JP5422936B2 - シクロペンテン開環重合体ゴムとその製造方法 - Google Patents
シクロペンテン開環重合体ゴムとその製造方法 Download PDFInfo
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- JP5422936B2 JP5422936B2 JP2008198591A JP2008198591A JP5422936B2 JP 5422936 B2 JP5422936 B2 JP 5422936B2 JP 2008198591 A JP2008198591 A JP 2008198591A JP 2008198591 A JP2008198591 A JP 2008198591A JP 5422936 B2 JP5422936 B2 JP 5422936B2
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- Prior art keywords
- polymer
- cyclopentene
- cyclopentene ring
- opening polymer
- ring
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- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical group C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims description 192
- 229920000642 polymer Polymers 0.000 title claims description 152
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims description 98
- 238000007142 ring opening reaction Methods 0.000 title claims description 68
- 229920001971 elastomer Polymers 0.000 title claims description 44
- 239000005060 rubber Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 46
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 238000005227 gel permeation chromatography Methods 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 41
- 239000000203 mixture Substances 0.000 description 34
- 239000010954 inorganic particle Substances 0.000 description 25
- 238000004132 cross linking Methods 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- -1 aluminum compound Chemical class 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VWMKUZYJGUVNJX-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1)C Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1)C VWMKUZYJGUVNJX-UHFFFAOYSA-L 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QHORRKSZGBYGPH-UHFFFAOYSA-L benzylidene(dichloro)ruthenium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1 QHORRKSZGBYGPH-UHFFFAOYSA-L 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 1
- ZXZSYHLGFSXNNU-UHFFFAOYSA-N [[methyl(4-trimethoxysilylbutyl)carbamothioyl]trisulfanyl] N-methyl-N-(4-trimethoxysilylbutyl)carbamodithioate Chemical compound CO[Si](CCCCN(C(=S)SSSSC(N(C)CCCC[Si](OC)(OC)OC)=S)C)(OC)OC ZXZSYHLGFSXNNU-UHFFFAOYSA-N 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
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- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
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- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
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- RMKXUYVJJQUSPL-UHFFFAOYSA-L dichloro(3,3-dimethylbut-1-enylidene)ruthenium Chemical compound CC(C)(C)C=C=[Ru](Cl)Cl RMKXUYVJJQUSPL-UHFFFAOYSA-L 0.000 description 1
- PGGLXJHJVXGLJA-UHFFFAOYSA-L dichloro(3,3-diphenylprop-1-enylidene)ruthenium;triphenylphosphane Chemical compound C=1C=CC=CC=1C(C=C=[Ru](Cl)Cl)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 PGGLXJHJVXGLJA-UHFFFAOYSA-L 0.000 description 1
- CSYMWOCQWBALLE-UHFFFAOYSA-L dichloro(ethoxymethylidene)ruthenium;tricyclohexylphosphane Chemical compound CCOC=[Ru](Cl)Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1 CSYMWOCQWBALLE-UHFFFAOYSA-L 0.000 description 1
- PAOXUKUJFRPEDY-UHFFFAOYSA-L dichloro(ethoxymethylidene)ruthenium;tricyclohexylphosphane Chemical compound CCOC=[Ru](Cl)Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PAOXUKUJFRPEDY-UHFFFAOYSA-L 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
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- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
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- 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
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Description
テトラヒドロフランを溶媒とするゲル・パーミエーション・クロマトグラフィー(GPC)により、重合体の数平均分子量(Mn)、重量平均分子量(Mw)および分子量分布(Mw/Mn)を、ポリスチレン換算値として測定した。
シクロペンテン開環重合体について、1H−NMRスペクトルの測定を行い、得られたスペクトルから主鎖中の炭素−炭素二重結合に帰属されるピークの積分値と、重合体鎖末端に導入された官能基に帰属されるピークの積分値と、数平均分子量(Mn)とから、一本の重合体鎖が2個の末端を有するものとして、(特定官能基が導入されたシクロペンテン開環重合体末端数/シクロペンテン開環重合体鎖末端全数)の百分率を官能基の導入率として算出した。
混練した重合体組成物2部を1000部のトルエンに72時間浸漬した後、100メッシュのフィルターで濾過して、フィルター残留部(フィルター上に残留したろ物)の重量を測定した。重合体鎖末端に官能基を導入していないシクロペンテン開環重合体を用いた場合におけるフィルター残留部重量を100としたときの、測定対象であるシクロペンテン開環重合体を用いた場合におけるフィルター残留部重量を求め、無機粒子親和性の指標とした。
窒素雰囲気下、磁気攪拌子を入れた耐圧ガラス反応容器に、シクロペンテン100部とアリルトリメトキシシラン0.10部を加えた。次に、トルエン10部に溶解した(1,3−ジメシチルイミダゾリジン−2−イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド0.062部を加え、重合温度0℃で10時間重合した。過剰のビニルエチルエーテルを加えて重合を停止した後、2,6−ジ−t−ブチル−p−クレゾール(BHT)を含む大過剰のイソプロパノールに注いだ。そして、沈殿したポリマーを回収し、イソプロパノールで洗浄後、40℃で3日間、真空乾燥することにより、25部のシクロペンテン開環重合体を得た。得られたシクロペンテン重合体は、Mn=45,600、Mw/Mn=1.89であった。重合体鎖末端への官能基の導入率は49%〔官能基を1つ含有する化合物(アリルトリメトキシシラン)を用いたので、理論上の最大値は50%である。〕であった。
重合温度を10℃、重合時間を20時間としたこと以外は、実施例1と同様にして重合を行い、89部のシクロペンテン開環重合体を得た。得られたシクロペンテン重合体は、Mn=137,200、Mw/Mn=1.50であった。重合体鎖末端への官能基の導入率は47%であった。
重合温度80℃としたこと以外は、実施例1と同様にして重合反応を行い、15部のシクロペンテン開環重合体を得た。得られたシクロペンテン重合体は、Mn=3,800、Mw/Mn=1.68であった。重合体鎖末端への官能基の導入率は5%以下であった。
アリルトリメトキシシラン0.10部に代えて、1−ヘキセン0.051部を加えたこと以外は、実施例1と同様にして重合を行い、重合体末端に官能基が導入されていないシクロペンテン開環重合体を合成した。得られたシクロペンテン重合体の収量は21部であり、Mn=37,800、Mw/Mn=1.87であった。
容量250mlのブラベンダータイプミキサー中で、実施例1、2および参考例1で得たシクロペンテン開環重合体100部を30秒素練りし、次いでプロセスオイル(フッコールM・フェレックスM:富士興産社製)10部、カーボン−シリカ デュアルフェイズフィラー(CRX2000、キャボット社製)40部およびシランカップリング剤(Si69、デグッサ社製)2.5部を添加して、110℃を開始温度として2分間混合後、カーボン−シリカ デュアルフェイズフィラー(CRX2000、キャボット社製)20部、酸化亜鉛(亜鉛華#1、本荘ケミカル社製、粒度0.4μm)3部、ステアリン酸2部および老化防止剤(ノクラック6C、大内新興社製)2部を添加し、さらに2分間混練した。混練した重合体組成物2部を1000部のトルエンに72時間浸漬した後、100メッシュのフィルターで濾過して、フィルター残留部の重量を測定した。参考例1の重合体を用いた場合(参考例2)の残留部重量を100としたときの、実施例1の重合体を用いた場合(実施例4)、および実施例2の重合体を用いた場合(実施例5)の残留部量はそれぞれ115、108であった。
Claims (2)
- シクロペンテンを開環重合してなる繰返し単位を含有するシクロペンテン開環重合体ゴムであって、該シクロペンテン開環重合体ゴムの重合体鎖末端の25%以上が、ケイ素原子を含有する官能基を有するものであり、かつ、ゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の数平均分子量(Mn)が20,000〜1,000,000である、タイヤ部材用に用いるシクロペンテン開環重合体ゴム。
- ケイ素原子を含有する官能基とエチレン性不飽和結合とを分子中に含有する化合物の存在下で、ルテニウム−カルベン錯体を触媒として用いて、20℃未満の重合温度でシクロペンテンを開環重合することを特徴とする請求項1記載のタイヤ部材用に用いるシクロペンテン開環重合体ゴムの製造方法。
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