JP4466273B2 - Ring-opening polymer, hydride of ring-opening polymer, production method thereof, and polymerization catalyst composition - Google Patents
Ring-opening polymer, hydride of ring-opening polymer, production method thereof, and polymerization catalyst composition Download PDFInfo
- Publication number
- JP4466273B2 JP4466273B2 JP2004235282A JP2004235282A JP4466273B2 JP 4466273 B2 JP4466273 B2 JP 4466273B2 JP 2004235282 A JP2004235282 A JP 2004235282A JP 2004235282 A JP2004235282 A JP 2004235282A JP 4466273 B2 JP4466273 B2 JP 4466273B2
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- Prior art keywords
- ring
- group
- polymer
- opening polymer
- hydride
- Prior art date
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- Expired - Lifetime
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- 229920000642 polymer Polymers 0.000 title claims description 117
- 238000007142 ring opening reaction Methods 0.000 title claims description 68
- 150000004678 hydrides Chemical class 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000002685 polymerization catalyst Substances 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title description 17
- 239000000178 monomer Substances 0.000 claims description 53
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 50
- 125000003367 polycyclic group Chemical group 0.000 claims description 28
- 150000003623 transition metal compounds Chemical class 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- -1 hexamethylene cycloheptanone decene compound Chemical class 0.000 description 37
- 125000001424 substituent group Chemical group 0.000 description 29
- 238000005984 hydrogenation reaction Methods 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000004104 aryloxy group Chemical group 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 5
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- FMZITCJWMYHQFG-UHFFFAOYSA-N 1,2,3,4,4a,5,8,8a-octahydro-2-methyl-1,4:5,8-dimethanonaphthalene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C FMZITCJWMYHQFG-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- JBOVEUMPNNXQMP-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)bicyclo[2.2.1]hepta-1,3-diene Chemical group C1CC2=C(C(F)(F)F)C(C(F)(F)F)=C1C2 JBOVEUMPNNXQMP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
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- 150000008064 anhydrides Chemical class 0.000 description 2
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- 125000001309 chloro group Chemical group Cl* 0.000 description 2
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- UEPFFTXSRHEQGL-UHFFFAOYSA-N phosphane trimethyl phosphate Chemical class P.COP(=O)(OC)OC UEPFFTXSRHEQGL-UHFFFAOYSA-N 0.000 description 1
- MRSDSBMESKXSNZ-UHFFFAOYSA-N phosphane;tricyclohexylphosphane Chemical class P.C1CCCCC1P(C1CCCCC1)C1CCCCC1 MRSDSBMESKXSNZ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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- 238000011002 quantification Methods 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は、シンジオタクティック構造を有するノルボルネン系開環重合体およびその水素化物、これらの製造方法、並びにこの製造方法に好適な重合触媒組成物に関する。 The present invention relates to a norbornene-based ring-opening polymer having a syndiotactic structure and a hydride thereof, a production method thereof, and a polymerization catalyst composition suitable for the production method.
ノルボルネン系開環重合体及びその水素化物が、透明性、耐熱性、低複屈折、成形加工性等に優れることは従来から知られており、光ディスクや光学レンズ用の材料として好適であることが提案されているが、低誘電性や耐薬品性等のその他の優れた特性も有するため、用途分野は光学用途以外にも広がりつつある。ここで用いられるノルボルネン系開環重合体及びその水素化物の構造は、通常アタクティックで非晶質の重合体であるが、光学用途以外の種々の用途に使用する場合には、機械強度、耐溶剤性、耐熱性等の一層の向上が望まれるため、その方策としてノルボルネン系単量体の立体規則性重合が提案されている。 Norbornene-based ring-opening polymers and their hydrides have been known to be excellent in transparency, heat resistance, low birefringence, moldability, etc., and may be suitable as materials for optical disks and optical lenses. Although proposed, it also has other excellent properties such as low dielectric properties and chemical resistance, so its application field is expanding beyond optical applications. The structure of the norbornene-based ring-opening polymer and its hydride used here is usually an atactic and amorphous polymer. However, when used in various applications other than optical applications, mechanical strength, Since further improvement in solvent resistance, heat resistance and the like is desired, stereoregular polymerization of norbornene monomers has been proposed as a countermeasure.
例えば、非特許文献1には、ビフェノキシ基とイミド基とが配位したモリブデン錯体を重合触媒として用いて重合した2,3−ビス(トリフルオロメチル)ノルボルナジエン開環重合体及び、2,3−ビス(ジカルボメトキシ)ノルボルナジエン開環重合体のタクティシティーについての記載がある。また、非特許文献2には、タンタル錯体を重合触媒として用いて重合したノルボルネン開環重合体水素化物のタクティシティーについての記載がある。さらに、非特許文献3には、ビフェノキシ基が2つ配位した、タングステンまたはモリブデンの錯体を用いて重合したジシクロペンタジエン開環重合体水素化物のタクティシティーについての記載がある。 For example, Non-Patent Document 1 discloses 2,3-bis (trifluoromethyl) norbornadiene ring-opening polymer obtained by polymerizing a molybdenum complex in which a biphenoxy group and an imide group are coordinated as a polymerization catalyst, and 2,3- There is a description about the tacticity of a bis (dicarbomethoxy) norbornadiene ring-opening polymer. Non-patent document 2 describes the tacticity of a hydride of norbornene ring-opened polymer obtained by polymerization using a tantalum complex as a polymerization catalyst. Further, Non-Patent Document 3 describes the tacticity of a dicyclopentadiene ring-opened polymer hydride polymerized using a tungsten or molybdenum complex in which two biphenoxy groups are coordinated.
しかしながら、これらはいずれもメソ・ダイアッドの割合が50%以上、すなわち、アイソタクチックな重合体であり、より高い耐熱性や機械的強度、およびより速い結晶化速度が期待できるシンジオタクティックな重合体ではなかった。 However, all of these are meso-dyad ratios of 50% or more, that is, isotactic polymers, and syndiotactic weights that can be expected to have higher heat resistance, mechanical strength, and faster crystallization speed. It was not a coalescence.
シンジオタクティックな構造を有するノルボルネン系開環重合体としては、アルコキシル基が2つ配位したモリブデン錯体を重合触媒として用いて重合した2,3−ビス(トリフルオロメチル)ノルボルナジエン開環重合体が開示されている(非特許文献4参照)。しかしながら、該重合体の耐熱性は十分ではなく、高い耐熱性を有する多環式ノルボルネン系開環重合体およびその水素化物で、シンジオタクティック構造を有するものはこれまで得られていなかった。 As the norbornene-based ring-opening polymer having a syndiotactic structure, 2,3-bis (trifluoromethyl) norbornadiene ring-opening polymer polymerized using a molybdenum complex in which two alkoxyl groups are coordinated is used as a polymerization catalyst. It is disclosed (see Non-Patent Document 4). However, the heat resistance of the polymer is not sufficient, and no polycyclic norbornene-based ring-opening polymer having high heat resistance and a hydride thereof having a syndiotactic structure have been obtained so far.
本発明は、上述した従来技術の実情に鑑みてなされたものであり、シンジオタクティック構造を有するノルボルネン系開環重合体およびその水素化物、これらの製造方法、並びにこの製造方法に好適な重合触媒組成物を提供することを課題とする。 The present invention has been made in view of the above-described prior art, and a norbornene-based ring-opening polymer having a syndiotactic structure, a hydride thereof, a production method thereof, and a polymerization catalyst suitable for the production method It is an object to provide a composition.
本発明者らは、前記課題を解決するために鋭意研究を行った結果、ヒドロキシル基を有するアリールオキシ基またはヒドロキシル基を有するアルコキシル基が結合した周期表第6族遷移金属化合物を重合触媒として用い、多環式ノルボルネン系単量体として、ジシクロペンタジエンなどの3環以上の多環式ノルボルネン系単量体を重合すると、得られる開環重合体がシンジオタクティック構造を有すること、およびその水素化物が結晶性を有することを見出した。また、該開環重合体およびその水素化物が高い耐熱性を有することを見出した。本発明は、これらの知見に基づいて完成するに至ったものである。 As a result of intensive studies to solve the above problems, the present inventors have used a periodic table Group 6 transition metal compound in which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded as a polymerization catalyst. When a polycyclic norbornene monomer such as dicyclopentadiene is polymerized as a polycyclic norbornene monomer, the resulting ring-opening polymer has a syndiotactic structure, and hydrogen It was found that the compound has crystallinity. Moreover, it discovered that this ring-opening polymer and its hydride had high heat resistance. The present invention has been completed based on these findings.
かくして本発明の第1によれば、重合体全繰返し単位中に3環以上の多環式ノルボルネン系単量体を開環重合してなる繰返し単位を含有し、重量平均分子量が500〜1,000,000であり、ラセモ・ダイアッドの割合が51%以上であることを特徴とする開環重合体が提供される。 Thus, according to the first aspect of the present invention, a repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene monomers in all the repeating units of the polymer has a weight average molecular weight of 500 to 1, There is provided a ring-opening polymer characterized in that the ratio of racemo dyad is 51% or more.
本発明の開環重合体は、ラセモ・ダイアッドの割合が70%以上であるものが好ましく、3環以上の多環式ノルボルネン系単量体が、ジシクロペンタジエンであるものが好ましい。 The ring-opening polymer of the present invention preferably has a racemo dyad ratio of 70% or more, and preferably a tricyclic or higher polycyclic norbornene monomer is dicyclopentadiene.
本発明の第2によれば、ヒドロキシル基を有するアリールオキシ基またはヒドロキシル基を有するアルコキシル基が結合した周期表第6族遷移金属化合物を重合触媒として用いて、3環以上の多環式ノルボルネン系単量体を重合することを特徴とする本発明の開環重合体の製造方法が提供される。 According to the second aspect of the present invention, a polycyclic norbornene system having 3 or more rings is used as a polymerization catalyst using a group 6 transition metal compound of a periodic table to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded. A method for producing the ring-opening polymer of the present invention, which comprises polymerizing monomers, is provided.
本発明の第3によれば、本発明の開環重合体の主鎖二重結合を50%以上水素化して得られる開環重合体水素化物が提供される。
本発明の開環重合体水素化物は、重合体全繰返し単位中に3環以上の多環式ノルボルネン系単量体由来の繰返し単位を含有し、重量平均分子量が500〜1,000,000であり、ラセモ・ダイアッドの割合が51%以上であるものが好ましく、結晶性であるものが好ましい。
According to the third aspect of the present invention, there is provided a hydrogenated ring-opening polymer obtained by hydrogenating 50% or more of the main chain double bond of the ring-opening polymer of the present invention.
The ring-opening polymer hydride of the present invention contains a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings in the entire repeating unit of the polymer, and has a weight average molecular weight of 500 to 1,000,000. The ratio of racemo dyad is preferably 51% or more, and crystalline is preferable.
本発明の第4によれば、ヒドロキシル基を有するアリールオキシ基またはヒドロキシル基を有するアルコキシル基が結合した周期表第6族遷移金属化合物を重合触媒として用いて、3環以上の多環式ノルボルネン系単量体を重合して開環重合体を得る工程、および該開環重合体中の炭素−炭素二重結合を水素化する工程を含む本発明の開環重合体水素化物の製造方法が提供される。 According to the fourth aspect of the present invention, a polycyclic norbornene system having 3 or more rings is used as a polymerization catalyst using a periodic table Group 6 transition metal compound to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded. Provided is a method for producing a hydride of a ring-opened polymer according to the present invention comprising a step of polymerizing a monomer to obtain a ring-opened polymer, and a step of hydrogenating a carbon-carbon double bond in the ring-opened polymer. Is done.
本発明の第5によれば、ヒドロキシル基を有するアリールオキシ基またはヒドロキシル基を有するアルコキシル基が結合した周期表第6族遷移金属化合物と活性化剤とからなる、3環以上の多環式ノルボルネン系単量体の重合触媒組成物が提供される。 According to the fifth aspect of the present invention, a polycyclic norbornene having three or more rings, comprising an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group and a periodic table Group 6 transition metal compound and an activator. A monomer-based polymerization catalyst composition is provided.
本発明によれば、3環以上の多環式ノルボルネン系単量体を開環重合してなる繰返し単位を含有し、シンジオタクティック構造を有する新規なノルボルネン系開環重合体およびその水素化物が得られる。得られる開環重合体水素化物は結晶性の重合体であり、耐熱性に優れ、かつシンジオタクティック構造を有し、結晶化速度が速いので、各種用途の成形用材料およびフィルム用材料として好適である。
本発明の製造方法によれば、本発明の開環重合体および開環重合体水素化物を効率よく製造することができる。
本発明の重合触媒組成物は、3環以上の多環式ノルボルネン系単量体を重合して本発明の開環重合体を得る反応に用いる重合触媒として有用である。
According to the present invention, a novel norbornene ring-opening polymer containing a repeating unit formed by ring-opening polymerization of a polycyclic norbornene monomer having three or more rings and having a syndiotactic structure and a hydride thereof are provided. can get. The resulting ring-opened polymer hydride is a crystalline polymer, has excellent heat resistance, has a syndiotactic structure, and has a high crystallization speed, making it suitable as a molding material and film material for various applications. It is.
According to the production method of the present invention, the ring-opened polymer and the ring-opened polymer hydride of the present invention can be efficiently produced.
The polymerization catalyst composition of the present invention is useful as a polymerization catalyst used in a reaction in which a polycyclic norbornene-based monomer having three or more rings is polymerized to obtain the ring-opened polymer of the present invention.
本発明の好ましい実施の形態について、以下に詳細に説明する。
[ノルボルネン系開環重合体]
本発明のノルボルネン系開環重合体は、重合体全繰り返し単位中に3環以上の多環式ノルボルネン系単量体を開環重合してなる繰返し単位を含有するものである。3環以上の多環式ノルボルネン系単量体を開環重合してなる繰り返し単位とは、分子内にノルボルネン環と、該ノルボルネン環と縮合している1つ以上の環とを有するノルボルネン系単量体を開環重合して得られる繰り返し単位である。その具体例としては、下記一般式(1)または(2)で表されるものが挙げられる。
Preferred embodiments of the present invention will be described in detail below.
[Norbornene-based ring-opening polymer]
The norbornene-based ring-opening polymer of the present invention contains a repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene-based monomers in all repeating units of the polymer. The repeating unit formed by ring-opening polymerization of three or more polycyclic norbornene monomers is a norbornene-based single unit having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. It is a repeating unit obtained by ring-opening polymerization of a monomer. Specific examples thereof include those represented by the following general formula (1) or (2).
(式中、R4〜R7はそれぞれ独立に水素原子;ハロゲン原子;置換基を有していてもよい炭素数1〜20の炭化水素基;又はケイ素原子、酸素原子もしくは窒素原子を含む置換基;を表し、R4とR6は互いに結合して環を形成していてもよい。mは1又は2である。) (Wherein R 4 to R 7 are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R 4 and R 6 may be bonded to each other to form a ring, and m is 1 or 2.)
本発明の開環重合体に含まれる、重合体全繰り返し単位に対する3環以上の多環式ノルボルネン系単量体を開環重合して得られる繰り返し単位の割合は、通常10モル%以上、好ましくは50モル%以上、より好ましくは70モル%以上、特に好ましくは90モル%以上である。3環以上の多環式ノルボルネン系単量体を開環重合して得られる繰り返し単位の割合がこの範囲にある開環重合体およびその水素化物は、耐熱性に優れている。 The ratio of the repeating unit obtained by ring-opening polymerization of a polycyclic norbornene-based monomer having 3 or more rings to the total repeating unit of the polymer contained in the ring-opening polymer of the present invention is usually 10 mol% or more, preferably Is at least 50 mol%, more preferably at least 70 mol%, particularly preferably at least 90 mol%. A ring-opening polymer in which the ratio of repeating units obtained by ring-opening polymerization of three or more polycyclic norbornene-based monomers is in this range and its hydride are excellent in heat resistance.
本発明の開環重合体のゲルパーミエーションクロマトグラフィーにより測定した重量平均分子量(Mw)は、ポリスチレン換算で500〜1,000,000、好ましくは1,000〜600,000、より好ましくは5,000〜400,000である。Mwが低すぎると機械強度が低下する場合があり、Mwが高すぎると成形が困難となる。
また、本発明の開環重合体のシス体の含有量は、通常80モル%以上、好ましくは85モル%以上である。
The weight average molecular weight (Mw) measured by gel permeation chromatography of the ring-opening polymer of the present invention is 500 to 1,000,000, preferably 1,000 to 600,000, more preferably 5, in terms of polystyrene. 000 to 400,000. If Mw is too low, the mechanical strength may decrease, and if Mw is too high, molding becomes difficult.
Further, the content of the cis isomer of the ring-opening polymer of the present invention is usually 80 mol% or more, preferably 85 mol% or more.
本発明の開環重合体は、前記一般式(1)または(2)において、(i)および(iii)で表される炭素が不斉炭素であるため、立体規則性(タクティシティー)が存在する。本発明の開環重合体は、ラセモ・ダイアッドの割合が51%以上であるシンジオタクティックな重合体であり、好ましくはラセモ・ダイアッドの割合が60%以上、より好ましくは70%以上である。メソ・ダイアッドとラセモ・ダイアッドの割合は、13C−NMRスペクトル分析で測定することができる。具体的には、本発明の開環重合体の前記一般式(1)または(2)における(i)〜(v)で表されるいずれか少なくとも1つの炭素原子のスペクトルを定量することで測定できる。 Since the carbon represented by (i) and (iii) is an asymmetric carbon in the general formula (1) or (2), the ring-opening polymer of the present invention has stereoregularity (tacticity). To do. The ring-opening polymer of the present invention is a syndiotactic polymer in which the ratio of racemo dyad is 51% or more, preferably the ratio of racemo dyad is 60% or more, more preferably 70% or more. The ratio of meso dyad and racemo dyad can be measured by 13 C-NMR spectral analysis. Specifically, it is measured by quantifying the spectrum of at least one carbon atom represented by (i) to (v) in the general formula (1) or (2) of the ring-opening polymer of the present invention. it can.
また、本発明の開環重合体の13C−NMRスペクトル測定で定量できない場合には、開環重合体の主鎖二重結合を水素化した水素化物の13C−NMRスペクトルを測定してメソ・ダイアッドとラセモ・ダイアッドの割合を決定することができる。 In addition, when the 13 C-NMR spectrum of the ring-opened polymer of the present invention cannot be quantified, the 13 C-NMR spectrum of a hydride obtained by hydrogenating the main chain double bond of the ring-opened polymer is measured to obtain a meso • The ratio of Dyad and Racemo Dyad can be determined.
定量の方法は、重合体によっても異なるが、例えばジシクロペンタジエンの開環重合体の場合、その水素化物について、オルトジクロロベンゼン−d4を溶媒として、150℃で13C−NMR測定を行い、メソ・ダイアッド由来の43.35ppmのシグナルと、ラセモ・ダイアッド由来の43.43ppmのシグナルの強度比からラセモ・ダイアッドの割合を決定できる。 Although the method of quantification varies depending on the polymer, for example, in the case of a ring-opened polymer of dicyclopentadiene, the hydrogenated product is subjected to 13 C-NMR measurement at 150 ° C. using orthodichlorobenzene-d 4 as a solvent, The ratio of racemo dyad can be determined from the intensity ratio of 43.35 ppm signal derived from meso dyad and 43.43 ppm signal derived from racemo dyad.
[開環重合体の製造方法]
本発明の開環重合体の製造方法は、上記本発明の開環重合体を製造する方法の一つの例であって、ヒドロキシル基を有するアリールオキシ基またはヒドロキシル基を有するアルコキシル基が結合した周期表第6族遷移金属化合物を含有する重合触媒を用いて、3環以上の多環式ノルボルネン系単量体を重合することを特徴とする。
[Method for producing ring-opening polymer]
The method for producing a ring-opening polymer of the present invention is one example of the method for producing the ring-opening polymer of the present invention, and is a cycle in which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded. A polymerization catalyst containing a Table 6 group 6 transition metal compound is used to polymerize a tricyclic or higher polycyclic norbornene-based monomer.
[単量体]
本発明においては、単量体として、3環以上の多環式ノルボルネン系単量体(以下、「多環式ノルボルネン系単量体(α)」ということがある)の一種、多環式ノルボルネン系単量体(α)の二種以上からなる組み合わせ、または多環式ノルボルネン系単量体(α)とこれと共重合可能な他の単量体の組み合わせを用いることができる。
[Monomer]
In the present invention, as a monomer, a polycyclic norbornene monomer having three or more rings (hereinafter sometimes referred to as “polycyclic norbornene monomer (α)”), a polycyclic norbornene. A combination of two or more types of monomer (α) or a combination of a polycyclic norbornene monomer (α) and another monomer copolymerizable therewith can be used.
3環以上の多環式ノルボルネン系単量体とは、分子内にノルボルネン環と、該ノルボルネン環と縮合している1つ以上の環とを有するノルボルネン系単量体である。その具体例としては一般式(3)または一般式(4)で示される単量体が挙げられる。 The polycyclic norbornene monomer having three or more rings is a norbornene monomer having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include monomers represented by general formula (3) or general formula (4).
(式中、R1〜R3は一般式(1)と同様である。) (Wherein, R 1 to R 3 are the same as in the general formula (1).)
(式中、R4〜R7およびmは一般式(2)と同様である。)
一般式(3)で示される単量体は、具体的には、ジシクロペンタジエン、メチルジシクロペンタジエン、トリシクロ[5.2.1.02,6]デカ−8−エンなどを挙げることができる。また、テトラシクロ[9.2.1.02,10.03,8]テトラデカ−3,5,7,12−テトラエン(1,4−メタノ−1,4,4a,9a−テトラヒドロ−9H−フルオレンともいう)、テトラシクロ[10.2.1.02,11.04,9]ペンタデカ−4,6,8,13−テトラエン(1,4−メタノ−1,4,4a,9,9a,10−ヘキサヒドロアントラセンともいう)、などの芳香環を有するノルボルネン誘導体も挙げることができる。
(In the formula, R 4 to R 7 and m are the same as those in the general formula (2).)
Specific examples of the monomer represented by the general formula (3) include dicyclopentadiene, methyldicyclopentadiene, and tricyclo [5.2.1.0 2,6 ] dec-8-ene. it can. In addition, tetracyclo [9.2.1.0 2,10. 0 3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 2 , 11 . Norbornene derivatives having an aromatic ring such as 0 4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene) Can also be mentioned.
一般式(4)で示される単量体としては、mが1であるテトラシクロドデセン類、mが2であるヘキサシクロヘプタデセン類が挙げられる。
テトラシクロドデセン類の具体例としては、テトラシクロドデセン、8−メチルテトラシクロドデセン、8−エチルテトラシクロドデセン、8−シクロヘキシルテトラシクロドデセン、8−シクロペンチルテトラシクロドデセンなどの無置換またはアルキル基を有するテトラシクロドデセン類;8−メチリデンテトラシクロドデセン、8−エチリデンテトラシクロドデセン、8−ビニルテトラシクロドデセン、8−プロペニルテトラシクロドデセン、8−シクロヘキセニルテトラシクロドデセン、8−シクロペンテニルテトラシクロドデセンなどの環外に二重結合を有するテトラシクロドデセン類;8−フェニルテトラシクロドデセンなどの芳香環を有するテトラシクロドデセン類;8−メトキシカルボニルテトラシクロドデセン、8−メチル−8−メトキシカルボニルテトラシクロドデセン、8−ヒドロキシメチルテトラシクロドデセン、8−カルボキシテトラシクロドデセン、テトラシクロドデセン−8,9−ジカルボン酸、テトラシクロドデセン−8,9−ジカルボン酸無水物などの酸素原子を含む置換基を有するテトラシクロドデセン類;8−シアノテトラシクロドデセン、テトラシクロドデセン−8,9−ジカルボン酸イミドなどの窒素原子を含む置換基を有するテトラシクロドデセン類;8−クロロテトラシクロドデセンなどのハロゲン原子を含む置換基を有するテトラシクロドデセン類;8−トリメトキシシリルテトラシクロドデセンなどのケイ素原子を含む置換基を有するテトラシクロドデセン類などが挙げられる。
Examples of the monomer represented by the general formula (4) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.
Specific examples of tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes having a substituted or alkyl group; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl -8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic acid Tetracyclododecenes having a substituent containing an oxygen atom such as anhydride; tetracyclododecene having a substituent containing a nitrogen atom such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide Dodecenes; tetracyclododecenes having substituents containing halogen atoms such as 8-chlorotetracyclododecene; tetracyclododecenes having substituents containing silicon atoms such as 8-trimethoxysilyltetracyclododecene And the like.
ヘキサシクロヘプタデセン類の具体例としては、ヘキサシクロヘプタデセン、12−メチルヘキサシクロヘプタデセン、12−エチルヘキサシクロヘプタデセン、12−シクロヘキシルヘキサシクロヘプタデセン、12−シクロペンチルヘキサシクロヘプタデセンなどの無置換またはアルキル基を有するヘキサシクロヘプタデセン類;12−メチリデンヘキサシクロヘプタデセン、12−エチリデンヘキサシクロヘプタデセン、12−ビニルヘキサシクロヘプタデセン、12−プロペニルヘキサシクロヘプタデセン、12−シクロヘキセニルヘキサシクロヘプタデセン、12−シクロペンテニルヘキサシクロヘプタデセンなどの環外に二重結合を有するヘキサシクロヘプタデセン類;12−フェニルヘキサシクロヘプタデセンなどの芳香環を有するヘキサシクロヘプタデセン類;12−メトキシカルボニルヘキサシクロヘプタデセン、12−メチル−12−メトキシカルボニルヘキサシクロヘプタデセン、12−ヒドロキシメチルヘキサシクロヘプタデセン、12−カルボキシヘキサシクロヘプタデセン、ヘキサシクロヘプタデセン12,13−ジカルボン酸、ヘキサシクロヘプタデセン12,13−ジカルボン酸無水物などの酸素原子を含む置換基を有するヘキサシクロヘプタデセン類;12−シアノヘキサシクロヘプタデセン、ヘキサシクロヘプタデセン12,13−ジカルボン酸イミドなどの窒素原子を含む置換基を有するヘキサシクロヘプタデセン類;12−クロロヘキサシクロヘプタデセンなどのハロゲン原子を含む置換基を有するヘキサシクロヘプタデセン類;12−トリメトキシシリルヘキサシクロヘプタデセンなどのケイ素原子を含む置換基を有するヘキサシクロヘプタデセン類などが挙げられる。 Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene and 12-cyclopentenylhexacycloheptadecene; aromatic rings such as 12-phenylhexacycloheptadecene Hexacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene Hexacycloheptadecenes having a substituent containing an oxygen atom such as 12,13-dicarboxylic acid and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13 A hexacycloheptadecene having a substituent containing a nitrogen atom such as dicarboxylic imide; a hexacycloheptadecene having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Such as hexamethylene cycloheptanone decene compound having a substituent containing a silicon atom such as trimethoxy silyl hexamethylene cycloheptanone decene and the like.
本発明の製造方法においては、重合反応時の立体規則性は単量体の開環反応に係る部分の立体構造に依存するので、上記いずれの単量体を用いてもラセモ・ダイアッドの割合が51%以上の開環重合体を得ることができる。なかでも、得られる開環重合体水素化物の結晶性が高いという点で、一般式(3)で示される単量体または一般式(4)においてmが1であるテトラシクロドデセン類が好ましい。これらの中でもジシクロペンタジエン、トリシクロ[5.2.1.02,6]デカ−8−エン、テトラシクロ[9.2.1.02,10.03,8]テトラデカ−3,5,7,12−テトラエン、テトラシクロ[10.2.1.02,11.04,9]ペンタデカ−4,6,8,13−テトラエン、テトラシクロドデセン、8−メチルテトラシクロドデセンがさらに好ましく、ジシクロペンタジエンが特に好ましい。 In the production method of the present invention, since the stereoregularity at the time of the polymerization reaction depends on the three-dimensional structure of the portion related to the ring-opening reaction of the monomer, the ratio of racemo dyad is not limited to any of the above monomers. 51% or more of the ring-opening polymer can be obtained. Among them, the monomer represented by the general formula (3) or the tetracyclododecenes in which m is 1 in the general formula (4) is preferable in that the obtained ring-opened polymer hydride has high crystallinity. . Among these, dicyclopentadiene, tricyclo [5.2.1.0 2,6] dec-8-ene, tetracyclo [9.2.1.0 2,10. 0 3,8] tetradec -3,5,7,12- tetraene, tetracyclo [10.2.1.0 2,11. 0 4,9] pentadeca -4,6,8,13- tetraene, tetracyclododecene, 8-methyl tetracyclododecene more preferably, dicyclopentadiene is particularly preferable.
本発明の製造方法において、上記多環式ノルボルネン系単量体(α)の使用量は、全単量体中、通常10モル%以上、好ましくは50モル%以上、より好ましくは70モル%以上、特に好ましくは90モル%以上である。 In the production method of the present invention, the amount of the polycyclic norbornene monomer (α) used is usually 10 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more, based on the total monomers. Especially preferably, it is 90 mol% or more.
上記の多環式ノルボルネン系単量体には、エンド体とエキソ体の異性体が含まれる。本発明に使用する単量体は、これら異性体の混合物であっても構わないが、結晶性をより高めるためには、異性体混合物中において、いずれかの異性体成分の組成比が高いほうが好ましい。具体的には、いずれかの異性体が70%以上、特には80%以上あるものが好ましい。いずれかの異性体成分の組成比を高くすることにより、得られる重合体が高度に結晶化するので、耐熱性をより高めることができる。 The polycyclic norbornene-based monomer includes an isomer of an endo isomer and an exo isomer. The monomer used in the present invention may be a mixture of these isomers. However, in order to further improve the crystallinity, the composition ratio of any isomer component in the isomer mixture should be higher. preferable. Specifically, it is preferable that any isomer is 70% or more, particularly 80% or more. By increasing the composition ratio of any of the isomer components, the resulting polymer is highly crystallized, so that the heat resistance can be further improved.
前記多環式ノルボルネン系単量体(α)と共重合可能な単量体としては、環状オレフィン類(β)が挙げられる。環状オレフィン類(β)としては、分子内にノルボルネン環と縮合する環を有しないノルボルネン系単量体、単環の環状オレフィンなどが挙げられる。 Examples of the monomer copolymerizable with the polycyclic norbornene monomer (α) include cyclic olefins (β). Examples of the cyclic olefins (β) include norbornene monomers that do not have a ring condensed with a norbornene ring in the molecule, and monocyclic olefins.
分子内にノルボルネン環と縮合する環を有しないノルボルネン系単量体の具体例としては、ノルボルネン、5−メチルノルボルネン、5−エチルノルボルネン、5−ブチルノルボルネン、5−ヘキシルノルボルネン、5−デシルノルボルネン、5−シクロヘキシルノルボルネン、5−シクロペンチルノルボルネンなどの無置換またはアルキル基を有するノルボルネン類;5−エチリデンノルボルネン、5−ビニルノルボルネン、5−プロペニルノルボルネン、5−シクロヘキセニルノルボルネン、5−シクロペンテニルノルボルネンなどのアルケニル基を有するノルボルネン類;5−フェニルノルボルネンなどの芳香環を有するノルボルネン類;5−メトキシカルボニルノルボルネン、5−エトキシカルボニルノルボルネン、5−メチル−5−メトキシカルボニルノルボルネン、5−メチル−5−エトキシカルボニルノルボルネン、ノルボルネニル−2−メチルプロピオネイト、ノルボルネニル−2−メチルオクタネイト、5−ヒドロキシメチルノルボルネン、5,6−ジ(ヒドロキシメチル)ノルボルネン、5,5−ジ(ヒドロキシメチル)ノルボルネン、5−ヒドロキシ−イソプロピルノルボルネン、5,6−ジカルボキシノルボルネン、5−メトキシカルボニル−6−カルボキシノルボルネン、などの酸素原子を含む極性基を有するノルボルネン類;5−シアノノルボルネンなどの窒素原子を含む極性基を有するノルボルネン類;などが挙げられる。 Specific examples of the norbornene-based monomer having no ring condensed with the norbornene ring in the molecule include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, Norbornenes having an unsubstituted or alkyl group such as 5-cyclohexylnorbornene and 5-cyclopentylnorbornene; alkenyl such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene and 5-cyclopentenylnorbornene Norbornenes having a group; norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5 Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5, Norbornenes having polar groups containing oxygen atoms, such as 5-di (hydroxymethyl) norbornene, 5-hydroxy-isopropylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene; 5-cyano And norbornenes having a polar group containing a nitrogen atom such as norbornene.
単環の環状オレフィン類は、炭素数4〜20の環状オレフィン又はジオレフィンとこれらの置換体であり、好ましくは炭素数4〜10の環状オレフィン又はジオレフィンとこれらの誘導体である。 The monocyclic olefins are cyclic olefins or diolefins having 4 to 20 carbon atoms and substituted products thereof, preferably cyclic olefins or diolefins having 4 to 10 carbon atoms and derivatives thereof.
単環の環状オレフィン類又はジオレフィン類の具体例としては、シクロブテン、シクロペンテン、メチルシクロペンテン、シクロヘキセン、メチルシクロヘキセン、シクロヘプテン、シクロオクテンなどの単環の環状オレフィン系単量体;シクロヘキサジエン、メチルシクロヘキサジエン、シクロオクタジエン、メチルシクロオクタジエン、フェニルシクロオクタジエンなどの環状ジオレフィン系単量体;を挙げることができる。 Specific examples of monocyclic olefins or diolefins include monocyclic olefin monomers such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene; cyclohexadiene, methylcyclohexadiene And cyclic diolefin monomers such as cyclooctadiene, methylcyclooctadiene, and phenylcyclooctadiene.
[重合触媒]
本発明では、ヒドロキシル基を有するアリールオキシ基またはヒドロキシル基を有するアルコキシル基が結合した周期表第6族遷移金属化合物(以下、「第6族遷移金属化合物」ということがある)を重合触媒して用いる。
[Polymerization catalyst]
In the present invention, a polymerization catalyst for a Group 6 transition metal compound (hereinafter sometimes referred to as “Group 6 transition metal compound”) to which an aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group is bonded is used. Use.
前記第6族遷移金属化合物の周期律表第6族遷移金属としては、クロム、モリブデン、タングステンなどが挙げられ、モリブデンおよびタングステンが好ましく、タングステンが特に好ましい。
第6族遷移金属化合物は、下記一般式(5)で表される構造を有する化合物である。
Examples of the Group 6 transition metal of the Group 6 transition metal compound include chromium, molybdenum, tungsten, and the like. Molybdenum and tungsten are preferable, and tungsten is particularly preferable.
The Group 6 transition metal compound is a compound having a structure represented by the following general formula (5).
(式中、Mは第6族遷移金属を表し、R8は置換基を有していてもよい二価の炭化水素基を表す。) (In the formula, M represents a Group 6 transition metal, and R 8 represents a divalent hydrocarbon group which may have a substituent.)
R8としては、具体的には、炭素数1〜20の二価の脂肪族炭化水素基、炭素数3〜20の二価の脂環族炭化水素基、炭素数6〜50の二価の芳香族炭化水素基、又はこれらが互いに結合した炭化水素基などが挙げられる。 Specific examples of R 8 include a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent aliphatic hydrocarbon group having 6 to 50 carbon atoms. An aromatic hydrocarbon group or a hydrocarbon group in which these are bonded to each other can be used.
前記第6族遷移金属化合物としては、上記ヒドロキシル基が第6族遷移金属化合物に中性配位子として配位した一般式(6)で表される化合物が好ましく、一般式(7)で表される化合物がより好ましい。 The group 6 transition metal compound is preferably a compound represented by the general formula (6) in which the hydroxyl group is coordinated to the group 6 transition metal compound as a neutral ligand. More preferred is a compound.
(式中、MおよびR8は前記と同じ意味を表す。) (In the formula, M and R 8 have the same meaning as described above.)
式(7)中、MおよびR8は前記と同じ意味を表す。
Zは酸素原子又はNR9で表される基を表し、NR9が好ましい。R9は置換基を有していてもよい炭化水素基を表す。R9としては、炭素数1〜20の直鎖又は分岐鎖状のアルキル基、炭素数3〜20のシクロアルキル基、置換基を有していてもよい炭素数6〜24のアリール基などが挙げられる。
In formula (7), M and R 8 represent the same meaning as described above.
Z represents a group represented by an oxygen atom or NR 9, NR 9 are preferred. R 9 represents a hydrocarbon group which may have a substituent. R 9 includes a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms which may have a substituent, and the like. Can be mentioned.
Xは、ハロゲン原子、炭化水素基、アルキルシリル基、アルコキシル基又はアリールオキシ基を表す。Xが複数個あるとき、Xは互いに同一であっても相異なっていてもよく、また、互いに結合していてもよい。 X represents a halogen atom, a hydrocarbon group, an alkylsilyl group, an alkoxyl group or an aryloxy group. When there are a plurality of X, Xs may be the same or different from each other, and may be bonded to each other.
前記Xのハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子が挙げられる。炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t−ブチル基、ペンチル基、ネオペンチル基、ベンジル基、ネオフィル基、フェニル基、ナフチル基などが挙げられる。アルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、t−ブチルジメチルシリル基などが挙げられる。アルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、t−ブトキシ基などが挙げられる。アリールオキシ基としては、フェノキシ基、2,6−ジメチルフェノキシ基、2,6−ジイソプロピルフェノキシ基などが挙げられる。また、複数のXが互いに結合した例として、ビフェノキシ基、フェニルジオキシ基などが挙げられる。
pは1または2を表し、1が好ましい。
Examples of the halogen atom for X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, benzyl group, neophyll group, phenyl group, and naphthyl group. . Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a t-butoxy group. Examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,6-diisopropylphenoxy group. Examples of a plurality of X bonded to each other include a biphenoxy group and a phenyldioxy group.
p represents 1 or 2, and 1 is preferable.
Lは電子供与性の中性配位子である。電子供与性の中性配位子としては、例えば、周期律表第14族又は第15族の原子を含有する電子供与性化合物が挙げられる。その具体例としては、トリメチルホスフィン、トリイソプロピルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィンなどのホスフィン類;ジエチルエーテル、ジブチルエーテル、1,2−ジメトキシエタン、テトラヒドロフランなどのエーテル類;トリメチルアミン、トリエチルアミン、ピリジン、ルチジンなどのアミン類;等を挙げることができる。中でも、エーテル類が好ましい。
bは0〜2の整数である。bが2のとき、Lは互いに同一であっても相異なっていてもよい。
L is an electron-donating neutral ligand. Examples of the electron-donating neutral ligand include electron-donating compounds containing atoms of Group 14 or Group 15 of the Periodic Table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, Amines such as lutidine; and the like. Of these, ethers are preferable.
b is an integer of 0-2. When b is 2, L may be the same as or different from each other.
式(7)で表される化合物において、より好ましい化合物として、式(8)〜(10)で表される化合物が挙げられる。 In the compound represented by formula (7), more preferred compounds include compounds represented by formulas (8) to (10).
式(8)〜(10)において、M、Z、X、L、bおよびpは前記と同じ意味を表す。
R10〜R27はそれぞれ独立に水素原子、炭素数1〜20の炭化水素基又はハロゲン原子、ケイ素原子、酸素原子もしくは窒素原子を含む置換基を示し、隣接する炭素原子に結合する基は互いに結合して環を形成してもよい。
In the formulas (8) to (10), M, Z, X, L, b, and p represent the same meaning as described above.
R 10 to R 27 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom, and groups bonded to adjacent carbon atoms are mutually They may combine to form a ring.
Qは、酸素原子、硫黄原子、および下記式(11)〜(14)から選ばれる一種である。 Q is a kind selected from an oxygen atom, a sulfur atom, and the following formulas (11) to (14).
式(11)〜(14)において、R28〜R32はそれぞれ独立に水素原子又は炭素数1〜6の炭化水素基を表す。 In formulas (11) to (14), R 28 to R 32 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
R10〜R27の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t‐ブチル基、フェニル基などが挙げられる。 Specific examples of R 10 to R 27 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and a phenyl group.
また、R10〜R27の隣接する炭素原子に結合する基が互いに結合して環を形成していてもよい。隣接する炭素原子に結合する基が互いに結合して環を形成する例としては、R11とR12が結合してナフタレン環を形成している化合物;R14とR15又はR18とR19が結合してアントラセン環を形成している化合物;R15とR16又はR17とR18が結合してフェナントレン環を形成している化合物;R22とR23および/又はR24とR25が結合してナフタレン環を形成している化合物;等を挙げることができる。
qは0または1である。
In addition, groups bonded to adjacent carbon atoms of R 10 to R 27 may be bonded to each other to form a ring. Examples of groups in which adjacent carbon atoms are bonded to each other to form a ring include compounds in which R 11 and R 12 are combined to form a naphthalene ring; R 14 and R 15 or R 18 and R 19 Are bonded to form an anthracene ring; R 15 and R 16 or R 17 and R 18 are bonded to form a phenanthrene ring; R 22 and R 23 and / or R 24 and R 25 And a compound in which a naphthalene ring is bonded to each other; and the like.
q is 0 or 1.
これらの中でも、本発明においては、前記第6族遷移金属化合物としては、下記一般式(a)で示される周期律表第6族遷移金属化合物が特に好ましい。 Among these, in the present invention, the Group 6 transition metal compound is particularly preferably a Group 6 transition metal compound of the periodic table represented by the following general formula (a).
式(a)中、M、X、Lおよびbは前記と同じ意味を表す。
Raは、3,4,5位のいずれかに置換基を有していてもよいフェニル基、または−CH2Rdで表される基を表す。
In formula (a), M, X, L and b represent the same meaning as described above.
R a represents a phenyl group which may have a substituent at any of the 3, 4, and 5 positions, or a group represented by —CH 2 R d .
前記3,4,5位のいずれかに置換基を有していてもよいフェニル基の置換基としては、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、イソブチル基、t−ブチル基等のアルキル基;シクロプロピル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フッ素原子、塩素原子、臭素原子等のハロゲン原子;メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、t−ブトキシ基等のアルコキシル基;等が挙げられる。 Examples of the substituent of the phenyl group which may have a substituent at any of the 3, 4 and 5 positions include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Alkyl groups such as isobutyl group and t-butyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, propoxy group, iso And alkoxyl groups such as propoxy group, butoxy group and t-butoxy group.
前記3,4,5位のいずれかに置換基を有していてもよいフェニル基の具体例としては、フェニル基;4−メチルフェニル基、4−クロロフェニル基、3−メトキシフェニル基、4−シクロヘキシルフェニル基、4−メトキシフェニル基等の一置換フェニル基:3,5−ジメチルフェニル基、3,5−ジクロロフェニル基、3,4−ジメチルフェニル基、3,5−ジメトキシフェニル基などの二置換フェニル基;3,4,5−トリメチルフェニル基、3,4,5−トリクロロフェニル基などの三置換フェニル基;などが挙げられる。また、2−ナフチル基、3−メチル−2−ナフチル基、4−メチル−2−ナフチル基などの置換基を有していてもよい2−ナフチル基であってもよい。 Specific examples of the phenyl group which may have a substituent at any of the 3, 4 and 5 positions include phenyl group; 4-methylphenyl group, 4-chlorophenyl group, 3-methoxyphenyl group, 4- Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group: Disubstituted groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, and 3,5-dimethoxyphenyl group And phenyl group; trisubstituted phenyl groups such as 3,4,5-trimethylphenyl group and 3,4,5-trichlorophenyl group; Moreover, the 2-naphthyl group which may have substituents, such as 2-naphthyl group, 3-methyl-2- naphthyl group, and 4-methyl-2-naphthyl group, may be sufficient.
前記−CH2RdのRdは、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、置換基を有していてもよいアルキル基が好ましい。 R d of the -CH 2 R d is a hydrogen atom, have an alkyl group or a substituted group which may have a substituent represents an even aryl group, an alkyl which may have a substituent Groups are preferred.
Rdの置換基を有していてもよいアルキル基の炭素数は、特に制限されないが、通常1〜20、好ましくは1〜10である。また、これらのアルキル基は直鎖状であっても分岐状であってもよい。Rdの置換基を有していてもよいアルキル基の置換基としては、例えば、フェニル基、4−メチルフェニル基などの置換基を有していてもよいフェニル基;メトキシ基、エトキシ基などのアルコキシル基;などが挙げられる。 The carbon number of the alkyl group which may have a substituent for R d is not particularly limited, but is usually 1 to 20, preferably 1 to 10. These alkyl groups may be linear or branched. Examples of the substituent of the alkyl group which may have a substituent for R d include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; a methoxy group, an ethoxy group and the like And the like.
Rdの置換基を有していてもよいアリール基のアリール基としては、好ましくは炭素数6〜20のものであり、その具体例としては、フェニル基、1−ナフチル基、2−ナフチル基などが挙げられる。Rdの置換基を有していてもよいアリール基の置換基としては、前記Raの3,4,5位のいずれかに置換基を有していてもよいフェニル基の置換基として例示したものと同様のものが挙げられる。 The aryl group which may have a substituent for R d is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Etc. Examples of the substituent of the aryl group which may have a substituent of R d are examples of the substituent of the phenyl group which may have a substituent at any of the 3, 4, and 5 positions of R a. The same thing as what was done is mentioned.
Yは、前記のヒドロキシル基を有するアリールオキシ基、またはヒドロキシル基を有するアルコキシル基を表す。 Y represents the above aryloxy group having a hydroxyl group or an alkoxyl group having a hydroxyl group.
前記第6族金属化合物は、第6族遷移金属のハロゲン化物、オキシハロゲン化物、ジオキシハロゲン化物、イミドハロゲン化物、ジイミドハロゲン化物又はイミドオキシハロゲン化物と、ジオール類と、電子供与性の中性配位子(L)とを混合することなどにより得られる。より具体的には、Journal of American Chemical Society,1993年,第115巻,p.7916−7917;Polyhedron,1992年,第11巻,p.2039−2044;Polyhedron,1995年,第14巻,p.3255−3271;などに記載された方法によって製造することができる。 The Group 6 metal compound includes a Group 6 transition metal halide, oxyhalide, dioxyhalide, imide halide, diimide halide or imideoxyhalide, diols, and electron-donating neutrality. It can be obtained by mixing with the ligand (L). More specifically, Journal of American Chemical Society, 1993, 115, p. 7916-7917; Polyhedron, 1992, Vol. 11, p. 2039-2044; Polyhedron, 1995, Vol. 14, p. 3255-3271; and the like.
本発明の製造方法においては、前記第6族遷移金属化合物を重合触媒として用い、前記の単量体と混合して重合を行う。単量体と重合触媒の使用量の割合は、モル比で(第6族遷移金属化合物:単量体)が、通常1:100〜1:2,000,000、好ましくは1:500〜1,000,000、より好ましくは1:1,000〜1:500,000である。触媒量が多すぎると触媒除去が困難となり、少なすぎると十分な重合活性が得られない。 In the production method of the present invention, the Group 6 transition metal compound is used as a polymerization catalyst, and the polymerization is performed by mixing with the monomer. As for the ratio of the amount of the monomer and the polymerization catalyst used, the molar ratio (Group 6 transition metal compound: monomer) is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1. 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of the catalyst is too large, it is difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity cannot be obtained.
また、本発明の製造方法においては、第6族遷移金属化合物を用いる場合に活性化剤を併用するのが好ましい。すなわち、第6族遷移金属化合物と活性化剤とからなる重合触媒組成物を用いることにより、より重合活性を向上させることができる。この第6族遷移金属化合物と活性化剤とからなる重合触媒組成物は、3環以上の多環式ノルボルネン系単量体の重合用触媒組成物として有用である。 Moreover, in the manufacturing method of this invention, when using a group 6 transition metal compound, it is preferable to use an activator together. That is, the polymerization activity can be further improved by using a polymerization catalyst composition comprising a Group 6 transition metal compound and an activator. This polymerization catalyst composition comprising a Group 6 transition metal compound and an activator is useful as a catalyst composition for polymerization of a tricyclic or higher polycyclic norbornene monomer.
前記活性化剤としては、炭素数1〜20の炭化水素基を有する周期表第1、2、12、13、14族の有機金属化合物を挙げることができる。なかでも、有機リチウム、有機マグネシウム、有機亜鉛、有機アルミニウム、有機スズが好ましく、有機アルミニウム、有機スズが特に好ましい。有機リチウムとしては、n−ブチルリチウム、メチルリチウム、フェニルリチウムなどを挙げることができる。有機マグネシウムとしては、ブチルエチルマグネシウム、ブチルオクチルマグネシウム、ジヘキシルマグネシウム、エチルマグネシウムクロリド、n−ブチルマグネシウムクロリド、アリルマグネシウムブロミドなどを挙げることができる。有機亜鉛としては、ジメチル亜鉛、ジエチル亜鉛、ジフェニル亜鉛などを挙げることができる。有機アルミニウムとしては、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、ジエチルアルミニウムクロリド、エチルアルミニウムセスキクロリド、エチルアルミニウムジクロリド、ジエチルアルミニウムエトキシド、ジイソブチルアルミニウムイソブトキシド、エチルアルミニウムジエトキシド、イソブチルアルミニウムジイソブトキシキドなどを挙げることができる。有機スズとしては、テトラメチルスズ、テトラ(n−ブチル)スズ、テトラフェニルスズなどを挙げることができる。 Examples of the activator include organometallic compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organic lithium, organic magnesium, organic zinc, organic aluminum, and organic tin are preferable, and organic aluminum and organic tin are particularly preferable. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
活性化剤の使用量は、前記第6族遷移金属化合物に対して、モル比で0.1〜100倍が好ましく、0.2〜50倍がより好ましく、0.5〜20倍が特に好ましい。使用量が少なすぎると重合活性が向上せず、多すぎると副反応が起こりやすくなる。 The amount of the activator used is preferably 0.1 to 100 times, more preferably 0.2 to 50 times, and particularly preferably 0.5 to 20 times in terms of molar ratio with respect to the Group 6 transition metal compound. . If the amount used is too small, the polymerization activity does not improve, and if it is too large, side reactions are likely to occur.
[溶媒]
本発明においては、重合反応を無溶媒で行うこともできるが、重合後、水素化反応を行う場合には、有機溶媒中で重合する(溶液重合)のが好ましい。本発明で用いる有機溶媒は、重合体及び重合体水素化物が所定の条件で溶解もしくは分散し、重合及び水素化を阻害しないものであれば、特に限定されない。
[solvent]
In the present invention, the polymerization reaction can be carried out in the absence of a solvent. However, when a hydrogenation reaction is carried out after the polymerization, the polymerization is preferably carried out in an organic solvent (solution polymerization). The organic solvent used in the present invention is not particularly limited as long as the polymer and the polymer hydride are dissolved or dispersed under predetermined conditions and do not inhibit polymerization and hydrogenation.
このような有機溶媒としては、具体的には、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ビシクロヘプタン、トリシクロデカン、ヘキサヒドロインデン、シクロオクタンなどの脂環族炭化水素;ベンゼン、トルエン、キシレンなどの芳香族炭化水素;ジクロロメタン、クロロホルム、1,2−ジクロロエタンなどのハロゲン系脂肪族炭化水素;クロロベンゼン、ジクロロベンゼンなどのハロゲン系芳香族炭化水素;ニトロメタン、ニトロベンゼン、アセトニトリルなどの含窒素炭化水素系溶媒;ジエチルエ−テル、テトラヒドロフランなどのエ−テル類などの溶媒を使用することができる。これらの溶媒の中でも、芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素およびエーテル類が好ましい。 Specific examples of such organic solvents include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, and bicyclohexane. Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Halogen-based aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; Diethyl ether, tetrahydrofuran, etc. D - it can be used solvents such as ethers. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers are preferable.
重合を有機溶媒中で行う場合には、単量体の濃度は、溶液中1〜50重量%が好ましく、2〜45重量%がより好ましく、3〜40重量%が特に好ましい。単量体の濃度が低すぎると生産性が悪く、高すぎる場合は重合後の溶液粘度が高すぎて、その後の水素化反応が困難となる場合がある。 When the polymerization is performed in an organic solvent, the concentration of the monomer is preferably 1 to 50% by weight in the solution, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. If the monomer concentration is too low, the productivity is poor, and if it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.
重合反応においては、活性調整剤を添加することもできる。活性調整剤は、重合触媒の安定化、重合反応の速度および重合体の分子量分布調整に用いる。活性調整剤は、官能基を有する有機化合物であれば特に制限されないが、含酸素、含窒素、含りん有機化合物が好ましい。具体的には、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、アニソール、フラン、テトラヒドロフランなどのエーテル類;アセトン、ベンゾフェノン、シクロヘキサノンなどのケトン類;エチルアセテートなどのエステル類;アセトニトリルベンゾニトリルなどのニトリル類;トリエチルアミン、トリイソプロピルアミン、キヌクリジン、N,N−ジエチルアニリンなどのアミン類;ピリジン、2,4−ルチジン、2,6−ルチジン、2−t−ブチルピリジンなどのピリジン類;トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフェ−ト、トリメチルホスフェ−トなどのホスフィン類;トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフェ−ト、トリメチルホスフェ−トなどのホスフィン類;トリフェニルホスフィンオキシドなどのホスフィンオキシド類;等が挙げられるが、これらに限定されない。これらは、1種単独で又は2種以上を混合して用いることができる。添加する活性調整剤の量は、重合触媒に対して0.01〜100モル%の間で任意に選択することができる。 In the polymerization reaction, an activity regulator can be added. The activity regulator is used to stabilize the polymerization catalyst, to adjust the polymerization reaction rate, and to adjust the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; and the like, but not limited thereto. These can be used individually by 1 type or in mixture of 2 or more types. The amount of the activity regulator to be added can be arbitrarily selected between 0.01 and 100 mol% with respect to the polymerization catalyst.
また、重合反応においては、重合体の分子量を調整するために分子量調整剤を添加することができる。分子量調整剤としては、1−ブテン、1−ペンテン、1−ヘキセン、1−オクテンなどのα−オレフィン類;スチレン、ビニルトルエンなどの芳香族ビニル化合物;エチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル、酢酸アリル、アリルアルコール、グリシジルメタクリレートなどの酸素含有ビニル化合物;アリルクロライドなどのハロゲン含有ビニル化合物;アクリルアミドなどの窒素含有ビニル化合物;1,4−ペンタジエン、1,4−ヘキサジエン、1,5−ヘキサジエン、1,6−ヘプタジエン、2−メチル−1,4−ペンタジエン、2,5−ジメチル−1,5−ヘキサジエンなどの非共役ジエン;1,3−ブタジエン、2−メチル−1,3−ブタジエン、2,3−ジメチル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエンなどの共役ジエン;を挙げることができる。添加する分子量調整剤の量は所望の分子量により、単量体に対して、0.1〜50モル%の間で任意に選択することができる。 In the polymerization reaction, a molecular weight modifier can be added to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol, and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1, - pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned. The amount of the molecular weight modifier to be added can be arbitrarily selected from 0.1 to 50 mol% based on the monomer depending on the desired molecular weight.
重合温度は特に制限はないが、一般には、−78℃〜200℃、好ましくは−30℃〜180℃である。重合時間は、1分間〜1000時間で、特に制限はない。 The polymerization temperature is not particularly limited, but is generally -78 ° C to 200 ° C, preferably -30 ° C to 180 ° C. The polymerization time is 1 minute to 1000 hours and is not particularly limited.
[ノルボルネン系開環重合体水素化物]
本発明のノルボルネン系開環重合体水素化物は、3環以上の多環式ノルボルネン系単量体由来の繰返し単位を含有するものである。本発明のノルボルネン系開環重合体水素化物において、3環以上の多環式ノルボルネン系単量体由来の繰返し単位とは、分子内にノルボルネン環と、該ノルボルネン環と縮合している一つ以上の環とを有するノルボルネン系単量体を開環重合し、次いで、得られた開環重合体中の主鎖二重結合を水素化して得られる繰返し単位である。
[Norbornene ring-opening polymer hydride]
The hydride of norbornene-based ring-opening polymer of the present invention contains a repeating unit derived from a tricyclic or more polycyclic norbornene-based monomer. In the hydride of norbornene-based ring-opening polymer of the present invention, the repeating unit derived from three or more polycyclic norbornene-based monomers is a norbornene ring in the molecule and one or more condensed with the norbornene ring. Is a repeating unit obtained by ring-opening polymerization of a norbornene-based monomer having the following ring, and then hydrogenating a main chain double bond in the obtained ring-opening polymer.
本発明のノルボルネン系開環重合体水素化物は、前記本発明の開環重合体の主鎖二重結合を50%以上水素化して得ることができる。本発明の開環重合体は、水素化後もタクティシティーを維持することができるので、得られる開環重合体水素化物はラセモ・ダイアッドの割合が51%以上、好ましくは60%以上、より好ましくは70%以上のシンジオタクティックな重合体である。水素化率は、好ましくは70%以上、より好ましくは80%以上、特に好ましくは90%以上である。水素化率が高いほど、開環重合体水素化物は耐熱性に優れる。 The hydrogenated norbornene-based ring-opening polymer of the present invention can be obtained by hydrogenating 50% or more of the main chain double bond of the ring-opening polymer of the present invention. Since the ring-opening polymer of the present invention can maintain tacticity after hydrogenation, the resulting ring-opening polymer hydride has a racemo dyad ratio of 51% or more, preferably 60% or more, more preferably. Is a syndiotactic polymer of 70% or more. The hydrogenation rate is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The higher the hydrogenation rate, the better the heat resistance of the ring-opening polymer hydride.
本発明の開環重合体水素化物は、通常結晶性であり、融点(Tm)を有する。融点は、示差走査熱量計にて測定したとき、重合体の結晶成分の溶融による吸熱ピークにより観測することができる。本発明の開環重合体水素化物は、通常150℃以上、好ましくは200℃〜400℃の融点を有している。 The ring-opening polymer hydride of the present invention is usually crystalline and has a melting point (Tm). The melting point can be observed by an endothermic peak due to melting of the crystalline component of the polymer when measured with a differential scanning calorimeter. The ring-opening polymer hydride of the present invention has a melting point of usually 150 ° C. or higher, preferably 200 ° C. to 400 ° C.
[水素化反応]
本発明の開環重合体水素化物の製造方法は、前記本発明の開環重合体の製造方法により開環重合体を得る工程と、該開環重合体の炭素−炭素二重結合を水素化する工程とを含む。水素化反応は、水素化触媒の存在下で、反応系内に水素を供給して行う。水素化触媒としては、オレフィン化合物の水素化に際して一般に使用されているものであれば使用可能であり、特に制限されないが、例えば、次のようなものが挙げられる。
[Hydrogenation reaction]
The method for producing a hydride of a ring-opened polymer according to the present invention comprises a step of obtaining a ring-opened polymer by the method for producing a ring-opened polymer according to the present invention, and hydrogenating a carbon-carbon double bond of the ring-opened polymer. Including the step of. The hydrogenation reaction is performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. Any hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.
均一系触媒としては、遷移金属化合物とアルカリ金属化合物の組み合わせからなる触媒系、例えば、酢酸コバルト/トリエチルアルミニウム、ニッケルアセチルアセトナート/トリイソブチルアルミニウム、チタノセンジクロリド/n−ブチルリチウム、ジルコノセンジクロリド/sec−ブチルリチウム、テトラブトキシチタネート/ジメチルマグネシウムなどの組み合わせが挙げられる。さらに、ジクロロビス(トリフェニルホスフィン)パラジウム、クロロヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム、クロロトリス(トリフェニルホスフィン)ロジウムなどの貴金属錯体触媒を挙げることができる。 As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Examples include butyl lithium, tetrabutoxy titanate / dimethyl magnesium, and the like. Further examples include noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, and chlorotris (triphenylphosphine) rhodium.
不均一触媒としては、ニッケル、パラジウム、白金、ロジウム、ルテニウム、又はこれらの金属をカーボン、シリカ、ケイソウ土、アルミナ、酸化チタンなどの担体に担持させた固体触媒、例えば、ニッケル/シリカ、ニッケル/ケイソウ土、ニッケル/アルミナ、パラジウム/カーボン、パラジウム/シリカ、パラジウム/ケイソウ土、パラジウム/アルミナなどの触媒系が挙げられる。 As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.
水素化反応は、通常、不活性有機溶媒中で実施する。このような不活性有機溶媒としては、ベンゼン、トルエンなどの芳香族炭化水素;ペンタン、ヘキサンなどの脂肪族炭化水素;シクロヘキサン、デカヒドロナフタレンなどの脂環族炭化水素;テトラヒドロフラン、エチレングリコールジメチルエーテルなどのエーテル類;などが挙げられる。
不活性有機溶媒は、通常は、重合反応に用いる溶媒と同じで良く、重合反応液にそのまま水素化触媒を添加して反応させればよい。
The hydrogenation reaction is usually carried out in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like.
The inert organic solvent is usually the same as the solvent used for the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and allowed to react.
水素化反応は、使用する水素化触媒によっても適する条件範囲が異なるが、反応温度は通常−20℃〜250℃、好ましくは−10℃〜220℃、より好ましくは0℃〜200℃である。水素化温度が低すぎると反応速度が遅く、高すぎると副反応が起こる場合がある。水素圧力は、通常0.01〜20MPa、好ましくは0.05〜15MPa、より好ましくは0.1〜10MPaである。水素圧力が低すぎると水素化速度が遅くなり、高すぎると高耐圧反応装置が必要となる。反応時間は所望の水素化率とできれば特に限定されないが、通常0.1〜10時間である。 The suitable conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst used, but the reaction temperature is usually -20 ° C to 250 ° C, preferably -10 ° C to 220 ° C, more preferably 0 ° C to 200 ° C. If the hydrogenation temperature is too low, the reaction rate is slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate is slow, and if it is too high, a high pressure reactor is required. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 10 hours.
以下に、実施例及び比較例を挙げて、本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではない。なお、製造例、実施例および比較例における部および%は、断りのない限り重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in a manufacture example, an Example, and a comparative example are a basis of weight.
(1)開環重合体の数平均分子量(Mn)および重量平均分子量(Mw)はクロロホルムを溶媒とするゲル・パーミエーション・クロマトグラフィー測定によりポリスチレン換算値として求めた。
(2)開環重合体の異性体比(シス/トランス比)および開環重合体水素化物の水素化率は、1H−NMR測定により求めた。
(3)開環重合体水素化物のラセモ・ダイアッドの割合は、オルトジクロロベンゼン−d4を溶媒として、150℃で13C−NMR測定を行い、メソ・ダイアッド由来の43.35ppmのシグナルと、ラセモ・ダイアッド由来の43.43ppmのシグナルの強度比から決定した。
(4)開環重合体水素化物のガラス転移温度(Tg)および融点(Tm)、ならびに融解熱(ΔH)は、示差走査熱量計を用いて、10℃/分で昇温して測定した。
(1) The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the ring-opening polymer were obtained as polystyrene conversion values by gel permeation chromatography measurement using chloroform as a solvent.
(2) The isomer ratio (cis / trans ratio) of the ring-opening polymer and the hydrogenation rate of the ring-opening polymer hydride were determined by 1 H-NMR measurement.
(3) The ratio of racemo dyad in the ring-opened polymer hydride was measured by performing 13 C-NMR measurement at 150 ° C. using orthodichlorobenzene-d 4 as a solvent, and a 43.35 ppm signal derived from meso dyad, It was determined from the intensity ratio of the 43.43 ppm signal from Racemo Dyad.
(4) The glass transition temperature (Tg) and melting point (Tm) and heat of fusion (ΔH) of the ring-opening polymer hydride were measured by raising the temperature at 10 ° C./min using a differential scanning calorimeter.
[製造例1]
攪拌機付きガラス製反応器に、タングステン(2,6−ジメチルフェニルイミド)テトラクロリドを1.35部と、ジエチルエーテル21部を添加し、これを−78℃に冷却した。さらにジエチルエーテル21部に溶解した3,3’,5,5’−テトラメチル−2,2’−ビフェノール0.74部を添加した。この混合物を0℃まで徐々に加温し、0℃を維持して24時間の反応を行った。反応後、ジエチルエーテルを留去することにより暗赤紫色の固形物を得た。
得られた固形物に、ヘキサン13部とジエチルエーテル4.2部を添加し、これを−78℃に冷却し1時間静置して、微結晶状の不溶物を析出させた。可溶部分をろ別し、残った不溶物をさらにヘキサン6.6部にて洗浄後、溶媒を留去して化合物(a)1.84部を得た。
[Production Example 1]
To a glass reactor equipped with a stirrer, 1.35 parts of tungsten (2,6-dimethylphenylimide) tetrachloride and 21 parts of diethyl ether were added and cooled to -78 ° C. Further, 0.74 part of 3,3 ′, 5,5′-tetramethyl-2,2′-biphenol dissolved in 21 parts of diethyl ether was added. The mixture was gradually warmed to 0 ° C., and maintained at 0 ° C. for 24 hours. After the reaction, diethyl ether was distilled off to obtain a dark red purple solid.
To the obtained solid, 13 parts of hexane and 4.2 parts of diethyl ether were added, and this was cooled to −78 ° C. and allowed to stand for 1 hour to precipitate a microcrystalline insoluble matter. The soluble part was filtered off, and the remaining insoluble matter was further washed with 6.6 parts of hexane, and then the solvent was distilled off to obtain 1.84 parts of compound (a).
この化合物(a)のC6D6中で測定した1H−NMRスペクトルは以下であった。
δppm:7.79(s,1H),6.98(d,1H),6.88(d,1H),6.77(s,2H),6.75(s,2H),6.26(t,1H),3.27(q,4H),3.07(s,6H),2.41(s,3H),2.37(s,3H),2.23(s,3H),2.05(s,3H),1.00(t,6H)
The 1 H-NMR spectrum measured in C 6 D 6 of this compound (a) was as follows.
δppm: 7.79 (s, 1H), 6.98 (d, 1H), 6.88 (d, 1H), 6.77 (s, 2H), 6.75 (s, 2H), 6.26 (T, 1H), 3.27 (q, 4H), 3.07 (s, 6H), 2.41 (s, 3H), 2.37 (s, 3H), 2.23 (s, 3H) , 2.05 (s, 3H), 1.00 (t, 6H)
この化合物(a)の元素分析の結果は、炭素46.39%、水素5.07%、窒素1.91%であった。この結果は、式(15)に示される化合物の元素組成の計算値、炭素46.40%、水素5.01%、窒素1.93%とよく一致した。以上の結果から、化合物(a)は式(15)で表される構造であることを確認した。 The results of elemental analysis of this compound (a) were carbon 46.39%, hydrogen 5.07%, and nitrogen 1.91%. This result was in good agreement with the calculated value of the elemental composition of the compound represented by formula (15), 46.40% carbon, 5.01% hydrogen, and 1.93% nitrogen. From the above results, it was confirmed that the compound (a) had a structure represented by the formula (15).
[製造例2]
タングステン(2,6−ジメチルフェニルイミド)テトラクロリド1.35gに代えて、タングステン(フェニルイミド)テトラクロリド・ジエチルエーテル錯体1.13部を用いたほかは、製造例1と同様にして化合物(b)1.34部を得た。
[Production Example 2]
Compound (b) was prepared in the same manner as in Production Example 1 except that 1.13 g of tungsten (phenylimide) tetrachloride / diethyl ether complex was used instead of 1.35 g of tungsten (2,6-dimethylphenylimide) tetrachloride. ) 1.34 parts were obtained.
この化合物(b)のC6D6中で測定した1H−NMRスペクトルは以下であった。
δppm:9.13(s,1H),7.29(s,1H),7.14(s,1H),6.80(d,2H),6.36(t,1H),3.33(q,4H),3.17(s,6H),1.40(s,9H),1.30(s,9H),1.12(t,6H)。
The 1 H-NMR spectrum measured in C 6 D 6 of this compound (b) was as follows.
δppm: 9.13 (s, 1H), 7.29 (s, 1H), 7.14 (s, 1H), 6.80 (d, 2H), 6.36 (t, 1H), 3.33 (Q, 4H), 3.17 (s, 6H), 1.40 (s, 9H), 1.30 (s, 9H), 1.12 (t, 6H).
この化合物(b)の元素分析の結果は、炭素44.91%、水素4.61%、窒素2.05%であった。この結果は、式(16)に示される化合物の元素組成の計算値、炭素44.82%、水素4.63%、窒素2.01%とよく一致した。この結果より、化合物(b)の構造は、式(16)によって示される構造であることを確認した。 The results of elemental analysis of this compound (b) were carbon 44.91%, hydrogen 4.61% and nitrogen 2.05%. This result was in good agreement with the calculated elemental composition of the compound represented by formula (16), 44.82% carbon, 4.63% hydrogen, and 2.01% nitrogen. From this result, it was confirmed that the structure of the compound (b) was a structure represented by the formula (16).
[実施例1]
攪拌機付きガラス製反応器に、重合触媒として、製造例1で得られた化合物(a)を0.082部とトルエン3.5部を添加し、これを−78℃に冷却した。さらにジエチルアルミニウムクロリド0.027部をトルエン0.87部に溶解した溶液を添加して、これを0℃まで戻し、1時間反応した。得られた混合物に、ジシクロペンタジエン7.5部、トルエン23部、1−オクテン0.65部を添加し、0℃において重合反応を行った。重合反応開始後、徐々に溶液の粘度が上昇した。24時間反応後、重合反応液に大量のメタノールを注いで沈殿物を凝集させ、濾別洗浄後、40℃で24時間減圧乾燥して、開環重合体(1)を7.4部得た。開環重合体(1)のMnは42,000、Mwは210,000であった。開環重合体主鎖の炭素−炭素二重結合のシス/トランス比は、93/7であった。
[Example 1]
0.082 parts of the compound (a) obtained in Production Example 1 and 3.5 parts of toluene were added as a polymerization catalyst to a glass reactor equipped with a stirrer, and this was cooled to -78 ° C. Further, a solution obtained by dissolving 0.027 part of diethylaluminum chloride in 0.87 part of toluene was added, and this was returned to 0 ° C. and reacted for 1 hour. To the resulting mixture, 7.5 parts of dicyclopentadiene, 23 parts of toluene, and 0.65 part of 1-octene were added, and a polymerization reaction was performed at 0 ° C. After the polymerization reaction started, the viscosity of the solution gradually increased. After the reaction for 24 hours, a large amount of methanol was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours to obtain 7.4 parts of the ring-opened polymer (1). . Mn of the ring-opening polymer (1) was 42,000, and Mw was 210,000. The cis / trans ratio of the carbon-carbon double bond of the ring-opening polymer main chain was 93/7.
[実施例2]
化合物(a)0.082部に代えて、重合触媒として、製造例2で得た化合物(b)を0.079部用いたほかは実施例1と同様にして、開環重合体(2)を7.1部得た。開環重合体(2)のMnは8,100、Mwは25,000であった。開環重合体主鎖の炭素−炭素二重結合のシス/トランス比は、92/8であった。
[Example 2]
In the same manner as in Example 1 except that 0.079 part of the compound (b) obtained in Production Example 2 was used as a polymerization catalyst instead of 0.082 part of the compound (a), a ring-opening polymer (2) 7.1 parts of was obtained. Mn of the ring-opening polymer (2) was 8,100, and Mw was 25,000. The cis / trans ratio of the carbon-carbon double bond of the ring-opening polymer main chain was 92/8.
[実施例3]
攪拌機付きオートクレーブに、実施例1で得た開環重合体(1)3部とシクロヘキサン47部を加えた。次いで、ビス(トリシクロヘキシルホスフィン)ベンジリデンルテニウム(IV)ジクロリド0.0187部及びエチルビニルエーテル0.45部をシクロヘキサン7.8部に溶解した水素化触媒溶液を添加し、水素圧0.8MPa、160℃で8時間水素化反応を行った。水素化反応液を多量のイソプロパノールに注いでポリマ−を完全に析出させ、濾別洗浄後、40℃で24時間減圧乾燥して、開環重合体水素化物(1)を得た。このものの1H−NMRを測定したところ、炭素−炭素二重結合由来のピークは観測されず、水素化率は99%以上であった。開環重合体水素化物(1)のラセモ・ダイアッドの割合は、68%であった。融点(Tm)は270℃、融解熱(ΔH)は49J/gであった。
[Example 3]
To an autoclave equipped with a stirrer, 3 parts of the ring-opening polymer (1) obtained in Example 1 and 47 parts of cyclohexane were added. Subsequently, a hydrogenation catalyst solution in which 0.0187 parts of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 parts of ethyl vinyl ether were dissolved in 7.8 parts of cyclohexane was added, and the hydrogen pressure was 0.8 MPa, 160 ° C. The hydrogenation reaction was carried out for 8 hours. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours to obtain a ring-opened polymer hydride (1). When 1 H-NMR of this product was measured, no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (1) was 68%. The melting point (Tm) was 270 ° C. and the heat of fusion (ΔH) was 49 J / g.
[実施例4]
開環重合体として、実施例2で得た開環重合体(2)3部を用いたほかは、実施例3と同様にして開環重合体水素化物(2)を得た。このものの1H−NMRを測定したところ、炭素−炭素二重結合由来のピークは観測されず、水素化率は99%以上であった。開環重合体水素化物(2)のラセモ・ダイアッドの割合は、80%であった。融点(Tm)は271℃、融解熱(ΔH)は49J/gであった。
[Example 4]
A hydrogenated ring-opened polymer (2) was obtained in the same manner as in Example 3 except that 3 parts of the ring-opened polymer (2) obtained in Example 2 was used as the ring-opened polymer. When 1 H-NMR of this product was measured, no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (2) was 80%. The melting point (Tm) was 271 ° C. and the heat of fusion (ΔH) was 49 J / g.
[比較例1]
化合物(a)0.082部に代えて、重合触媒として、タングステンオキシテトラクロリドを0.05部用いたほかは実施例1と同様にして、開環重合体(3)を7.4部得た。開環重合体(3)のMnは5,200、Mwは26,100であった。開環重合体主鎖の炭素−炭素二重結合のシス/トランス比は、80/20であった。
[Comparative Example 1]
7.4 parts of ring-opened polymer (3) were obtained in the same manner as in Example 1 except that 0.05 part of tungstenoxytetrachloride was used as a polymerization catalyst instead of 0.082 part of compound (a). It was. Mn of the ring-opening polymer (3) was 5,200, and Mw was 26,100. The cis / trans ratio of the carbon-carbon double bond of the ring-opening polymer main chain was 80/20.
[比較例2]
比較例1で得た開環重合体(3)を用いて、実施例3と同様に水素化反応を行うことにより、開環重合体水素化物(3)を得た。このものの1H−NMRを測定したところ、炭素−炭素二重結合由来のピークは観測されず、水素化率は99%以上であった。開環重合体水素化物(3)のラセモ・ダイアッドの割合は、50%であった。融点(Tm)は観測されず、ガラス転移点(Tg)が98℃に観測された。
以上の結果を第1表に示す。
[Comparative Example 2]
Using the ring-opening polymer (3) obtained in Comparative Example 1, a hydrogenation reaction was carried out in the same manner as in Example 3 to obtain a ring-opening polymer hydride (3). When 1 H-NMR of this product was measured, no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (3) was 50%. The melting point (Tm) was not observed, and the glass transition point (Tg) was observed at 98 ° C.
The above results are shown in Table 1.
これに対し、比較例1では、シス体の含有量(シス/トランス比)が比較的低い開環重合体(3)が得られた。また、このものを水素化することで得られた開環重合体水素化物(3)は、ラセモ・ダイアッドの割合が50%であって、融点を示さない非晶性の重合体であり、ガラス転移温度が103℃と低く、耐熱性が低いものであった(比較例1,2)。
On the other hand, in Comparative Example 1, a ring-opening polymer (3) having a relatively low cis content (cis / trans ratio) was obtained. Further, the hydrogenated ring-opening polymer (3) obtained by hydrogenating this product is an amorphous polymer having a racemo dyad ratio of 50% and showing no melting point. The transition temperature was as low as 103 ° C. and the heat resistance was low (Comparative Examples 1 and 2).
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