 g / (hr · L) and ethylene at a rate of 29.4 g / (hr · L) per unit time and unit polymerization tank volume. VO (O (iso-C 3 H 7 )) 0.8 Cl 2.2 was fed to the second polymerization tank at a rate of 26.7 mg / (hr · L). Further, ethylaluminum sesquichloride (EASC) and hydrogen were supplied to the polymerization tank at a rate of 339.3 mg / (hr · L) and 0.12 NL / (hr · L), respectively. Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 0.15 g / (hr · L) per hour. The temperature of the polymerization tank was kept at 60 ° C.
As a result of analyzing the polymerization solution extracted from the second polymerization tank, the production amount of the copolymer rubber composition (hereinafter referred to as EPDM-A) was 64 g / (hr) per unit time / unit polymerization tank volume. L), and the copolymer rubber composition has an ethylene unit amount / propylene unit amount (molar ratio) of 0.73 / 0.27 and an iodine value of 24.8 (g / 100 g polymer). The intrinsic viscosity was 2.2 dl / g and the molecular weight distribution was 3.6.
In the second polymerization tank, 21 g / (hr · L) copolymer rubber is produced per unit time / unit polymerization tank volume, and the ethylene unit amount / propylene unit amount (molar ratio) of the copolymer rubber is 0. The iodine value was found to be 11.9 (g / 100 g polymer).
(添加剤の配合)
工程−1
100重量部のEPDM−Aと、5重量部の酸化亜鉛(井上石灰社製 メタZ−L102)と、1重量部のステアリン酸と、102重量部のSRFカーボンブラック(旭カーボン社製 旭50HG)、22重量部のタルク(日本タルク社製 ミストロンベーパー)、60重量部のプロセスオイル(出光興産社製 ダイアナPS430)をバンバリーミキサーで混練して、混練物を得た。混練においては、混練開始時のバンバリーミキサーの温度を80℃とし、ローター回転数を60rpmとし、混練時間を5分間とした。
(Mixing of additives)
Step-1
100 parts by weight of EPDM-A, 5 parts by weight of zinc oxide (Meta Z-L102 manufactured by Inoue Lime), 1 part by weight of stearic acid, and 102 parts by weight of SRF carbon black (Asahi 50HG, manufactured by Asahi Carbon Co., Ltd.) 22 parts by weight of talc (Mistrone vapor manufactured by Nippon Talc Co., Ltd.) and 60 parts by weight of process oil (Diana PS430 manufactured by Idemitsu Kosan Co., Ltd.) were kneaded with a Banbury mixer to obtain a kneaded product. In the kneading, the temperature of the Banbury mixer at the start of kneading was 80 ° C., the rotor rotation speed was 60 rpm, and the kneading time was 5 minutes.
工程−2
上記混練物と、該混練物中のEPDM−A100重量部あたり、3重量部の酸化カルシウム(井上石灰社製 ベスタPP)、3.4重量部の4,4’−オキシビス(ベンゼンスルホニルヒドラジド)(永和化成社製 ネオセルボンN1000SW)、1.8重量部のアゾジカルボンアミド(永和化成社製 ビニホールAC#3)、0.63重量部のジメチルジチオカルバミン酸亜鉛(ラインケミー社製 レノグランZDMC−80)、1.13重量部のジブチルジチオカルバミン酸亜鉛(ラインケミー社製 レノグランZDBC−80)、0.72重量部のジペンタメチレンチウラムテトラスルフィド(ラインケミー社製 レノグランDPTT−70)、1.88重量部の2−メルカプトベンゾチアゾール(ラインケミー社製 レノグランMBT−80)、1.75重量部の2−メルカプトイミダゾリン(ラインケミー社製 レノグランETU−80)、0.75重量部のモルホリンジスルフィド(大内新興化学社製 ノックマスターR80E)、0.4重量部の2−メルカプトベンゾチアゾール亜鉛塩(川口化学社製 アクセルMZ)、1.2重量部のイオウを、ロール温度50℃の8インチのオープンロールで混合して、共重合体ゴム組成物を得た。
Step-2
3 parts by weight of calcium oxide (Vesta PP manufactured by Inoue Lime Co., Ltd.), 3.4 parts by weight of 4,4′-oxybis (benzenesulfonylhydrazide) per 100 parts by weight of EPDM-A in the kneaded product Neocerbon N1000SW manufactured by Eiwa Chemical Co., Ltd., 1.8 parts by weight of azodicarbonamide (Vinole AC # 3 manufactured by Eiwa Chemical Co., Ltd.), zinc dimethyldithiocarbamate (Renogran ZDMC-80 manufactured by Rhein Chemie), 1. 13 parts by weight of zinc dibutyldithiocarbamate (Rheingran ZDBC-80 manufactured by Rhein Chemie), 0.72 parts by weight of dipentamethylene thiuram tetrasulfide (Renogran DPTT-70 manufactured by Rhein Chemie), 1.88 parts by weight of 2-mercaptobenzo Thiazole (Rhein Gran MBT-80, manufactured by Rhein Chemie) 1.75 parts by weight of 2-mercaptoimidazoline (Renogran ETU-80, manufactured by Rhein Chemie), 0.75 parts by weight of morpholine disulfide (Knock Master R80E, manufactured by Ouchi Shinsei Chemical), 0.4 parts by weight of 2-mercaptobenzo Thiazole zinc salt (Axel MZ manufactured by Kawaguchi Chemical Co., Ltd.) and 1.2 parts by weight of sulfur were mixed with an 8-inch open roll having a roll temperature of 50 ° C. to obtain a copolymer rubber composition.
(ゴム発泡体の調製)
工程−2で得られた共重合体ゴム組成物を、45mmφベント式押出機(中田造機社製 45VAK EXTRUDER)を用いて、幅20mm、厚さ2mmのシートに押出成形した。次に、該シートを230℃の熱空気加硫装置(ミクロ電子社製 HAV)に5分間投入し、発泡と加硫を同時に行って、ゴム発泡体を得た。該発泡体の評価結果を表1に示す。
(Preparation of rubber foam)
The copolymer rubber composition obtained in Step-2 was extruded into a sheet having a width of 20 mm and a thickness of 2 mm using a 45 mmφ vent type extruder (45VAK EXTRUDER manufactured by Nakata Engineering Co., Ltd.). Next, the sheet was put into a hot air vulcanizer (HAV manufactured by Micro Electronics Co., Ltd.) at 230 ° C. for 5 minutes, and foaming and vulcanization were performed simultaneously to obtain a rubber foam. The evaluation results of the foam are shown in Table 1.
比較例1
(共重合体ゴム組成物の調製)
攪拌機を備えたステンレススチール製の第1重合槽に、単位時間・単位重合槽容積あたり、ヘキサンを1118g/(hr・L)、エチレン、プロピレンを各々33.4g/(hr・L)、165.2g/(hr・L)の速度で供給した。VOCl3を60.7mg/(hr・L)の速度で該重合槽に供給した。また、エチルアルミニウムセスキクロライド(EASC)、水素を各々364.4mg/(hr・L)、0.022NL/(hr・L)の速度で該重合槽に供給した。更に5−エチリデン−2−ノルボルネンを毎時8.87g/(hr・L)の速度で該重合槽に供給した。該重合槽の温度を38℃に保った。該重合槽で、単位時間・単位重合槽容積あたり、40g/(hr・L)の共重合体ゴムが生成した。該共重合体ゴムのエチレン単位量/プロピレン単位量(モル比)は0.63/0.37であり、ヨウ素価は24.0(g/100gポリマー)であった。
Comparative Example 1
(Preparation of copolymer rubber composition)
In a first polymerization tank made of stainless steel equipped with a stirrer, 1118 g / (hr · L) of hexane, 33.4 g / (hr · L) of ethylene and propylene, and 165. It was supplied at a rate of 2 g / (hr · L). VOCl 3 was fed to the polymerization tank at a rate of 60.7 mg / (hr · L). Further, ethylaluminum sesquichloride (EASC) and hydrogen were supplied to the polymerization tank at a rate of 364.4 mg / (hr · L) and 0.022 NL / (hr · L), respectively. Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 8.87 g / (hr · L) per hour. The temperature of the polymerization tank was kept at 38 ° C. In the polymerization tank, 40 g / (hr · L) of copolymer rubber was produced per unit time / unit polymerization tank volume. The copolymer rubber had an ethylene unit amount / propylene unit amount (molar ratio) of 0.63 / 0.37 and an iodine value of 24.0 (g / 100 g polymer).
第1重合槽と同容積の攪拌機を備えたステンレススチール製の第2重合槽に、第1重合槽から抜き出された重合溶液をフィードした。単位時間・単位重合槽容積あたり、ヘキサンを539g/(hr・L)、エチレンを8.8g/(hr・L)の速度で供給した。VOCl3を41.8mg/(hr・L)の速度で第2重合槽に供給した。また、エチルアルミニウムセスキクロライド(EASC)を250.6mg/(hr・L)の速度で該重合槽に供給した。更に5−エチリデン−2−ノルボルネンを毎時1.21g/(hr・L)の速度で該重合槽に供給した。該重合槽の温度を48℃に保った。
第2重合槽から抜き出された重合溶液を分析した結果、共重合体ゴム組成物(以下、EPDM−Bと記す。)の生成量は、単位時間・単位重合槽容積あたり、60g/(hr・L)であり、該共重合体ゴム組成物のエチレン単位量/プロピレン単位量(モル比)は0.64/0.36であり、ヨウ素価は23.5(g/100gポリマー)であり、極限粘度は2.0dl/g、分子量分布は2.7であった。
第2重合槽では、単位時間・単位重合槽容積あたり、20g/(hr・L)の共重合体ゴムが生成し、該共重合体ゴムのエチレン単位量/プロピレン単位量(モル比)は0.63/0.37であり、ヨウ素価は22.4(g/100gポリマー)であることがわかった。
The polymerization solution extracted from the first polymerization tank was fed into a second polymerization tank made of stainless steel equipped with a stirrer having the same volume as the first polymerization tank. Hexane was supplied at a rate of 539 g / (hr · L) and ethylene at a rate of 8.8 g / (hr · L) per unit time and unit polymerization tank volume. VOCl 3 was fed to the second polymerization tank at a rate of 41.8 mg / (hr · L). Further, ethylaluminum sesquichloride (EASC) was supplied to the polymerization tank at a rate of 250.6 mg / (hr · L). Further, 5-ethylidene-2-norbornene was fed to the polymerization tank at a rate of 1.21 g / (hr · L) per hour. The temperature of the polymerization vessel was kept at 48 ° C.
As a result of analyzing the polymerization solution extracted from the second polymerization tank, the production amount of the copolymer rubber composition (hereinafter referred to as EPDM-B) was 60 g / (hr) per unit time / unit polymerization tank volume. L), ethylene unit amount / propylene unit amount (molar ratio) of the copolymer rubber composition is 0.64 / 0.36, and iodine value is 23.5 (g / 100 g polymer). The intrinsic viscosity was 2.0 dl / g and the molecular weight distribution was 2.7.
In the second polymerization tank, 20 g / (hr · L) of copolymer rubber is produced per unit time and unit polymerization tank volume, and the ethylene unit amount / propylene unit amount (molar ratio) of the copolymer rubber is 0. The iodine value was found to be 22.4 (g / 100 g polymer).
(添加剤の配合、ゴム発泡体の調製)
EPDM−AにかえてEPDM−Bを用いた以外は、実施例1の「添加剤の配合」および「ゴム発泡体の調製」と同様にして、ゴム発泡体を得た。該発泡体の評価結果を表1に示す。
(Addition of additives, preparation of rubber foam)
Except for using EPDM-B instead of EPDM-A, a rubber foam was obtained in the same manner as in “Additive compounding” and “Preparation of rubber foam” in Example 1. The evaluation results of the foam are shown in Table 1.
Claims (3)
重合工程(A):
下記一般式(1)で表されるバナジウム化合物と下記一般式(2)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒の存在下、エチレンとα−オレフィンと非共役ポリエンとを共重合する工程
一般式(1)
VO(OR)mX3-m(式中、Rは炭素原子数1〜8の直鎖状炭化水素基を表し、Xはハロゲン原子を表し、mは0≦m≦3を充足する数を表す。)
一般式(2)
R”jAlX”3-j(式中、R”は炭化水素基を表し、X”はハロゲン原子を表し、jは0<j≦3を充足する数を表す。)
重合工程(B):
下記一般式(3)で表されるバナジウム化合物と下記一般式(4)で表される有機アルミニウム化合物とを重合触媒成分とする重合触媒の存在下、エチレンとα−オレフィンとを共重合、あるいは、エチレンとα−オレフィンと非共役ポリエンとを共重合する工程
一般式(3)
VO(OR’)nX’3-n(式中、R’は炭素原子数3〜8の第2級または第3級炭化水素基を表し、X’はハロゲン原子を表し、nは0<n≦3を充足する数を表す。)
一般式(4)
R'''kAlX'''3-k(式中、R'''は炭化水素基を表し、X'''はハロゲン原子を表し、kは0<k≦3を充足する数を表す。) A method for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition by continuous solution polymerization using a polymerization reaction apparatus in which two or more reaction vessels are connected in series, which comprises the following polymerization step ( A process for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition comprising A) and a polymerization step (B).
Polymerization step (A):
In the presence of a polymerization catalyst comprising a vanadium compound represented by the following general formula (1) and an organoaluminum compound represented by the following general formula (2) as a polymerization catalyst component, ethylene, an α-olefin and a non-conjugated polyene are produced. Step of copolymerization General formula (1)
VO (OR) m X 3-m (wherein R represents a linear hydrocarbon group having 1 to 8 carbon atoms, X represents a halogen atom, and m represents a number satisfying 0 ≦ m ≦ 3) To express.)
General formula (2)
R ″ j AlX ″ 3-j (wherein R ″ represents a hydrocarbon group, X ″ represents a halogen atom, and j represents a number satisfying 0 <j ≦ 3).
Polymerization step (B):
In the presence of a polymerization catalyst comprising a vanadium compound represented by the following general formula (3) and an organoaluminum compound represented by the following general formula (4) as a polymerization catalyst component, ethylene and an α-olefin are copolymerized, or Step of copolymerizing ethylene, α-olefin and non-conjugated polyene General formula (3)
VO (OR ′) n X ′ 3-n (wherein R ′ represents a secondary or tertiary hydrocarbon group having 3 to 8 carbon atoms, X ′ represents a halogen atom, and n is 0 < It represents the number that satisfies n ≦ 3.)
General formula (4)
R ′ ″ k AlX ′ ″ 3-k (wherein R ′ ″ represents a hydrocarbon group, X ′ ″ represents a halogen atom, and k represents a number satisfying 0 <k ≦ 3) .)
重合工程(B)で製造された共重合体が、エチレンに基づく単量体単位の含有量が70モル%を超え95モル%以下、α−オレフィンに基づく単量体単位の含有量が30モル%未満5モル%以上(ただし、エチレンに基づく単量体単位とα−オレフィンに基づく単量体単位との合計を100モル%とする。)であり、ヨウ素価が0以上50以下であるエチレン−α−オレフィン系共重合体ゴムであり、
重合工程(A)で製造された共重合体ゴムの量と重合工程(B)で製造された共重合体ゴムの量との合計を100重量%として、重合工程(A)で製造された共重合体ゴムの量が40重量%以上90重量%以下であり、重合工程(B)で製造された共重合体ゴムの量が60重量%以下10重量%以上である
ことを特徴とする請求項1に記載のエチレン−α−オレフィン−非共役ポリエン系共重合体ゴム組成物の製造方法。 In the copolymer produced in the polymerization step (A), the content of monomer units based on ethylene is 40 mol% or more and 70 mol% or less, and the content of monomer units based on α-olefin is 60 mol%. 30% by mole or more (provided that the total of monomer units based on ethylene and monomer units based on α-olefin is 100% by mole), and ethylene having an iodine value of 1 to 50 α-olefin-nonconjugated polyene copolymer rubber,
The copolymer produced in the polymerization step (B) is such that the content of monomer units based on ethylene is more than 70 mol% and not more than 95 mol%, and the content of monomer units based on α-olefin is 30 mol. Less than 5% by mole (provided that the total of the monomer units based on ethylene and the monomer units based on α-olefin is 100% by mole), and the iodine value is 0 or more and 50 or less. -Α-olefin copolymer rubber,
The total amount of the copolymer rubber produced in the polymerization step (A) and the amount of the copolymer rubber produced in the polymerization step (B) is 100% by weight, and the copolymer produced in the polymerization step (A) is The amount of the polymer rubber is 40 wt% or more and 90 wt% or less, and the amount of the copolymer rubber produced in the polymerization step (B) is 60 wt% or less and 10 wt% or more. 2. The method for producing an ethylene-α-olefin-nonconjugated polyene copolymer rubber composition according to 1.
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