JP2011026587A - Cyclic olefin ring-opened copolymer - Google Patents
Cyclic olefin ring-opened copolymer Download PDFInfo
- Publication number
- JP2011026587A JP2011026587A JP2010149831A JP2010149831A JP2011026587A JP 2011026587 A JP2011026587 A JP 2011026587A JP 2010149831 A JP2010149831 A JP 2010149831A JP 2010149831 A JP2010149831 A JP 2010149831A JP 2011026587 A JP2011026587 A JP 2011026587A
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- JP
- Japan
- Prior art keywords
- group
- cyclic olefin
- formula
- represented
- iii
- 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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- -1 Cyclic olefin Chemical group 0.000 title claims abstract description 109
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229920001577 copolymer Polymers 0.000 title claims abstract description 64
- 238000007142 ring opening reaction Methods 0.000 claims description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 125000002723 alicyclic group Chemical group 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000004185 ester group Chemical group 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 19
- 230000003287 optical effect Effects 0.000 abstract description 17
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000000178 monomer Substances 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 23
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 15
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas 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
- 150000002576 ketones Chemical class 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N phenyl acetate Chemical compound CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- 150000003282 rhenium compounds Chemical class 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- LCSLWNXVIDKVGD-KQQUZDAGSA-N (3e,7e)-deca-3,7-diene Chemical compound CC\C=C\CC\C=C\CC LCSLWNXVIDKVGD-KQQUZDAGSA-N 0.000 description 1
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- QKIFGRYSZYUWIW-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)-3-phenoxypropan-1-one Chemical compound C1C(C=C2)CC2C1C(=O)CCOC1=CC=CC=C1 QKIFGRYSZYUWIW-UHFFFAOYSA-N 0.000 description 1
- BMGNRARLBKEEBP-UHFFFAOYSA-N 1-(5-methyl-5-bicyclo[2.2.1]hept-2-enyl)-3-phenoxypropan-1-one Chemical compound C1C(C=C2)CC2C1(C)C(=O)CCOC1=CC=CC=C1 BMGNRARLBKEEBP-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- CZYVCAJKUNEWLC-UHFFFAOYSA-N 2-(5-bicyclo[2.2.1]hept-2-enyl)ethanol Chemical compound C1C2C(CCO)CC1C=C2 CZYVCAJKUNEWLC-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UUXSQYBBYLTUFV-UHFFFAOYSA-N 3,4,5-trichlorotricyclo[5.2.1.02,6]dec-8-ene Chemical compound C1=CC2CC1C1C2C(Cl)C(Cl)C1Cl UUXSQYBBYLTUFV-UHFFFAOYSA-N 0.000 description 1
- VVTDTFZJQATPOK-UHFFFAOYSA-N 3,4-dichlorotricyclo[5.2.1.02,6]dec-8-ene Chemical compound C1=CC2CC1C1C2CC(Cl)C1Cl VVTDTFZJQATPOK-UHFFFAOYSA-N 0.000 description 1
- WNINKGHPMVAQAF-UHFFFAOYSA-N 3,4-dimethyltricyclo[5.2.1.02,6]dec-8-ene Chemical compound C1=CC2CC1C1C2CC(C)C1C WNINKGHPMVAQAF-UHFFFAOYSA-N 0.000 description 1
- XILKQRVUDGEVPJ-UHFFFAOYSA-N 3-cyclohexyltricyclo[5.2.1.02,6]dec-8-ene Chemical compound C12C(C=C3)CC3C2CCC1C1CCCCC1 XILKQRVUDGEVPJ-UHFFFAOYSA-N 0.000 description 1
- WLTSXAIICPDFKI-UHFFFAOYSA-N 3-dodecene Chemical compound CCCCCCCCC=CCC WLTSXAIICPDFKI-UHFFFAOYSA-N 0.000 description 1
- LPYAZTKEHOROKS-UHFFFAOYSA-N 3-ethyltricyclo[5.2.1.02,6]dec-8-ene Chemical compound C1C2C3C(CC)CCC3C1C=C2 LPYAZTKEHOROKS-UHFFFAOYSA-N 0.000 description 1
- KEKIZNQLKOYQFU-UHFFFAOYSA-N 3-methyltricyclo[5.2.1.02,6]dec-8-ene Chemical compound C1C2C3C(C)CCC3C1C=C2 KEKIZNQLKOYQFU-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- CXRLCUNVNDFXHW-UHFFFAOYSA-N 3-phenyltricyclo[5.2.1.02,6]dec-8-ene Chemical compound C12C(C=C3)CC3C2CCC1C1=CC=CC=C1 CXRLCUNVNDFXHW-UHFFFAOYSA-N 0.000 description 1
- GEFNCTGUCDGFNE-UHFFFAOYSA-N 4-methyltricyclo[6.2.1.02,7]undec-9-ene Chemical compound C12CC(C)CCC2C2C=CC1C2 GEFNCTGUCDGFNE-UHFFFAOYSA-N 0.000 description 1
- LJIYSFUQNXCTGY-UHFFFAOYSA-N 4-phenyltricyclo[6.2.1.02,7]undec-9-ene Chemical compound C1C2C=CC1C1CC(CCC21)c1ccccc1 LJIYSFUQNXCTGY-UHFFFAOYSA-N 0.000 description 1
- STFDQHZRZOJUMK-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl benzoate Chemical compound C1C(C=C2)CC2C1OC(=O)C1=CC=CC=C1 STFDQHZRZOJUMK-UHFFFAOYSA-N 0.000 description 1
- MGAPHSQFYKGSGL-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylidenemethanone Chemical compound C1C2C(=C=O)CC1C=C2 MGAPHSQFYKGSGL-UHFFFAOYSA-N 0.000 description 1
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 description 1
- LVXDMUDXBUNBQY-UHFFFAOYSA-N 5-cyclohexylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1CCCCC1 LVXDMUDXBUNBQY-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- GOLQZWYZZWIBCA-UHFFFAOYSA-N 5-octylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCC)CC1C=C2 GOLQZWYZZWIBCA-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- AKHDGSRSWWFVIZ-UHFFFAOYSA-N 5-propylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCC)CC1C=C2 AKHDGSRSWWFVIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- LUPHKYVTPGNIBI-UHFFFAOYSA-N C1=CC2CC1C1C2C(C)C(C)C1C Chemical compound C1=CC2CC1C1C2C(C)C(C)C1C LUPHKYVTPGNIBI-UHFFFAOYSA-N 0.000 description 1
- IFXFEOFPNCLYQM-UHFFFAOYSA-N C1=CC=CC1.C1=CC=CC1.CCC=CCCC=CCC Chemical compound C1=CC=CC1.C1=CC=CC1.CCC=CCCC=CCC IFXFEOFPNCLYQM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
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- 239000012965 benzophenone Substances 0.000 description 1
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- MKOSBHNWXFSHSW-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-en-5-ol Chemical compound C1C2C(O)CC1C=C2 MKOSBHNWXFSHSW-UHFFFAOYSA-N 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- UCQHUEOREKHIBP-UHFFFAOYSA-N heptacyclo[9.6.1.14,7.113,16.02,10.03,8.012,17]icosa-5,14-diene Chemical compound C1C(C23)C4C(C=C5)CC5C4C1C3CC1C2C2C=CC1C2 UCQHUEOREKHIBP-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- AINYFZUYWPYGJW-UHFFFAOYSA-N methyl 3-methylbicyclo[2.2.1]heptane-3-carboxylate Chemical compound C1CC2C(C(=O)OC)(C)CC1C2 AINYFZUYWPYGJW-UHFFFAOYSA-N 0.000 description 1
- VVXOXOIAKZHMCU-UHFFFAOYSA-N methyl 5-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)(C(F)(F)F)CC1C=C2 VVXOXOIAKZHMCU-UHFFFAOYSA-N 0.000 description 1
- AEBDJCUTXUYLDC-UHFFFAOYSA-N methyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)(C)CC1C=C2 AEBDJCUTXUYLDC-UHFFFAOYSA-N 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- RUHONYMXXQEISE-UHFFFAOYSA-N pentacosa-6,16-diene Chemical compound CCCCCC=CCCCCCCCCC=CCCCCCCCC RUHONYMXXQEISE-UHFFFAOYSA-N 0.000 description 1
- SHORALNJFMTEDT-UHFFFAOYSA-N pentadeca-4,10-diene Chemical compound CCCCC=CCCCCC=CCCC SHORALNJFMTEDT-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- UAKXMUQGRAINJV-UHFFFAOYSA-N phenyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1(C)C(=O)OC1=CC=CC=C1 UAKXMUQGRAINJV-UHFFFAOYSA-N 0.000 description 1
- WLVPQQDEYVVXJF-UHFFFAOYSA-N phenyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1C(=O)OC1=CC=CC=C1 WLVPQQDEYVVXJF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- SDTYFWAQLSIEBH-UHFFFAOYSA-N undec-3-ene Chemical compound CCCCCCCC=CCC SDTYFWAQLSIEBH-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、屈折率およびａｂｂｅ数が高く、光学材料用途に有用な環状オレフィン系開環共重合体に関する。 The present invention relates to a cyclic olefin ring-opening copolymer having a high refractive index and abbe number and useful for optical material applications.
環状オレフィン系開環（共）重合体、特に水素添加されてなる環状オレフィン系開環（共）重合体は、光線透過率や耐熱性に優れた熱可塑性透明樹脂として着目され、光学レンズや光ファイバー、光学フィルムなどの光学材料分野において、その用途が広がっている。また、これらが組み込まれている携帯電話などのモバイル機器は、より小型化・高性能化する方向で開発が進められており、その構成デバイスには、より一層の小型化・軽量化・高機能化が求められている。そしてレンズ用樹脂にも、小さく、また薄くても機能できる様、より高い屈折率と、高いａｂｂｅ数をもつことが要求されている。 Cyclic olefin ring-opening (co) polymers, especially hydrogenated cyclic olefin ring-opening (co) polymers, are attracting attention as thermoplastic transparent resins with excellent light transmittance and heat resistance, and are used for optical lenses and optical fibers. Applications are expanding in the field of optical materials such as optical films. In addition, mobile devices such as mobile phones in which these are incorporated are being developed in the direction of further miniaturization and higher performance, and the components are further miniaturized, lighter and more functional. Is required. Also, the lens resin is required to have a higher refractive index and a higher abebe number so that it can function even if it is small and thin.
一方、レンズの薄肉化に伴い、薄くしても割れにくい、靭性の高い成形体が得られる樹脂が求められている。樹脂の靭性を確保するためには、ポリマーの分子量を一定量以上に設計する必要があるが、その反面、高分子量化するとポリマーの溶媒への溶解性が低下して析出してしまい、従来の溶液重合・水素化法では製造できなくなってしまうという問題が生じていた。既存の溶液重合プロセスにて、高屈折率・高ａｂｂｅ数を有し、かつレンズ用樹脂に必要な分子量を有するポリマーを製造するためには、高い光学性能と高い溶解性を両立させるポリマー設計を実現する必要がある。 On the other hand, with the thinning of the lens, there is a demand for a resin capable of obtaining a molded article having high toughness that is difficult to break even if it is thinned. In order to ensure the toughness of the resin, it is necessary to design the molecular weight of the polymer to be a certain amount or more. On the other hand, if the molecular weight is increased, the solubility of the polymer in the solvent is reduced and the conventional polymer is precipitated. There has been a problem that the solution polymerization / hydrogenation method cannot be produced. In order to produce a polymer with a high refractive index, a high abbe number, and a molecular weight necessary for a lens resin in an existing solution polymerization process, a polymer design that achieves both high optical performance and high solubility is required. It needs to be realized.
ポリマーの溶解性を高めるには、側鎖にエステル基などの官能基を導入することが有効であることが知られている（特許文献１）。一方で官能基の存在は高屈折率化の妨げとなる。そこで発明者は、官能基を持たないモノマーとの共重合ポリマーで、溶解性と高屈折率化の両立を図る予備検討を行った。しかし、官能基を持たないモノマーとして代表的なトリシクロ［４．３．０．１2,5］デカ−３，７−ジエン（ジシクロペンタジエン）やテトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン（ＤＭＯＮ）などでは、屈折率の改善効果が小さく、既存樹脂より劣る値(ｎD＜１．５２５)しか実現できなかった。 In order to increase the solubility of the polymer, it is known that it is effective to introduce a functional group such as an ester group into the side chain (Patent Document 1). On the other hand, the presence of a functional group hinders an increase in refractive index. Therefore, the inventor conducted a preliminary study to achieve both solubility and high refractive index with a copolymer polymer with a monomer having no functional group. However, typical tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (dicyclopentadiene) or tetracyclo [4.4.0.1 2,5 as a monomer having no functional group. . 1 7,10] etc. is dodeca-3-ene (DMON), the effect of improving the refractive index is small, previously only possible inferior existing resin values (n D <1.525).
高屈折率化と溶媒への溶解性を両立させる他の技術としては、官能基を導入したポリマーとポリスチレンとのブレンド化がある（特許文献２参照）。この技術では、ポリスチレンのブレンド量に比例して高屈折率化を図ることができるが、一方で、ａｂｂｅ数が低下してしまい、レンズの色収差が大きくなるといいう欠点があった。 As another technique for achieving both high refractive index and solubility in a solvent, there is a blending of a polymer into which a functional group is introduced and polystyrene (see Patent Document 2). With this technique, the refractive index can be increased in proportion to the blend amount of polystyrene, but on the other hand, the abbe number decreases, and the chromatic aberration of the lens increases.
このため、ポリスチレンをブレンドせず、環状オレフィン系開環共重合水素化体の単体のみで、高ａｂｂｅ数を有し、かつ、高屈折率を示す樹脂の出現が求められていた。すなわち、トルエンなどの溶媒への溶解性、高屈折率、高ａｂｂｅ数を全て実現するためには、屈折率改善効果の高い新たなモノマーの探索と、目標の諸特性を両立させる共重合モノマー組成の開発が必要であった。 For this reason, there has been a demand for the appearance of a resin having a high abbe number and a high refractive index, which is not blended with polystyrene, but is a single unit of a cyclic olefin ring-opening copolymer hydride. That is, in order to achieve all of the solubility in solvents such as toluene, high refractive index, and high abebe number, a copolymer monomer composition that achieves both the search for a new monomer with a high refractive index improvement effect and the target characteristics. Development was necessary.
この背景の基、本発明者は、高屈折率・高ａｂｂｅ数を実現し得る共重合モノマーを探索した。その結果、シクロペンタジエンの三量体であるペンタシクロ［６．５．１．０2,7．１3,6．０9,13］ペンタデカ−４，１０−ジエン（トリシクロペンタジエン）を共重合することで、従来のモノマーを凌駕する高屈折率化と高ａｂｂｅ数化を実現し、また官能基を有するモノマーとの適当な組成の共重合体とすることで、溶媒への溶解性も確保できることを見出した。 Based on this background, the present inventors searched for a copolymerizable monomer capable of realizing a high refractive index and a high abe number. As a result, pentacyclo [6.5.1.0 2,7 . 1 3,6 . 0 9,13] pentadeca-4,10-by copolymerizing diene (tricyclopentadiene), to achieve a high refractive index and high abbe number of surpassing the conventional monomers and a monomer having a functional group It was found that the solubility in a solvent can be secured by using a copolymer having an appropriate composition.
本発明は、屈折率およびａｂｂｅ数が高く、溶媒への溶解性を有し、光学材料用途に有用な環状オレフィン系開環共重合体を提供することを課題とする。 An object of the present invention is to provide a cyclic olefin-based ring-opening copolymer having a high refractive index and abbe number, solubility in a solvent, and useful for optical material applications.
本発明の環状オレフィン系開環共重合体は、下記式（Ｉ）で表わされる構造単位（Ｉ）と、下記式（II）で表わされる構造単位（II）とを有することを特徴としている。 The cyclic olefin ring-opening copolymer of the present invention is characterized by having a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II).
（式（Ｉ）中、ｍは１〜３の整数であり、Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基であり、Ｙは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基であり、Ｒは水素原子、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基である。） (In formula (I), m is an integer of 1 to 3, X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —, Y is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —, R is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, An alicyclic hydrocarbon group or an aromatic hydrocarbon group.)
（式（II）中、ｎは０〜３の整数であり、Ａ1〜Ａ4は、それぞれ独立に下記（i）〜（iv）のいずれかを表し、このうちの少なくとも１つは、(iii)を表す。
（i）水素原子、
（ii）ハロゲン原子、
（iii）アルコキシ基、水酸基、エステル基、シアノ基、アミノ基およびチオール基よりなる群から選ばれた極性基、
（iv）ハロゲン原子または前記極性基（iii）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基。Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。）
このような本発明の環状オレフィン系開環共重合体は、下記式（III）で表わされる構造単位（III）をさらに有することが好ましい。
(In the formula (II), n is an integer of 0 to 3, and A 1 to A 4 each independently represents any of the following (i) to (iv), and at least one of these is: iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group,
(Iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom or the polar group (iii). X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —. )
Such a cyclic olefin ring-opening copolymer of the present invention preferably further has a structural unit (III) represented by the following formula (III).
（式（III）中、Ｂ1〜Ｂ4は、それぞれ独立に、下記（ｉ）〜（ｖ）のいずれかを表す。
（i）水素原子、
（ii）ハロゲン原子、
（iii）ハロゲン原子により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基、
（iv）Ｂ1とＢ2、またはＢ3とＢ4が、相互に結合してアルキリデン基を形成し、前記結合に関与しないＢ1〜Ｂ4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す、（ｖ）Ｂ1とＢ3、Ｂ1とＢ4、Ｂ2とＢ3、またはＢ2とＢ4が、相互に結合して、それぞれが結合する炭素原子とともに環状構造を形成し、前記結合に関与しないB1〜B4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す。Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。）
本発明の環状オレフィン系開環共重合体は、重量平均分子量がポリスチレン換算で２０，０００以上、１５０，０００以下であることが好ましい。
(In formula (III), B < 1 > -B < 4 > represents either of the following (i)-(v) each independently.
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom,
(Iv) B 1 and B 2 , or B 3 and B 4 are bonded to each other to form an alkylidene group, and B 1 to B 4 not participating in the bonding are independently of each other (i) to (iii (V) B 1 and B 3 , B 1 and B 4 , B 2 and B 3 , or B 2 and B 4 are bonded to each other, together with the carbon atoms to which they are bonded B 1 to B 4 that form a cyclic structure and do not participate in the bond are independently selected from the above (i) to (iii). X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —. )
The cyclic olefin ring-opening copolymer of the present invention preferably has a weight average molecular weight of 20,000 or more and 150,000 or less in terms of polystyrene.
本発明の環状オレフィン系開環共重合体は、共重合体中において、前記Ｘで表わされる基のうち、式：−ＣＨ2ＣＨ2−で表される基の割合が８０モル％以上であることが好ましい。 In the cyclic olefin-based ring-opening copolymer of the present invention, the ratio of the group represented by the formula: —CH 2 CH 2 — among the groups represented by X is 80 mol% or more. It is preferable.
本発明の環状オレフィン系開環共重合体は、屈折率ｎDが１．５２５以上であり、かつａｂｂｅ数が５３以上であることが好ましい。 The cyclic olefin ring-opening copolymer of the present invention preferably has a refractive index n D of 1.525 or more and an abbe number of 53 or more.
本発明によれば、屈折率およびａｂｂｅ数が高く、溶媒への溶解性を有し、光学材料用途に有用な環状オレフィン系開環共重合体を提供することができる。 According to the present invention, it is possible to provide a cyclic olefin-based ring-opening copolymer having a high refractive index and abbe number, solubility in a solvent, and useful for optical material applications.
以下、本発明について具体的に説明する。 Hereinafter, the present invention will be specifically described.
環状オレフィン系開環共重合体
本発明の環状オレフィン系開環共重合体は、下記式（Ｉ）で表わされる構造単位（Ｉ）と、下記式（II）で表わされる構造単位（II）とを有する。
Cyclic olefin ring-opening copolymer The cyclic olefin ring-opening copolymer of the present invention comprises a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II): Have
（式（Ｉ）中、ｍは１〜３の整数であり、Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基であり、Ｙは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基であり、Ｒは水素原子、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基である。） (In formula (I), m is an integer of 1 to 3, X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —, Y is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —, R is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, An alicyclic hydrocarbon group or an aromatic hydrocarbon group.)
（式（II）中、ｎは０〜３の整数であり、Ａ1〜Ａ4は、それぞれ独立に下記（i）〜（iv）のいずれかを表し、このうちの少なくとも１つは、(iii)を表す。
（i）水素原子、
（ii）ハロゲン原子、
（iii）アルコキシ基、水酸基、エステル基、シアノ基、アミノ基およびチオール基よりなる群から選ばれた極性基、
（iv）ハロゲン原子または前記極性基（iii）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基。Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。）
また本発明の環状オレフィン系開環共重合体は、前記構造単位（Ｉ）および（II）で表わされる構造単位に加えて、下記式（III）で表わされる構造単位（III）をさらに有することが好ましい。
(In the formula (II), n is an integer of 0 to 3, and A 1 to A 4 each independently represents any of the following (i) to (iv), and at least one of these is: iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group,
(Iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom or the polar group (iii). X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —. )
The cyclic olefin ring-opening copolymer of the present invention further has a structural unit (III) represented by the following formula (III) in addition to the structural units represented by the structural units (I) and (II). Is preferred.
（式（III）中、Ｂ1〜Ｂ4は、それぞれ独立に、下記（ｉ）〜（ｖ）のいずれかを表す。
（i）水素原子、
（ii）ハロゲン原子、
（iii）ハロゲン原子により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基、
（iv）Ｂ1とＢ2、またはＢ3とＢ4が、相互に結合してアルキリデン基を形成し、前記結合に関与しないＢ1〜Ｂ4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す、（ｖ）Ｂ1とＢ3、Ｂ1とＢ4、Ｂ2とＢ3、またはＢ2とＢ4が、相互に結合して、それぞれが結合する炭素原子とともに環状構造を形成し、前記結合に関与しないB1〜B4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す。Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。） ここで、構造単位（Ｉ）は後述する環状オレフィン系化合物（１）から、構造単位（II）は後述する環状オレフィン系化合物（２）から、構造単位（III）は後述する環状オレフィン系化合物（３）から、開環共重合により誘導されて好適に形成される構造単位である。
(In formula (III), B < 1 > -B < 4 > represents either of the following (i)-(v) each independently.
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom,
(Iv) B 1 and B 2 , or B 3 and B 4 are bonded to each other to form an alkylidene group, and B 1 to B 4 not participating in the bonding are independently of each other (i) to (iii (V) B 1 and B 3 , B 1 and B 4 , B 2 and B 3 , or B 2 and B 4 are bonded to each other, together with the carbon atoms to which they are bonded B 1 to B 4 that form a cyclic structure and do not participate in the bond are independently selected from the above (i) to (iii). X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —. Here, the structural unit (I) is from a cyclic olefin compound (1) to be described later, the structural unit (II) is from a cyclic olefin compound (2) to be described later, and the structural unit (III) is a cyclic olefin compound to be described later. From (3), the structural unit is preferably formed by being derived from ring-opening copolymerization.
本発明の環状オレフィン系開環共重合体において、各構造単位の含有割合は、特に限定されるものではないが、構造単位（Ｉ）が全構造単位中に好ましくは３０〜９０モル％、より好ましくは４０〜９０モル％程度含まれ、また、構造単位（II）が全構造単位中に好ましくは５〜５０モル％程度含まれ、さらに共重合体が構造単位（III）を有する場合には、構造単位（III）が全構造単位中に好ましくは１〜４０モル％、より好ましくは１〜３０モル％程度含まれる。 In the cyclic olefin-based ring-opening copolymer of the present invention, the content ratio of each structural unit is not particularly limited, but the structural unit (I) is preferably 30 to 90 mol% in all the structural units. Preferably, it is contained in an amount of about 40 to 90 mol%, and the structural unit (II) is preferably contained in the total structural unit in an amount of about 5 to 50 mol%, and the copolymer further has a structural unit (III). The structural unit (III) is preferably contained in the total structural unit in an amount of about 1 to 40 mol%, more preferably about 1 to 30 mol%.
本発明の環状オレフィン系開環重合体の分子量は、用途などに応じて適宜調整して製造することができ、特に限定されるものではないが、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定されるポリスチレン換算の数平均分子量（Ｍｗ）が、２０，０００〜１５０，０００である必要がある。分子量が過小である場合には、成形品の強度が低いものとなることがある。一方、分子量が過大である場合には、溶液粘度が高くなりすぎて、本発明の環状オレフィン系共重合体の生産性や成形性、加工性が悪化することがある。 The molecular weight of the cyclic olefin-based ring-opened polymer of the present invention can be appropriately adjusted and produced according to the use and the like, and is not particularly limited, but is measured by gel permeation chromatography (GPC). The number average molecular weight (Mw) in terms of polystyrene needs to be 20,000 to 150,000. If the molecular weight is too small, the strength of the molded product may be low. On the other hand, when the molecular weight is excessive, the solution viscosity becomes too high, and the productivity, moldability, and processability of the cyclic olefin copolymer of the present invention may be deteriorated.
また、本発明に係る環状オレフィン系重合体の分子量分布（Ｍｗ／Ｍｎ）は、特に限定されるものではないが、例えばフィルム用途などに用いる場合には、通常１．５〜１０、好ましくは２〜８、さらに好ましくは２．２〜５であるのが望ましい。 In addition, the molecular weight distribution (Mw / Mn) of the cyclic olefin polymer according to the present invention is not particularly limited. However, for example, when used for a film application, it is usually 1.5 to 10, preferably 2. It is desirable to be -8, more preferably 2.2-5.
本発明の環状オレフィン系開環共重合体は、開環共重合体の水素化物であることが好ましく、前記式（I）、（II）および（III）中の、ＸおよびＹで表わされる基全量のうち、式：−ＣＨ2ＣＨ2−で表される基の割合が好ましくは８０モル％以上、より好ましくは９０モル％以上、さらに好ましくは９５モル％以上であることが望ましい。 The cyclic olefin-based ring-opening copolymer of the present invention is preferably a hydride of the ring-opening copolymer, and the groups represented by X and Y in the above formulas (I), (II) and (III). Of the total amount, the ratio of the group represented by the formula: —CH 2 CH 2 — is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.
本発明の環状オレフィン系開環共重合体は、構造単位（Ｉ）を有することにより、高い屈折率および高いａｂｂｅ数を示す。 The cyclic olefin-based ring-opening copolymer of the present invention has a high refractive index and a high abebe number by having the structural unit (I).
すなわち本発明の環状オレフィン系開環共重合体は、好ましくは屈折率ｎDが１．５２５以上、より好ましくは１．５３０以上であるのが望ましい。本発明において屈折率ｎDとは、プリズムカプラを用いて、４０８ｎｍ，６３３ｎｍ、および８３０ｎｍのレーザー光源により、フィルムサンプルの任意の５箇所の屈折率を測定し、得られた値をコーシーの式にて回帰計算して、５８９ｎｍにおける屈折率を算出して求めた値である。 That is, the cyclic olefin ring-opening copolymer of the present invention preferably has a refractive index n D of 1.525 or more, more preferably 1.530 or more. In the present invention, the refractive index n D is a refractive index measured at any five points of a film sample with a laser light source of 408 nm, 633 nm, and 830 nm using a prism coupler, and the obtained value is expressed as a Cauchy equation. This is a value obtained by regression calculation and calculating the refractive index at 589 nm.
また、本発明の環状オレフィン系開環共重合体は、好ましくはａｂｂｅ数が５３以上、より好ましくは５５以上の範囲であるのが望ましい。本発明においてａｂｂｅ数（ν）とは、ν＝（ｎD−１）／（ｎF−ｎC）の式により算出された値を意味する。ここで言うｎD、ｎF、ｎCは、上記回帰計算により求めた５８９．２ｎｍ、４８６．１ｎｍ、６５６．３ｎｍにおける屈折率である。 The cyclic olefin-based ring-opening copolymer of the present invention preferably has an abbe number of 53 or more, more preferably 55 or more. In the present invention, the Abbe number (ν) means a value calculated by the formula ν = (n D −1) / (n F −n C ). Here, n D , n F , and n C are refractive indexes at 589.2 nm, 486.1 nm, and 656.3 nm obtained by the above regression calculation.
更に、本発明の環状オレフィン系開環共重合体のＴｇは、１２５℃〜２００℃であることが好ましく、１３０〜１９０℃であることが、より好ましい。Ｔｇが１２５℃より低い値になると、光学レンズなどの最終商品が実用に耐えられなくなる場合がある。一方、Ｔｇが２００℃以上であると、射出成形温度を３００℃以上の高温にしなければならず、樹脂の着色が生じる場合がある。 Furthermore, Tg of the cyclic olefin ring-opening copolymer of the present invention is preferably 125 ° C to 200 ° C, more preferably 130 to 190 ° C. If Tg is lower than 125 ° C., the final product such as an optical lens may not be able to withstand practical use. On the other hand, if the Tg is 200 ° C. or higher, the injection molding temperature must be 300 ° C. or higher, and the resin may be colored.
このような本発明の環状オレフィン系開環共重合体は、環状オレフィン系開環共重合体の製造方法により好適に製造することができる。 Such a cyclic olefin ring-opening copolymer of the present invention can be suitably produced by a method for producing a cyclic olefin ring-opening copolymer.
環状オレフィン系開環共重合体の製造方法
本発明の環状オレフィン系開環共重合体は、環状オレフィン系化合物を含む環状オレフィン系モノマーを、開環共重合することにより、さらに必要に応じて水素添加することにより得ることができる。
Method for Producing Cyclic Olefin-Based Ring-Opening Copolymer The cyclic olefin-based ring-opening copolymer of the present invention is obtained by subjecting a cyclic olefin-based monomer containing a cyclic olefin-based compound to ring-opening copolymerization, and further hydrogen as required. It can be obtained by adding.
＜環状オレフィン系モノマー＞
本発明で用いる環状オレフィン系モノマーは、下記式（１）で表わされる少なくとも一種の環状オレフィン系化合物（１）と、下記式（２）で表わされる少なくとも一種の環状オレフィン系化合物（２）とを含有する。
<Cyclic olefin monomer>
The cyclic olefin monomer used in the present invention comprises at least one cyclic olefin compound (1) represented by the following formula (1) and at least one cyclic olefin compound (2) represented by the following formula (2). contains.
［式（１）中、ｍは１〜３の整数であり、Ｒは水素原子、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基である。］ [In Formula (1), m is an integer of 1-3, R is a hydrogen atom, a C1-C10 aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]
［式（２）中、ｎは０〜３の整数であり、Ａ1〜Ａ4は、それぞれ独立に下記（i）〜（iv）のいずれかを表し、このうちの少なくとも１つは、(iii)を表す。
（i）水素原子、
（ii）ハロゲン原子、
（iii）アルコキシ基、水酸基、エステル基、シアノ基、アミノ基およびチオール基よりなる群から選ばれた極性基、
（iv）ハロゲン原子または前記極性基（iii）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基。］
また本発明で用いる環状オレフィン系モノマーは、下記式（３）で表わされる少なくとも一種の環状オレフィン系化合物（３）をさらに含んでもよい。環状オレフィン系モノマーが環状オレフィン系化合物（３）を適切な量で含むことにより、得られる共重合体のガラス転移温度（Ｔｇ）を容易に調節することができる。
[In Formula (2), n is an integer of 0-3, A < 1 > -A < 4 > represents either of the following (i)-(iv) each independently, and at least 1 of these is ( iii).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group,
(Iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom or the polar group (iii). ]
The cyclic olefin monomer used in the present invention may further contain at least one cyclic olefin compound (3) represented by the following formula (3). When the cyclic olefin monomer contains the cyclic olefin compound (3) in an appropriate amount, the glass transition temperature (Tg) of the obtained copolymer can be easily adjusted.
［式（３）中、Ｂ1〜Ｂ4は、それぞれ独立に、下記（ｉ）〜（ｖ）のいずれかを表す。
（i）水素原子、
（ii）ハロゲン原子、
（iii）ハロゲン原子により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基、
（iv）Ｂ1とＢ2、またはＢ3とＢ4が、相互に結合してアルキリデン基を形成し、前記結合に関与しないＢ1〜Ｂ4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す、（ｖ）Ｂ1とＢ3、Ｂ1とＢ4、Ｂ2とＢ3、またはＢ2とＢ4が、相互に結合して、それぞれが結合する炭素原子とともに環状構造を形成し、前記結合に関与しないB1〜B4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す。］
上記環状オレフィン系化合物（１）のうちでは、
ペンタシクロ［６．５．１．０2,7．１3,6．０9,13］ペンタデカ−４，１０−ジエン（以下、「トリシクロペンタジエン」ともいう。）（ｍ＝１）、
ヘプタシクロ［８．７．０．１2,9．０3,8．１4,7．１11,17．０12,16］エイコサ−５，１３−ジエン（以下、「テトラシクロペンタジエン」ともいう。）（ｍ＝２）、および
ノナシクロ［１０．９．１．０2,11．１3,10．０4,9．１5,8．０13,21．１14,20．０15,19］ペンタコサ−６，１６−ジエン（以下、「ペンタシクロペンタジエン」ともいう。）（ｍ＝３）
が好ましく、これらの中でも、合成および入手が容易な、トリシクロペンタジエンが特に好ましく用いられる。
[In Formula (3), B < 1 > -B < 4 > represents either of the following (i)-(v) each independently.
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom,
(Iv) B 1 and B 2 , or B 3 and B 4 are bonded to each other to form an alkylidene group, and B 1 to B 4 not participating in the bonding are independently of each other (i) to (iii (V) B 1 and B 3 , B 1 and B 4 , B 2 and B 3 , or B 2 and B 4 are bonded to each other, together with the carbon atoms to which they are bonded B 1 to B 4 that form a cyclic structure and do not participate in the bond are independently selected from the above (i) to (iii). ]
Among the cyclic olefin compounds (1),
Pentacyclo [6.5.1.0 2,7 . 1 3,6 . 0 9,13] pentadeca-4,10-diene (hereinafter, also referred to as "tricyclopentadiene".) (M = 1),
Heptacyclo [8.7.0.1 2,9 . 0 3,8 . 1 4,7 . 1 11,17 . 0 12,16] eicosa 5,13-diene (hereinafter, also referred to as "tetra cyclopentadiene".) (M = 2), and Nonashikuro [10.9.1.0 2,11. 1 3,10 . 0 4,9 . 1 5,8 . 0 13,21 . 1 14,20 . 0 15,19 ] pentacosa-6,16-diene (hereinafter also referred to as “pentacyclopentadiene”) (m = 3)
Among these, tricyclopentadiene, which is easy to synthesize and obtain, is particularly preferably used.
上記環状オレフィン系化合物（２）および環状オレフィン系化合物（３）において、ハロゲン原子としては、フッ素原子、塩素原子および臭素原子が挙げられる。 In the cyclic olefin compound (2) and the cyclic olefin compound (3), examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
上記環状オレフィン系化合物（２）において、極性基としては、アルコキシ基、水酸基、エステル基、シアノ基、アミノ基およびチオール基が挙げられる。アルコキシ基としては、例えばメトキシ基、エトキシ基などが挙げられ、炭素原子数１〜１０のアルコキシ基が好ましい。エステル基としては、例えばメトキシカルボニル基、エトキシカルボニル基などのアルコキシカルボニル基、フェノキシカルボニル基、ナフチルオキシカルボニル基、フルオレニルオキシカルボニル基、ビフェニリルオキシカルボニル基などのアリーロキシカルボニル基等が挙げられ、炭素数１〜１０のものが好ましい。アミノ基としては第１級アミノ基が好ましく挙げられ、炭素数１〜１０のものが好ましい。 In the cyclic olefin compound (2), examples of the polar group include an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group. Examples of the alkoxy group include a methoxy group and an ethoxy group, and an alkoxy group having 1 to 10 carbon atoms is preferable. Examples of the ester group include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aryloxycarbonyl groups such as phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, and biphenylyloxycarbonyl group. And those having 1 to 10 carbon atoms are preferred. The amino group is preferably a primary amino group, preferably having 1 to 10 carbon atoms.
上記環状オレフィン系化合物（２）および（３）において、炭素原子数１〜１０の脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基などのアルキル基、ビニル基、アリル基、プロペニル基などのアルケニル基が挙げられる。脂環族炭化水素基としては、炭素原子数５〜１０のものが好ましく、シクロペンチル基、シクロヘキシル基などのシクロアルキル基が挙げられる。芳香族炭化水素基としては、炭素原子数６〜２０のものが好ましく、たとえばフェニル基、ナフチル基、ビフェニル基、インデニル基、フルオレニル基、アントラセニル基などが挙げられる。 In the cyclic olefin compounds (2) and (3), examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group such as a methyl group, an ethyl group, and a propyl group, a vinyl group, an allyl group, Examples include alkenyl groups such as propenyl group. As an alicyclic hydrocarbon group, a C5-C10 thing is preferable and cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group, are mentioned. As the aromatic hydrocarbon group, those having 6 to 20 carbon atoms are preferable, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, an indenyl group, a fluorenyl group, and an anthracenyl group.
環状オレフィン系化合物（２）としては、具体的には、
５−メトキシカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−フェノキシカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−フェノキシエチルカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−フェニルカルボニルオキシ−ビシクロ［２．２．１］ヘプト−２−エン、
５−トリフロオロメチル−５−メトキシカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−メチル−５−メトキシカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−メチル−５−フェノキシカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−メチル−５−フェノキシエチルカルボニル−ビシクロ［２．２．１］ヘプト−２−エン、
５−ヒドロキシ−ビシクロ［２．２．１］ヘプト−２−エン、
５−ヒドロキシエチル−ビシクロ［２．２．１］ヘプト−２−エン、
５−シアノ−ビシクロ［２．２．１］ヘプト−２−エン、
５−アミノ−ビシクロ［２．２．１］ヘプト−２−エン、
８−メトキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−フェノキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−フェノキシエチルカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−フェニルカルボニルオキシ−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−メチル−８−メトキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−トリフロオロメチル−８−メトキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−メチル−８−フェノキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−メチル−８−フェノキシエチルカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−ヒドロキシ−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−ヒドロキシエチル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−メチル−８−ヒドロキシエチル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−シアノ−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、
８−アミノ−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン
等を挙げることができる。
Specifically, as the cyclic olefin compound (2),
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene,
5-trifluoromethyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
5-hydroxy-bicyclo [2.2.1] hept-2-ene,
5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene,
5-cyano-bicyclo [2.2.1] hept-2-ene,
5-amino-bicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-phenoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-phenylcarbonyloxy-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-trifluoromethyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-hydroxy-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-hydroxyethyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-cyano-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene,
8-amino-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene and the like.
本発明ではこのうち、環状オレフィン系化合物（２）として、８−メチル−８−メトキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エンが好ましく用いられる。 Of these, in the present invention, as the cyclic olefin compound (2), 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene is preferably used.
環状オレフィン系化合物（３）としては、具体的には、
ビシクロ［２．２．１］ヘプタ−２−エン（ノルボルネン）、
５―メチル−ビシクロ［２．２．１］ヘプタ−２−エン、
５―エチル−ビシクロ［２．２．１］ヘプタ−２−エン、
５―プロピル−ビシクロ［２．２．１］ヘプタ−２−エン、
５―ブチル−ビシクロ［２．２．１］ヘプタ−２−エン、
５―ヘキシル−ビシクロ［２．２．１］ヘプタ−２−エン、
５―オクチル−ビシクロ［２．２．１］ヘプタ−２−エン、
５―ヘキシル−ビシクロ［２．２．１］ヘプタ−２−エン、
５−シクロヘキシル−ビシクロ［２．２．１］ヘプタ−２−エン、
５−フェニル−ビシクロ［２．２．１］ヘプタ−２−エン、
トリシクロ［４．３．０．１2,5］デカ−３−エン、
トリシクロ［４．３．０．１2,5］デカ−３，７−ジエン（ジシクロペンタジエン）、
トリシクロ［４．４．０．１2,5］ウンデカ−３−エン、
７−メチル−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７−エチル−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７−シクロヘキシル−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７−フェニル−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７−（４−ビフェニル）−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７，８−ジメチル−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７，８，９−トリメチル−トリシクロ［４．３．０．１2,5］デカ−３−エン、
８−メチル−トリシクロ［４．４．０．１2,5］ウンデカ−３−エン、
８−フェニル−トリシクロ［４．４．０．１2,5］ウンデカ−３−エン、
７，８−ジクロロ−トリシクロ［４．３．０．１2,5］デカ−３−エン、
７，８，９−トリクロロ−トリシクロ［４．３．０．１2,5］デカ−３−エン、
このうち、ビシクロ［２．２．１］ヘプタ−２−エン、トリシクロ［４．３．０．１2,5］デカ−３−エンなどが好ましく用いられる。
Specifically, as the cyclic olefin compound (3),
Bicyclo [2.2.1] hept-2-ene (norbornene),
5-methyl-bicyclo [2.2.1] hept-2-ene,
5-ethyl-bicyclo [2.2.1] hept-2-ene,
5-propyl-bicyclo [2.2.1] hept-2-ene,
5-butyl-bicyclo [2.2.1] hept-2-ene,
5-hexyl-bicyclo [2.2.1] hept-2-ene,
5-octyl-bicyclo [2.2.1] hept-2-ene,
5-hexyl-bicyclo [2.2.1] hept-2-ene,
5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,
5-phenyl-bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 2,5 ] dec-3-ene,
Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (dicyclopentadiene),
Tricyclo [4.4.0.1 2,5 ] undec-3-ene,
7-methyl-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7-ethyl-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7-cyclohexyl-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7-phenyl-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7- (4-biphenyl) -tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7,8-dimethyl-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7,8,9-trimethyl-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
8-methyl-tricyclo [4.4.0.1 2,5 ] undec-3-ene,
8-phenyl-tricyclo [4.4.0.1 2,5 ] undec-3-ene,
7,8-dichloro-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
7,8,9-trichloro-tricyclo [4.3.0.1 2,5 ] dec-3-ene,
Of these, bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 2,5 ] dec-3-ene and the like are preferably used.
環状オレフィン系モノマーが、このような環状オレフィン系化合物（３）を含有することにより、環状オレフィン系モノマーを開環共重合して得られる本発明の環状オレフィン系重合体、およびその水素化物は、そのガラス転移温度（Ｔｇ）を容易に調節することができ、たとえば、成形体用途として望ましい１１０℃〜１８０℃の範囲の所望の温度とすることが可能となる。本発明の環状オレフィン系開環共重合体の製造方法において、環状オレフィン系モノマーが環状オレフィン系化合物（３）を含有する場合には、環状オレフィン系化合物（３）の含有量が多いほど、得られる開環共重合体のＴｇが低下する傾向を示すため、モノマー中の化合物（１）および化合物（２）の必要量とのバランスにより、開環共重合体のＴｇが所望の温度となる量を適宜選択することができ、これによりＴｇを調節することができる。 When the cyclic olefin monomer contains such a cyclic olefin compound (3), the cyclic olefin polymer of the present invention obtained by ring-opening copolymerization of the cyclic olefin monomer, and a hydride thereof, The glass transition temperature (Tg) can be easily adjusted. For example, the glass transition temperature (Tg) can be set to a desired temperature in a range of 110 ° C. to 180 ° C. that is desirable for a molded body. In the method for producing a cyclic olefin-based ring-opening copolymer of the present invention, when the cyclic olefin-based monomer contains the cyclic olefin-based compound (3), the larger the content of the cyclic olefin-based compound (3), the more Since the Tg of the resulting ring-opening copolymer tends to be lowered, the amount by which the Tg of the ring-opening copolymer becomes a desired temperature due to the balance with the required amount of the compound (1) and the compound (2) in the monomer Can be selected as appropriate, and Tg can be adjusted accordingly.
本発明に係る環状オレフィン系モノマーは、上述した環状オレフィン系化合物（１）、（２）および（３）以外の共重合性モノマーを含んでいてもよいが、その含有量は１０重量％以下、好ましくは５重量％以下、特に好ましくは、環状オレフィン系モノマーが、環状オレフィン系化合物（１）、（２）および必要に応じて（３）のみから構成されるのが望ましい。 The cyclic olefin monomer according to the present invention may contain a copolymerizable monomer other than the above-mentioned cyclic olefin compounds (1), (2) and (3), and the content thereof is 10% by weight or less, Preferably, it is 5 wt% or less, and particularly preferably, the cyclic olefin monomer is composed of only the cyclic olefin compounds (1) and (2) and, if necessary, (3).
＜開環共重合＞
本発明の環状オレフィン系開環共重合体の製造では、上述した環状オレフィン系モノマーを開環共重合する工程を有する。
<Ring-opening copolymerization>
The production of the cyclic olefin-based ring-opening copolymer of the present invention includes a step of ring-opening copolymerization of the cyclic olefin-based monomer described above.
開環共重合工程には、環状オレフィン系化合物の開環共重合に使用可能な触媒を制限なく用いることができるが、下記触媒成分（ａ）、（ｂ）および（ｃ）を用いて行うことが好ましい。
（a）有機アルミニウム化合物、
（b）ニトリル、ケトン、エーテル、およびエステルからなる群より選ばれる少なくとも一種の化合物、
（c）タングステン化合物、モリブデン化合物、レニウム化合物、バナジウム化合物、チタン化合物からなる群から選ばれる少なくとも一種の化合物。
In the ring-opening copolymerization step, a catalyst that can be used for ring-opening copolymerization of a cyclic olefin compound can be used without limitation, but the following catalyst components (a), (b), and (c) are used. Is preferred.
(A) an organoaluminum compound,
(B) at least one compound selected from the group consisting of nitriles, ketones, ethers, and esters,
(C) At least one compound selected from the group consisting of tungsten compounds, molybdenum compounds, rhenium compounds, vanadium compounds, and titanium compounds.
触媒成分（ａ）である有機アルミニウム化合物としては、下記式（１０）で表されるものが好ましい。
ＡｌＲnＸ3-n・・・（１０）
[式（１０）中、Ｒは、直鎖アルキル基あるいは分枝アルキル基を表し、Ｘはハロゲン原子を表す。]
また、有機アルミニウム化合物（ａ）として、アルミニウムオキシ化合物を用いることもできる。
As an organoaluminum compound which is a catalyst component (a), what is represented by following formula (10) is preferable.
AlR n X 3-n (10)
[In Formula (10), R represents a linear alkyl group or a branched alkyl group, and X represents a halogen atom. ]
Moreover, an aluminum oxy compound can also be used as the organoaluminum compound (a).
具体的には、たとえば、（Ｃ2Ｈ5）3Ａｌ、（iＢｕ）3Ａｌ、（Ｃ2Ｈ5）2ＡｌＣｌ、（Ｃ2Ｈ5）1.5ＡｌＣｌ1.5、（Ｃ2Ｈ5）ＡｌＣｌ2、メチルアルモキサンなどが挙げられる。 Specifically, for example, (C 2 H 5) 3 Al, (i Bu) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1.5, (C 2 H 5) AlCl 2 And methylalumoxane.
これらの有機アルミニウム化合物（ａ）は、１種単独でも、２種以上を組み合わせても使用することができる。 These organoaluminum compounds (a) can be used singly or in combination of two or more.
触媒成分（ｂ）としては、ニトリル基含有化合物、ケトン化合物、エーテル基含有化合物、およびエステル基化合物からなる群より選ばれる少なくとも一種の化合物を特に制限なく用いることができる。好ましいニトリル基含有化合物としては、下記式（１１）で表される化合物をあげることができ、好ましいケトンは下記式（１２）で表される化合物をあげることができ、好ましいエーテル基含有化合物は下記式（１３）で表される化合物をあげることができ、好ましいエステル基含有化合物としては下記式（１４）で表される化合物をあげることができる。 As the catalyst component (b), at least one compound selected from the group consisting of nitrile group-containing compounds, ketone compounds, ether group-containing compounds, and ester group compounds can be used without particular limitation. Preferred nitrile group-containing compounds include compounds represented by the following formula (11), preferred ketones include compounds represented by the following formula (12), and preferred ether group-containing compounds are: The compound represented by Formula (13) can be mentioned, As a preferable ester group containing compound, the compound represented by following formula (14) can be mentioned.
Ｒ−ＣＮ …（１１）
Ｒ−ＣＯ−Ｒ' …（１２）
Ｒ−Ｏ−（Ｚ−Ｏ）ｐ−Ｒ' …（１３）
Ｒ' '−ＣＯ2−Ｒ' …（１４）
[式（１１）〜（１４）中、Ｒ、Ｒ' および Ｒ' 'は、炭素数１〜２０の直鎖状または分枝状のアルキル基、炭素数５〜２０の脂環式炭化水素基、炭素数２〜２０の直鎖状または分岐状のアルケニル基、炭素数６〜２０のアリール基を表す。Ｚはメチレン、炭素数２〜４のアルキレン基、ｐは０〜３の整数を表す。ただし、Ｒ' 'の任意の水素原子が、水酸基で置換されていてもよい。]
たとえば、式（１１）の化合物としては、アセトニトリル、ベンゾニトリルなどが挙げられる。
式（１２）の化合物としては、たとえば、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノンなどが挙げられる。
式（１３）の化合物としては、たとえば、ジメチルエーテル、ジエチルエーテル、ジブチルエーテル、メチルエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテルなどが挙げられる。
式（１４）の化合物としては、酢酸メチルエステル、酢酸エチルエステル、酢酸ブチルエステル、酢酸フェニルエステル、乳酸エチルエステル、乳酸ブチルエステル、安息香酸メチルエステル、安息香酸エチルエステル、５−メチル−５−メトキシカルボニル−ビシクロ［２．２．１］ヘプタ−２−エン、２−メチル−２−メトキシカルボニル−ビシクロ［２．２．１］ヘプタン、８−メチル−８−メトキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカ−３−エン、２−メチル−２−メトキシカルボニル−テトラシクロ［４．４．０．１2,5．１7,10］ドデカンなどが挙げられる。
R-CN (11)
R-CO-R '(12)
R—O— (Z—O) p—R ′ (13)
R ′ ′ — CO 2 —R ′ (14)
[In the formulas (11) to (14), R, R ′ and R ′ ′ represent a linear or branched alkyl group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Represents a linear or branched alkenyl group having 2 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Z represents methylene, an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 0 to 3. However, any hydrogen atom of R ′ ′ may be substituted with a hydroxyl group. ]
For example, examples of the compound of the formula (11) include acetonitrile and benzonitrile.
Examples of the compound of the formula (12) include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and the like.
Examples of the compound of the formula (13) include dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol. Examples include dibutyl ether, dipropylene glycol dimethyl ether, and triethylene glycol dimethyl ether.
Examples of the compound of the formula (14) include acetic acid methyl ester, acetic acid ethyl ester, acetic acid butyl ester, acetic acid phenyl ester, lactic acid ethyl ester, lactic acid butyl ester, benzoic acid methyl ester, benzoic acid ethyl ester, 5-methyl-5-methoxy. Carbonyl-bicyclo [2.2.1] hept-2-ene, 2-methyl-2-methoxycarbonyl-bicyclo [2.2.1] heptane, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4. 0.1 2,5 . 1 7,10 ] dodec-3-ene, 2-methyl-2-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane and the like.
これらの触媒成分（ｂ）は、１種単独でも２種以上を組み合わせても使用することができる。 These catalyst components (b) can be used singly or in combination of two or more.
触媒成分（ｃ）としては、タングステン化合物、モリブデン化合物、レニウム化合物、バナジウム化合物、チタン化合物からなる群から選ばれる少なくとも一種の化合物を特に制限なく使用することができる。触媒成分（ｃ）として好適に用いられる化合物としては、Olefin Metathesis and Metathesis Polymerization（K.J.IVIN, J.C.MOL, Academic Press 1997）に記載されている化合物、たとえば、ＷＣｌ6、ＷOＣｌ4、Ｗ（ＣＯ）6、ＭｏＣｌ5、ＭｏＣｌ5、ＭｏＯ3、Ｍｏ（ＣＯ）6、ＲｅＣｌ5、Ｒｅ2Ｏ7、ＲｅＯＣｌ3、ＶＣｌ4、ＶＯＣｌ3、Ｖ2Ｏ5、ＴｉＣｌ4などが挙げられる。これらは、１種単独でも２種以上を組み合わせても使用することができる。 As the catalyst component (c), at least one compound selected from the group consisting of tungsten compounds, molybdenum compounds, rhenium compounds, vanadium compounds, and titanium compounds can be used without particular limitation. Examples of the compound suitably used as the catalyst component (c) include compounds described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997), for example, WCl 6 , WOCl 4 , W (CO) 6 , MoCl 5 , MoCl 5 , MoO 3 , Mo (CO) 6 , ReCl 5 , Re 2 O 7 , ReOCl 3 , VCl 4 , VOCl 3 , V 2 O 5 , TiCl 4 and the like. These can be used singly or in combination of two or more.
環状オレフィン系開環共重合体の製造においては、開環共重合触媒として、上述した触媒成分（ａ）、（ｂ）および（ｃ）を併用することが好ましいが、触媒成分（ａ）および（ｂ）をあらかじめ接触させてなる混合物（Ａ）と、触媒成分（ｂ）および（ｃ）をあらかじめ接触させてなる混合物（Ｂ）とを用いて開環共重合を行うことがより好ましい。 In the production of the cyclic olefin-based ring-opening copolymer, the catalyst components (a), (b) and (c) described above are preferably used in combination as the ring-opening copolymerization catalyst, but the catalyst components (a) and ( It is more preferable to perform ring-opening copolymerization using a mixture (A) obtained by bringing b) into contact with each other and a mixture (B) obtained by bringing the catalyst components (b) and (c) into contact with each other in advance.
触媒成分（ａ）および（ｂ）を接触させて、混合物（Ａ）を調製する操作は、窒素やアルゴンなどの不活性ガス雰囲気下、室温から１００℃の範囲で好適に実施することができる。混合比は特に限定されないが、触媒活性上、（ｂ）／（ａ）のモル比で、１／１〜１００／１の範囲が好ましい。混合時に使用する溶媒は、トルエン、シクロヘキサンなどの炭化水素系溶媒を用いることができる。この混合液は、作成後、直ちに重合に使用することができる。 The operation of preparing the mixture (A) by bringing the catalyst components (a) and (b) into contact with each other can be preferably carried out in the range of room temperature to 100 ° C. in an inert gas atmosphere such as nitrogen or argon. Although the mixing ratio is not particularly limited, the molar ratio of (b) / (a) is preferably in the range of 1/1 to 100/1 in view of catalyst activity. As the solvent used at the time of mixing, a hydrocarbon solvent such as toluene or cyclohexane can be used. This mixed solution can be used for polymerization immediately after preparation.
また、触媒成分（ｂ）および（ｃ）を接触させて、混合物（Ｂ）を調製する操作も、窒素やアルゴンなどの不活性ガス雰囲気下、室温から１００℃の範囲で好適に実施することができる。混合比は特に限定されないが、触媒活性上、（ｂ）／（ｃ）のモル比で、１／１〜１００／１の範囲が好ましい。混合時に使用する溶媒も混合物（Ａ）と同じく、トルエン、シクロヘキサンなどの炭化水素系溶媒を用いることができる。この混合液についても、作成後、直ちに重合に使用することができるが、添加する触媒成分（ｂ）の種類によって経時的に変質する場合があるため、作成後１時間以内に使用することが望ましく、更に３０分以内に使用することがより望ましい。
環状オレフィン系モノマーの共重合を、予め触媒成分（ａ）および（ｂ）を接触させた混合物（Ａ）と、予め触媒成分（ｂ）および（ｃ）を接触させた混合物（Ｂ）とを用いて行うことにより、それぞれを別個に重合系に添加する場合よりも、分子量分布が狭い共重合体を容易に製造することができる。このことにより、分子量分布の広い共重合体中に含まれる、溶媒に溶解しにくい高分子量成分を実質的に含まず、光学用途の成形体の製造により好適な環状オレフィン系共重合体を得ることができる。
In addition, the operation of preparing the mixture (B) by bringing the catalyst components (b) and (c) into contact with each other can be preferably carried out in the range of room temperature to 100 ° C. in an inert gas atmosphere such as nitrogen or argon. it can. Although the mixing ratio is not particularly limited, the molar ratio of (b) / (c) is preferably in the range of 1/1 to 100/1 in view of catalyst activity. The solvent used at the time of mixing can use hydrocarbon type solvents, such as toluene and a cyclohexane similarly to the mixture (A). This mixed solution can also be used for polymerization immediately after preparation, but it may be altered over time depending on the type of catalyst component (b) to be added, so it is desirable to use it within one hour after preparation. More preferably, it is used within 30 minutes.
For the copolymerization of the cyclic olefin monomer, a mixture (A) in which the catalyst components (a) and (b) are contacted in advance and a mixture (B) in which the catalyst components (b) and (c) are contacted in advance are used. As a result, a copolymer having a narrow molecular weight distribution can be easily produced as compared with the case where each is added separately to the polymerization system. As a result, a cyclic olefin copolymer that is substantially free of high molecular weight components that are difficult to dissolve in a solvent and contained in a copolymer having a wide molecular weight distribution and that is more suitable for the production of a molded article for optical use is obtained. Can do.
重合系に添加する混合物（Ａ）（（ａ）＋（ｂ）成分）と、混合物（Ｂ）（（ｂ）＋（ｃ）成分）の使用割合は、特に限定は無いが、触媒活性上、（ａ）／（ｃ）の金属原子（モル）比が、１／１〜５０／１を満たす範囲であるのが好ましく、更に１．５／１〜３０／１を満たす範囲がより好ましい。 The ratio of the mixture (A) ((a) + (b) component) and the mixture (B) ((b) + (c) component) to be added to the polymerization system is not particularly limited. The metal atom (mole) ratio of (a) / (c) is preferably in a range satisfying 1/1 to 50/1, and more preferably in a range satisfying 1.5 / 1 to 30/1.
環状オレフィン系モノマーに対する触媒成分（ｃ）の使用量は、モノマー全量とのモル比、「モノマー全量／触媒成分（ｃ）」が、５００／１より大きい範囲が好ましく、更に１，０００／１より大となる範囲がより好ましい。この比率が小さく、触媒量が多い範囲だと、得られる共重合体中に残留する触媒量が多くなってしまい、ポリマーの色相、劣化性に大きな影響をおよぼす場合がある。 The amount of the catalyst component (c) used with respect to the cyclic olefin-based monomer is preferably such that the molar ratio with respect to the total amount of monomers and the “total amount of monomer / catalyst component (c)” is greater than 500/1, more preferably 1,000 / 1. A larger range is more preferable. If this ratio is small and the amount of catalyst is large, the amount of catalyst remaining in the resulting copolymer increases, which may greatly affect the hue and deterioration of the polymer.
重合溶媒としては、環状オレフィン系モノマーと、触媒成分（ａ）〜（ｃ）とを溶解あるいは分散するものを用いることができる。重合溶媒の具体例としては、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカンなどのアルカン類、シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナンなどのシクロアルカン類、ベンゼン、トルエン、キシレン、エチルベンゼン、クメンなどの芳香族炭化水素、クロロブタン、ブロムヘキサン、塩化メチレン、ジクロロエタン、ヘキサメチレンジブロミド、クロロベンゼン、クロロホルム、テトラクロロエチレンなどのハロゲン化アルカン、酢酸エチル、酢酸ｎ−ブチル、酢酸ｉｓｏ−ブチル、プロピオン酸メチルなどの飽和カルボン酸エステル類、ジブチルエーテル、テトラヒドロフラン、ジメトキシエタンなどのエーテル類を挙げることができる。本発明で用いる重合溶媒は、これらの中でも、環状オレフィン系化合物（２）を共重合したポリマーの溶解性が良好な、芳香族炭化水素を含有することが好ましい。また、これらの重合溶媒は単独でまたは２種以上を組み合わせて用いることができる。 As the polymerization solvent, a solvent that dissolves or disperses the cyclic olefin monomer and the catalyst components (a) to (c) can be used. Specific examples of the polymerization solvent include alkanes such as pentane, hexane, heptane, octane, nonane, decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, benzene, toluene, xylene, ethylbenzene, cumene. Aromatic hydrocarbons such as, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, etc. And saturated ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. Among these, the polymerization solvent used in the present invention preferably contains an aromatic hydrocarbon in which the polymer obtained by copolymerizing the cyclic olefin compound (2) has good solubility. Moreover, these polymerization solvents can be used alone or in combination of two or more.
環状オレフィン系開環共重合体の製造においては、得られる環状オレフィン系共重合体が、用途に応じて所望の分子量となるよう、適宜開環共重合反応条件を調整することができ、開環共重合反応において、分子量調節剤を用いることもできる。 In the production of the cyclic olefin-based ring-opening copolymer, the ring-opening copolymerization reaction conditions can be appropriately adjusted so that the obtained cyclic olefin-based copolymer has a desired molecular weight depending on the application. In the copolymerization reaction, a molecular weight modifier can also be used.
好適に用いることのできる分子量調節剤の具体例としては、エチレン、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−デセンなどのα−オレフィン類およびスチレンなどを挙げることができ、これらのうち、１−ブテン、１−ヘキセンが特に好ましい。これらの化合物は、単独であるいは２種以上を組み合わせて分子量調節剤として用いることができる。 Specific examples of molecular weight regulators that can be suitably used include α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. Examples thereof include olefins and styrene. Among these, 1-butene and 1-hexene are particularly preferable. These compounds can be used as molecular weight regulators alone or in combination of two or more.
分子量調節剤の使用量としては、特に限定されるものではないが、開環共重合反応に供される環状オレフィン系モノマー１モルに対して、好ましくは０．００５〜０．６モル、より好ましくは０．０２〜０．５モルの範囲であるのが望ましい。 The amount of the molecular weight regulator used is not particularly limited, but is preferably 0.005 to 0.6 mol, more preferably, with respect to 1 mol of the cyclic olefin monomer used for the ring-opening copolymerization reaction. Is preferably in the range of 0.02 to 0.5 mol.
開環共重合反応を行う際の反応時間は特に限定されないが、生産上、０．１〜１０時間、好ましくは０．１〜５時間、より好ましくは０．１〜３時間であるのが望ましい。また、反応温度は５０〜１８０℃、好ましくは７０〜１６０℃程度の範囲であることが望ましい。 The reaction time for carrying out the ring-opening copolymerization reaction is not particularly limited, but is desirably 0.1 to 10 hours, preferably 0.1 to 5 hours, and more preferably 0.1 to 3 hours in production. . The reaction temperature is desirably in the range of 50 to 180 ° C, preferably about 70 to 160 ° C.
＜水素化＞
上述のように、環状オレフィン系モノマーを開環重合しただけの環状オレフィン系開環重合体は、そのままで用いることもできるが、分子内にオレフィン性不飽和結合を有しており、用途によっては耐熱性が充分でないことから、さらに水素化（水素添加反応）を行うことが好ましい。
<Hydrogenation>
As described above, the cyclic olefin-based ring-opening polymer obtained by ring-opening polymerization of the cyclic olefin-based monomer can be used as it is, but has an olefinically unsaturated bond in the molecule, depending on the application. Since heat resistance is not sufficient, it is preferable to perform further hydrogenation (hydrogenation reaction).
本発明における水素化の工程には、公知の方法を適用できる。例えば、特開昭６３−２１８７２６号公報、特開平１−１３２６２６号公報、特開平１−２４０５１７号公報、特開平２−１０２２１号公報、特開２００５−１６２６１７公報、特開２００５−１６２６１８公報、特開２００５−２１３３７０公報、特開２００７−１９６７公報、特開２００７−１０６９３２公報などに記載された触媒や溶媒および温度条件などを適用することで、水素化の工程を実施することができる。 A known method can be applied to the hydrogenation step in the present invention. For example, Japanese Patent Laid-Open Nos. 63-218726, 1-126626, 1-224017, 2-102221, 2005-162617, 2005-162618, The hydrogenation step can be performed by applying the catalyst, solvent, temperature conditions, and the like described in Japanese Unexamined Patent Application Publication Nos. 2005-213370, 2007-1967, and 2007-106932.
環状オレフィン系開環重合体のオレフィン性不飽和結合の水素添加率としては、通常８０モル％以上、好ましくは９０モル％以上、より好ましくは９５モル％以上、さらに好ましくは９９モル％以上であることが望ましい。なお、本発明における水素化とは、分子内のオレフィン性不飽和結合に対するものであり、環状オレフィン系開環重合体が芳香族基を有する場合、係る芳香族基は屈折率など光学的な特性や耐熱性において有利に作用することもあるので、必ずしも水素化される必要はない。 The hydrogenation rate of the olefinically unsaturated bond of the cyclic olefin-based ring-opening polymer is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more. It is desirable. The hydrogenation in the present invention refers to olefinic unsaturated bonds in the molecule, and when the cyclic olefin-based ring-opening polymer has an aromatic group, the aromatic group has optical characteristics such as refractive index. In some cases, it does not necessarily have to be hydrogenated.
上述のようにして、環状オレフィン系モノマーを開環共重合し、必要に応じて水素化して得られた環状オレフィン系開環共重合体は、必要に応じて公知の方法で、精製、脱触媒、脱溶媒などの処理をして用いてもよい。 As described above, a cyclic olefin-based ring-opening copolymer obtained by ring-opening copolymerization of a cyclic olefin-based monomer and hydrogenating as necessary can be purified, decatalyzed, if necessary, by a known method. , And may be used after treatment such as desolvation.
＜添加剤＞
本発明の環状オレフィン系共重合体は、そのまま成形に用いてもよいが、耐熱劣化性や耐光性の改良のために公知の酸化防止剤や紫外線吸収剤などの添加剤を添加して用いることができる。添加剤としては、例えば、樹脂への添加剤として公知のフェノール系化合物、チオール系化合物、スルフィド系化合物、ジスルフィド系化合物、リン系化合物などを用いることができ、これらの少なくとも１種の化合物を、本発明の環状オレフィン系開環重合体１００重量部に対して０．０１〜１０重量部添加することで、耐熱劣化性や耐光性などの特性を向上させることができる。
<Additives>
The cyclic olefin copolymer of the present invention may be used for molding as it is, but it is used by adding additives such as known antioxidants and ultraviolet absorbers for improving heat resistance and light resistance. Can do. As the additive, for example, known phenol compounds, thiol compounds, sulfide compounds, disulfide compounds, phosphorus compounds and the like can be used as additives to the resin, and at least one of these compounds is used as an additive. By adding 0.01 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin-based ring-opening polymer of the present invention, characteristics such as heat deterioration resistance and light resistance can be improved.
また、本発明の環状オレフィン系開環共重合体には、目的とする成形体の特性等に応じて、その他の添加剤を添加して用いてもよい。たとえば、着色されたフィルムを得ることを目的として、染料、顔料等の着色剤を添加してもよく、得られるフィルムの平滑性を向上させることを特徴としてレベリング剤を添加してもよい。レベリング剤としては、たとえば、フッ素系ノニオン界面活性剤、特殊アクリル樹脂系レベリング剤、シリコーン系レベリング剤などが挙げられる。 In addition, other additives may be added to the cyclic olefin-based ring-opening copolymer of the present invention depending on the properties of the objective molded article. For example, for the purpose of obtaining a colored film, colorants such as dyes and pigments may be added, and a leveling agent may be added to improve the smoothness of the resulting film. Examples of the leveling agent include a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, and a silicone leveling agent.
＜用途＞
本発明に係る環状オレフィン系開環共重合体、特に水素化物である環状オレフィン系開環共重合体は、たとえばレンズ状、フィルム状、シート状、などの所望の形状に公知の方法により成形して用いることができ、光学フィルムなどの各種光学部品等の用途に好適に用いることができる。
<Application>
The cyclic olefin ring-opening copolymer according to the present invention, particularly the cyclic olefin ring-opening copolymer that is a hydride, is formed into a desired shape such as a lens shape, a film shape, or a sheet shape by a known method. And can be suitably used for various optical parts such as an optical film.
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。以下の実施例および比較例において、重合反応、触媒調製、水素化反応などの各工程は、窒素雰囲気下で実施した。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following Examples and Comparative Examples, each step such as polymerization reaction, catalyst preparation, hydrogenation reaction and the like was performed under a nitrogen atmosphere.
また以下の実施例および比較例において、各性状の測定及び評価は、以下の方法により行った。 In the following examples and comparative examples, each property was measured and evaluated by the following methods.
ガラス転移温度（Ｔｇ）
示差走査熱量計（セイコーインスツルメンツ社製、商品名：ＤＳＣ６２００）を用いて、日本工業規格Ｋ７１２１に従って補外ガラス転移開始温度（以下、単にガラス転移温度（Ｔｇ）という）を求めた。
Glass transition temperature (Tg)
Using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.), an extrapolated glass transition start temperature (hereinafter simply referred to as glass transition temperature (Tg)) was determined according to Japanese Industrial Standard K7121.
重量平均分子量および分子量分布
ゲルパーミエーションクロマトグラフィー（ＧＰＣ、東ソー株式会社製、商品名：ＨＬＣ-８０２０）を用い、溶媒としてテトラヒドロフラン（ＴＨＦ）を用いて、ポリスチレン換算の重量平均分子量（Ｍw）および分子量分布（Ｍw／Ｍn）を測定した。
Weight average molecular weight and molecular weight distribution Gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020), tetrahydrofuran (THF) as a solvent, polystyrene equivalent weight average molecular weight (M w ) and The molecular weight distribution (M w / M n ) was measured.
1 Ｈ−ＮＭＲ分析
超伝導核磁気共鳴吸収装置（ＮＭＲ、Ｂｒｕｋｅｒ社製、商品名：ＡＶＡＮＣＥ５００）を用い、重水素化クロロホルム中で1Ｈ−ＮＭＲを測定し、共重合組成比および水素添加率を算出した。
1 H-NMR analysis Using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500), 1 H-NMR was measured in deuterated chloroform to determine the copolymer composition ratio and hydrogenation rate. Calculated.
モノマーの転化率分析
ガスクロマトグラフィー（株式会社島津製作所製、商品名：ＧＣ-２０１４）を用いて反応溶液中に含まれる残モノマーの量を分析し、算出した。
Conversion analysis of monomer The amount of residual monomer contained in the reaction solution was analyzed and calculated using gas chromatography (manufactured by Shimadzu Corporation, trade name: GC-2014).
屈折率
メトリコン社製ＰＣ−２０１０型プリズムカプラを用い、フィルムサンプルの任意の５箇所の屈折率を測定し、最大値および最小値を除く３点の平均値を採用した。なお、光源には４０８ｎｍ，６３３ｎｍ、および８３０ｎｍのレーザー光源を用い、得られた屈折率からコーシーの式を用いた回帰計算により５８９ｎｍにおける屈折率を算出した。
Refractive index Using a PC-2010 type prism coupler manufactured by Metricon, the refractive index was measured at any five locations of the film sample, and an average value of three points excluding the maximum value and the minimum value was adopted. Note that 408 nm, 633 nm, and 830 nm laser light sources were used as the light source, and the refractive index at 589 nm was calculated from the obtained refractive index by regression calculation using Cauchy's equation.
ａｂｂｅ数
下記式により、ａｂｂｅ数νを算出した。
Abbe number Abbe number ν was calculated by the following equation.
ν＝（ｎD−１）／（ｎF−ｎC）
前記式中、ｎD、ｎF、ｎCは、それぞれ屈折率の測定結果から回帰計算により求めた５８９．２ｎｍ、４８６．１ｎｍ、６５６．３ｎｍにおける屈折率である。
ν = (n D −1) / (n F −n C )
In the above formula, n D , n F , and n C are refractive indexes at 589.2 nm, 486.1 nm, and 656.3 nm, respectively, obtained by regression calculation from the refractive index measurement results.
［実施例１］
環状オレフィン系モノマーとして、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセン（７９．９ｇ、３４４ｍｍｏｌ）、トリシクロペンタジエン（１０２.３ｇ、５１６ｍｍｏｌ）、分子量調節剤として１−ヘキセン（２．９ｇ、３４．４ｍｍｏｌ）をトルエン（２７３ｇ）に添加し、１０５℃に加熱撹拌した。別途に、（ｉ−Ｂｕ3）Ａｌ（１０７μｍｏｌ）とＢｕ2Ｏ（８６μｍｏｌ）を室温で混合させたトルエン溶液（１．９ｍＬ）と、ＷＣｌ6（４３μｍｏｌ）と８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセン（８６μｍｏｌ）を室温で混合させたトルエン溶液（２．１ｍＬ）を準備した。前述のモノマートルエン溶液に対し、（ｉ−Ｂｕ3）ＡｌとＢｕ2Ｏの混合溶液、ＷＣｌ6と８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンの混合溶液の順で、順次に添加し、重合反応を開始した。重合１時間の後に反応停止剤としてＬｉＯＨ（２５８μｍｏｌ）を添加し、開環共重合体（１）のトルエン溶液を得た。モノマーの転化率を測定したところ９７％であった。この一部を多量のメタノール中で沈殿、減圧乾燥させることにより、開環共重合体（１）を得た。1Ｈ−ＮＭＲの分析により、ポリマー中のモノマー組成は、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンが５９．８ｍｏｌ％、トリシクロペンタジエンが４０．２ｍｏｌ％であった。ＧＰＣを測定したところ、重量平均分子量（Ｍw）＝５５，０００、分子量分布（Ｍw／Ｍn）＝３．６であった。
[Example 1]
As the cyclic olefin monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (79.9 g, 344 mmol), tricyclopentadiene (102.3 g, 516 mmol) and 1-hexene (2.9 g, 34.4 mmol) as a molecular weight regulator in toluene (273 g) The mixture was added and heated to 105 ° C with stirring. Separately, a toluene solution (1.9 mL) in which (i-Bu 3 ) Al (107 μmol) and Bu 2 O (86 μmol) were mixed at room temperature, WCl 6 (43 μmol), and 8-methyl-8-methoxycarbonyltetra Cyclo [4.4.0.1 2,5 . A toluene solution (2.1 mL) was prepared by mixing 1 7,10 ] -3-dodecene (86 μmol) at room temperature. A mixed solution of (i-Bu 3 ) Al and Bu 2 O, WCl 6 and 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene was added sequentially in the order of the mixed solution to start the polymerization reaction. After 1 hour of polymerization, LiOH (258 μmol) was added as a reaction terminator to obtain a toluene solution of the ring-opening copolymer (1). The monomer conversion was measured and found to be 97%. A part of this was precipitated in a large amount of methanol and dried under reduced pressure to obtain a ring-opening copolymer (1). According to 1 H-NMR analysis, the monomer composition in the polymer was found to be 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene was 59.8 mol% and tricyclopentadiene was 40.2 mol%. When GPC was measured, it was weight average molecular weight (M w ) = 55,000 and molecular weight distribution (M w / M n ) = 3.6.
［実施例２］
実施例１で得られた開環重合体（１）の溶液を水添反応容器に移液し、トルエン（４５６ｇ）を加え撹拌して均一溶液とし、水素添加反応触媒であるＲｕ［４−ＣＨ3（ＣＨ2）4Ｃ6Ｈ4ＣＯ2］Ｈ（ＣＯ）［Ｐ（Ｃ6Ｈ5）3］（６１．０ｍｇ、７２μｍｏｌ）を添加した。９０℃まで温度を上げてから、水素を７ＭＰａまで導入した後、最終的に１６０〜１６５℃まで温度を上げ、導入水素ガス圧を９〜１０ＭＰａとし３時間反応させた。得られた生成物を多量のメタノール中で沈殿、減圧乾燥させることにより、開環共重合水素化体（１）を得た。1Ｈ−ＮＭＲの分析により水素化率は、９９％であった。ＤＳＣの測定によりＴｇ＝１７３℃であった。ＧＰＣを測定したところ、重量平均分子量（Ｍw）＝５７，０００、分子量分布（Ｍw／Ｍn）＝３．４であった。また屈折率はnD=１．５２７、ａｂｂｅ数は５６であった。
[Example 2]
The solution of the ring-opening polymer (1) obtained in Example 1 was transferred to a hydrogenation reaction vessel, toluene (456 g) was added and stirred to obtain a homogeneous solution, and Ru [4-CH as a hydrogenation reaction catalyst. 3 (CH 2) 4 C 6 H 4 CO 2] H (CO) [P (C 6 H 5) 3] (61.0mg, 72μmol) was added. After the temperature was raised to 90 ° C., hydrogen was introduced to 7 MPa, and finally the temperature was raised to 160 to 165 ° C., and the introduced hydrogen gas pressure was set to 9 to 10 MPa and reacted for 3 hours. The obtained product was precipitated in a large amount of methanol and dried under reduced pressure to obtain a ring-opening copolymerized hydrogenated product (1). The hydrogenation rate was 99% by analysis of 1 H-NMR. It was Tg = 173 degreeC by the measurement of DSC. When GPC was measured, it was weight average molecular weight (M w ) = 57,000 and molecular weight distribution (M w / M n ) = 3.4. The refractive index was n D = 1.527, and the abbe number was 56.
［実施例３］
環状オレフィン系モノマーとして、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセン（３０．０ｇ、１２９ｍｍｏｌ）、トリシクロペンタジエン（９７．５ｇ、４９２ｍｍｏｌ）、ビシクロ［２．２．１］ヘプト−２−エン（２２．５ｇ、２３９ｍｍｏｌ）、トルエン（２１５ｇ）を用いた他は、実施例１と同じ操作を実施し、開環共重合体（２）のトルエン溶液を得た。モノマーの転化率を測定したところ９８％であった。この一部を多量のメタノール中で沈殿、減圧乾燥させることにより、開環共重合体（２）を得た。1Ｈ−ＮＭＲの分析により、ポリマー中のモノマー組成は、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンが１４．３ｍｏｌ％、トリシクロペンタジエンが５７．３ｍｏｌ％、ビシクロ［２．２．１］ヘプタ−２−エンが２８．４ｍｏｌ％であった。ＧＰＣ測定の結果、重量平均分子量（Ｍw）＝４９，０００、分子量分布（Ｍw／Ｍn）＝３．３であった。
[Example 3]
As the cyclic olefin monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (30.0 g, 129 mmol), tricyclopentadiene (97.5 g, 492 mmol), bicyclo [2.2.1] hept-2-ene (22.5 g, 239 mmol), toluene Except for using (215 g), the same operation as in Example 1 was performed to obtain a toluene solution of the ring-opening copolymer (2). The monomer conversion was measured and found to be 98%. A part of this was precipitated in a large amount of methanol and dried under reduced pressure to obtain a ring-opening copolymer (2). According to 1 H-NMR analysis, the monomer composition in the polymer was found to be 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene was 14.3 mol%, tricyclopentadiene was 57.3 mol%, and bicyclo [2.2.1] hept-2-ene was 28.4 mol%. As a result of the GPC measurement, the weight average molecular weight (M w ) = 49,000 and the molecular weight distribution (M w / M n ) = 3.3.
［実施例４］
実施例３で得た開環重合体（２）を、実施例２と同様の操作で水素化することにより、開環共重合水素化体（２）を得た。1Ｈ−ＮＭＲの分析により水素化率は、９９％であった。ＤＳＣの測定によりＴｇ＝１４５℃であった。ＧＰＣを測定したところ、重量平均分子量（Ｍw）＝５１，０００、分子量分布（Ｍw／Ｍn）＝３．１であった。また屈折率はｎD=１．５３１、ａｂｂｅ数は５６であった。
[Example 4]
The ring-opening polymer (2) obtained in Example 3 was hydrogenated in the same manner as in Example 2 to obtain a ring-opening copolymerized hydrogenated product (2). The hydrogenation rate was 99% by analysis of 1 H-NMR. It was Tg = 145 degreeC by the measurement of DSC. When GPC was measured, it was weight average molecular weight (M w ) = 51,000 and molecular weight distribution (M w / M n ) = 3.1. The refractive index was n D = 1.531, and the abbe number was 56.
［比較例１］
環状オレフィン系モノマーとして、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセン（６３．５ｇ、２７３ｍｍｏｌ）、ジシクロペンタジエン（７７．５ｇ、５８７ｍｍｏｌ）、トルエン（２１２ｇ）を用いた他は、実施例１と同じ操作を実施し、開環共重合体（３）のトルエン溶液を得た。モノマーの転化率を測定したところ９７％であった。1Ｈ−ＮＭＲの分析により、ポリマー中のモノマー組成は、８−メチル−８−メトキシカルボニルテトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンが３０．６ｍｏｌ％、ジシクロペンタジエンが６９．４ｍｏｌ％であった。続いて、実施例２と同じ操作により水素化反応を実施した結果、開環共重合水素化体（３）を得た。1Ｈ−ＮＭＲの分析により水素化率は、９９％であった。ＤＳＣの測定によりＴｇは、１２７℃と、実用温度の下限に近い値であった。ＧＰＣを測定したところ、重量平均分子量（Ｍw）＝５２，０００、分子量分布（Ｍw／Ｍn）＝２．７であった。しかし、ａｂｂｅ数は５６になったものの、屈折率はｎD=１．５２２にとどまり、目的の光学性能を実現することはできなかった。
[Comparative Example 1]
As the cyclic olefin monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (63.5 g, 273 mmol), dicyclopentadiene (77.5 g, 587 mmol) and toluene (212 g) were used, and the same operation as in Example 1 was carried out. A toluene solution of copolymer (3) was obtained. The monomer conversion was measured and found to be 97%. According to 1 H-NMR analysis, the monomer composition in the polymer was found to be 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene was 30.6 mol%, and dicyclopentadiene was 69.4 mol%. Then, as a result of implementing hydrogenation reaction by the same operation as Example 2, the ring-opening copolymerization hydrogenation body (3) was obtained. The hydrogenation rate was 99% by analysis of 1 H-NMR. According to the DSC measurement, Tg was 127 ° C., which was close to the lower limit of the practical temperature. When GPC was measured, it was weight average molecular weight (M w ) = 52,000 and molecular weight distribution (M w / M n ) = 2.7. However, although the abbe number is 56, the refractive index is only n D = 1.522, and the target optical performance cannot be realized.
［比較例２］
環状オレフィン系モノマーとして、テトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセン（５５．１ｇ、３４４ｍｍｏｌ）、トリシクロペンタジエン（１０２.３ｇ、５１６ｍｍｏｌ）を用いた他は、実施例１と同じ操作を実施し、開環共重合体（４）のトルエン溶液を得た。モノマーの転化率を測定したところ９８％であった。ポリマー溶液は流動性をもっているものの、白濁が生じており、透明性は失われていた。1Ｈ−ＮＭＲの分析により、ポリマー中のモノマー組成は、テトラシクロ［４．４．０．１2,5．１7,10］−３−ドデセンが５１ｍｏｌ％、トリシクロペンタジエンが４９ｍｏｌ％であった。続いて、実施例２と同じ操作により水素化反応を実施したところ、トルエンに不溶な成分が生成してしまい、流動性のあるポリマー溶液を得ることができなかった。
[Comparative Example 2]
As the cyclic olefin monomer, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene (55.1 g, 344 mmol) and tricyclopentadiene (102.3 g, 516 mmol) were used in the same manner as in Example 1 to obtain a ring-opening copolymer (4 ) Was obtained. The monomer conversion was measured and found to be 98%. Although the polymer solution had fluidity, white turbidity occurred and transparency was lost. According to 1 H-NMR analysis, the monomer composition in the polymer was tetracyclo [4.4.0.1 2,5 . 1 7,10 ] -3-dodecene was 51 mol% and tricyclopentadiene was 49 mol%. Subsequently, when the hydrogenation reaction was carried out by the same operation as in Example 2, a component insoluble in toluene was generated, and a fluid polymer solution could not be obtained.
本発明に係る環状オレフィン系開環共重合体、特に水素化物である環状オレフィン系開環水素化共重合体は、光線透過率や耐熱性に優れた熱可塑性透明樹脂として光学部品として好適に用いることができる。光学部品としては、光学レンズ、フィルム、シートを挙げることができ、これらの具体例として、撮像レンズ、導光板、位相差フィルム、保護フィルム、接着フィルム、タッチパネル、透明電極基板、ＴＦＴ用基板、カラーフィルター基板などが挙げられる。特に本発明に係る環状オレフィン系開環共重合体、特に水素化物である環状オレフィン系開環水素化共重合体は、高い屈折率と、高いａｂｂｅ数を有するため各種成形体製造用途に好適に使用でき、特にレンズ、フィルムなどの各種光学用途に用いる成形体の製造用途に好適に用いることができ、中でも光学レンズ用途に好適に用いることができる。 The cyclic olefin ring-opening copolymer according to the present invention, particularly the cyclic olefin ring-opening hydrogenated copolymer that is a hydride, is suitably used as an optical component as a thermoplastic transparent resin excellent in light transmittance and heat resistance. be able to. Examples of optical components include optical lenses, films, and sheets. Specific examples thereof include imaging lenses, light guide plates, retardation films, protective films, adhesive films, touch panels, transparent electrode substrates, TFT substrates, and colors. Examples include a filter substrate. In particular, the cyclic olefin-based ring-opening copolymer according to the present invention, particularly the cyclic olefin-based ring-opening hydrogenated copolymer, which is a hydride, has a high refractive index and a high abebe number, and thus is suitable for various molded article production applications. In particular, it can be suitably used for the production of molded articles used for various optical applications such as lenses and films, and can be suitably used for optical lens applications.
Claims (5)
（i）水素原子、
（ii）ハロゲン原子、
（iii）アルコキシ基、水酸基、エステル基、シアノ基、アミノ基およびチオール基よりなる群から選ばれた極性基、
（iv）ハロゲン原子または前記極性基（iii）により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基。Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。） A cyclic olefin ring-opening copolymer comprising a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II):
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group,
(Iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom or the polar group (iii). X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —. )
（i）水素原子、
（ii）ハロゲン原子、
（iii）ハロゲン原子により置換されていてもよい、炭素数１〜１０の脂肪族炭化水素基、脂環族炭化水素基、または芳香族炭化水素基、
（iv）Ｂ1とＢ2、またはＢ3とＢ4が、相互に結合してアルキリデン基を形成し、前記結合に関与しないＢ1〜Ｂ4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す、（ｖ）Ｂ1とＢ3、Ｂ1とＢ4、Ｂ2とＢ3、またはＢ2とＢ4が、相互に結合して、それぞれが結合する炭素原子とともに環状構造を形成し、前記結合に関与しないB1〜B4は相互に独立に前記（ｉ）〜（iii）より選ばれるものを表す。Ｘは独立に式：−ＣＨ＝ＣＨ−で表される基または式：−ＣＨ2ＣＨ2−で表される基である。） The cyclic olefin ring-opening copolymer according to claim 1, further comprising a structural unit (III) represented by the following formula (III).
(I) a hydrogen atom,
(Ii) a halogen atom,
(Iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom,
(Iv) B 1 and B 2 , or B 3 and B 4 are bonded to each other to form an alkylidene group, and B 1 to B 4 not participating in the bonding are independently of each other (i) to (iii (V) B 1 and B 3 , B 1 and B 4 , B 2 and B 3 , or B 2 and B 4 are bonded to each other, together with the carbon atoms to which they are bonded B 1 to B 4 that form a cyclic structure and do not participate in the bond are independently selected from the above (i) to (iii). X is independently a group represented by the formula: —CH═CH— or a group represented by the formula: —CH 2 CH 2 —. )
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| JP2011026588A (en) * | 2009-06-30 | 2011-02-10 | Jsr Corp | Method for producing cyclic olefin ring-opened copolymer |
| JP2013144773A (en) * | 2011-12-16 | 2013-07-25 | Jsr Corp | Cyclic olefin ring-opened copolymer |
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| JP2012149151A (en) * | 2011-01-18 | 2012-08-09 | Jsr Corp | Resin for etching mask, coating material for etching mask and method for forming pattern on sapphire substrate |
| US11597797B2 (en) | 2012-12-27 | 2023-03-07 | Rimtec Corporation | Liquid blend for reaction injection molding, method for producing reaction injection molded body, and reaction injection molded body |
| WO2014103830A1 (en) * | 2012-12-27 | 2014-07-03 | Rimtec株式会社 | Liquid blend for reaction injection molding, method for producing reaction injection molded body, and reaction injection molded body |
| US20170114160A1 (en) | 2014-06-27 | 2017-04-27 | Rimtec Corporation | Liquid formulation for reaction injection molding and manufacturing method thereof |
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| JP2013144773A (en) * | 2011-12-16 | 2013-07-25 | Jsr Corp | Cyclic olefin ring-opened copolymer |
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| JP2011026588A (en) | 2011-02-10 |
| JP5545078B2 (en) | 2014-07-09 |
| JP5545079B2 (en) | 2014-07-09 |
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