JP4605712B2 - Ring-opening polymer of norbornene derivative and process for producing the same - Google Patents
Ring-opening polymer of norbornene derivative and process for producing the same Download PDFInfo
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- JP4605712B2 JP4605712B2 JP2005267127A JP2005267127A JP4605712B2 JP 4605712 B2 JP4605712 B2 JP 4605712B2 JP 2005267127 A JP2005267127 A JP 2005267127A JP 2005267127 A JP2005267127 A JP 2005267127A JP 4605712 B2 JP4605712 B2 JP 4605712B2
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- 229920000642 polymer Polymers 0.000 title claims description 35
- 238000007142 ring opening reaction Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 6
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 title claims 12
- -1 cyanoformate ester Chemical class 0.000 claims description 113
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 26
- 150000002430 hydrocarbons Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 17
- 125000003368 amide group Chemical group 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 12
- 230000000737 periodic effect Effects 0.000 claims description 12
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 12
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002685 polymerization catalyst Substances 0.000 claims description 7
- 150000003623 transition metal compounds Chemical class 0.000 claims description 5
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 3
- 125000002872 norbornadienyl group Chemical class C12=C(C=C(CC1)C2)* 0.000 claims 2
- 150000002848 norbornenes Chemical class 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 0 *C1=C(*)C2C=CC1C2 Chemical compound *C1=C(*)C2C=CC1C2 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- HJMZMZRCABDKKV-UHFFFAOYSA-M cyanoformate Chemical compound [O-]C(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-M 0.000 description 6
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 6
- MSMGXWFHBSCQFB-UHFFFAOYSA-N ethyl cyanoformate Chemical compound CCOC(=O)C#N MSMGXWFHBSCQFB-UHFFFAOYSA-N 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 150000002846 norbornadienes Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- PGKLXLJJGUJWJX-UHFFFAOYSA-N butyl bicyclo[2.2.1]hept-2-ene-4-carboxylate Chemical compound C1CC2C=CC1(C(=O)OCCCC)C2 PGKLXLJJGUJWJX-UHFFFAOYSA-N 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- HWNBJKGDFORPGF-UHFFFAOYSA-N propyl bicyclo[2.2.1]hept-2-ene-4-carboxylate Chemical compound C1CC2C=CC1(C(=O)OCCC)C2 HWNBJKGDFORPGF-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- HUSVRHCQCBQEDY-UHFFFAOYSA-N 3-propylbicyclo[2.2.1]hepta-2,5-diene Chemical compound C1C2C(CCC)=CC1C=C2 HUSVRHCQCBQEDY-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000006269 biphenyl-2-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(*)C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LURVUWBWEGPODG-UHFFFAOYSA-L dichlororuthenium;tricyclohexylphosphane Chemical compound [Cl-].[Cl-].[Ru+2].C1CCCCC1P(C1CCCCC1)C1CCCCC1 LURVUWBWEGPODG-UHFFFAOYSA-L 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical group CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- OBWFJXLKRAFEDI-UHFFFAOYSA-N methyl cyanoformate Chemical compound COC(=O)C#N OBWFJXLKRAFEDI-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- MLLYPIKBTHTPEJ-UHFFFAOYSA-N propan-2-yl cyanoformate Chemical compound CC(C)OC(=O)C#N MLLYPIKBTHTPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- INQJNNVLABTDDI-UHFFFAOYSA-N 2,2-dimethylpropyl cyanoformate Chemical compound CC(C)(C)COC(=O)C#N INQJNNVLABTDDI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は、エキソ選択的にシアノ基およびエステル基を導入したノルボルネン誘導体の開環重合体およびその製造方法に関する。 The present invention relates to a ring-opening polymer of a norbornene derivative into which a cyano group and an ester group are introduced exoselectively and a method for producing the same.
極性基を有するノルボルネン誘導体の開環重合体は、耐熱性、透明性などに優れ、耐熱性光学材料として有用である。 A ring-opening polymer of a norbornene derivative having a polar group is excellent in heat resistance and transparency, and is useful as a heat-resistant optical material.
極性基を有するノルボルネン誘導体の開環重合体を製造する方法としては、極性基を有するノルボルネン誘導体を製造し、これを開環重合することにより製造する方法が知られている。極性基を有するノルボルネン誘導体の製造方法としては、シクロペンタジエンと極性基を有するオレフィンとのＤｉｅｌｓ−Ａｌｄｅｒ反応により製造する方法が知られている。しかし、この方法で得られるノルボルネン誘導体は、エキソ体とエンド体の混合物となり、その生成比は立体的要因により、エンド体のほうが大きくなる傾向がある。開環メタセシス重合では、エンド体と比較してエキソ体の反応性が高いことなどから（非特許文献１参照。）、エキソ体の分離あるいはエンド体からエキソ体への異性化等が検討されている。しかしながら、選択的にエキソ位に極性基を有するノルボルネン誘導体を得ることは容易ではない。したがって、エキソ位に選択的に極性基を有するノルボルネン誘導体の開環メタセシス重合体の製造は困難なものであった。 As a method for producing a ring-opening polymer of a norbornene derivative having a polar group, a method for producing a norbornene derivative having a polar group and subjecting it to ring-opening polymerization is known. As a method for producing a norbornene derivative having a polar group, a method of producing a norbornene derivative by a Diels-Alder reaction between cyclopentadiene and an olefin having a polar group is known. However, the norbornene derivative obtained by this method is a mixture of exo and endo isomers, and the production ratio tends to be larger in the endo isomer due to steric factors. In ring-opening metathesis polymerization, since the reactivity of the exo-isomer is higher than that of the endo-isomer (see Non-Patent Document 1), separation of the exo-isomer or isomerization from the endo-isomer to the exo-isomer has been studied. Yes. However, it is not easy to selectively obtain a norbornene derivative having a polar group at the exo position. Accordingly, it has been difficult to produce a ring-opening metathesis polymer of a norbornene derivative having a polar group selectively at the exo position.
本発明者らは、極性基としてシアノ基とエステル基をエキソ位選択的に導入したノルボルネン誘導体の製造方法を見出している（特許文献１、非特許文献２）。
本発明の課題は、極性基としてシアノ基とエステル基をエキソ選択的に導入したノルボルネン誘導体の開環重合体並びにその製造方法の提供することにある。 An object of the present invention is to provide a ring-opening polymer of a norbornene derivative in which a cyano group and an ester group are introduced exoselectively as polar groups, and a method for producing the same.
本発明者らは上記課題を達成するため鋭意検討の結果、極性基としてシアノ基とエステル基がエキソ選択的に導入したノルボルネン誘導体を開環メタセシス重合触媒を用いて開環重合させることにより、シアノ基とエステル基がエキソ選択的に導入されたノルボルネン誘導体の開環重合体を製造できることを見出した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have carried out ring-opening polymerization of a norbornene derivative in which a cyano group and an ester group are exoselectively introduced as polar groups using a ring-opening metathesis polymerization catalyst. It has been found that a ring-opening polymer of a norbornene derivative in which a group and an ester group are introduced exoselectively can be produced.
すなわち本発明は、分子内に、一般式（１） That is, the present invention provides a compound represented by the general formula (1)
（一般式（１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、炭素数１〜２０の炭化水素基、置換シリル基、置換アミド基、置換アルコキシ基、置換アリーロキシ基、ハロゲン原子、または置換シリル基、周期表第１５族，１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基を表す。Ｅ１，Ｅ２の一方はシアノ基、他方はエステル基［−Ｃ（Ｏ）ＯＲ３］を表す。ここで、Ｒ３は水素原子、炭素数１〜２０の炭化水素基、置換シリル基、置換アミド基、置換アルコキシ基、置換アリーロキシ基、ハロゲン原子、または置換シリル基、周期表第１５族，１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基である。）
または、一般式（２）
(In General Formula (1), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group, a substituted amide group, a substituted alkoxy group, a substituted aryloxy group, or a halogen atom. Represents an atom or a substituted silyl group, an atom of Groups 15 and 16 of the periodic table, or a hydrocarbon group containing 1 to 20 carbon atoms, one of E 1 and E 2 being a cyano group, the other being an ester group [ —C (O) OR 3 ], wherein R 3 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group, a substituted amide group, a substituted alkoxy group, a substituted aryloxy group, a halogen atom, or A substituted silyl group, an atom of Groups 15 and 16 of the periodic table, or a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom.)
Or general formula (2)
（一般式（２）中、Ｒ１〜Ｒ３、Ｅ１およびＥ２は前記一般式（１）と同じである。）で表される繰り返し単位を有することを特徴とするノルボルネン誘導体の開環重合体、ならびに一般式（３） (In the general formula (2), R 1 to R 3 , E 1 and E 2 are the same as those in the general formula (1)). Polymer and general formula (3)
（一般式（３）中、Ｒ１〜Ｒ３、Ｅ１およびＥ２は前記一般式（１）と同じである。）または、一般式（４） (In General Formula (3), R 1 to R 3 , E 1 and E 2 are the same as those in General Formula (1)) or General Formula (4)
（一般式（４）中、Ｒ１〜Ｒ３、Ｅ１およびＥ２は前記一般式（１）と同じである。）で表されるノルボルネン誘導体を、開環メタセシス重合触媒の存在下において開環メタセシス重合させることを特徴とするノルボルネン誘導体の開環重合体の製造方法に関するものである。 (In the general formula (4), R 1 to R 3 , E 1 and E 2 are the same as those in the general formula (1).) The norbornene derivative represented by the above formula is opened in the presence of a ring-opening metathesis polymerization catalyst. The present invention relates to a method for producing a ring-opening polymer of a norbornene derivative, characterized by carrying out ring metathesis polymerization.
本発明により、選択的にエキソ位にシアノ基とエステル基を有するノルボルネン誘導体の開環重合体を製造することが可能となった。本発明のノルボルネン誘導体の開環重合体は、耐熱性、透明性などに優れ、耐熱性光学材料として有用である。 According to the present invention, a ring-opening polymer of a norbornene derivative having a cyano group and an ester group at an exo position can be selectively produced. The ring-opening polymer of the norbornene derivative of the present invention is excellent in heat resistance and transparency, and is useful as a heat resistant optical material.
以下本発明を詳細に説明する。ただし、説明の中で具体例を挙げるがこれらに限定されるものではない。 The present invention will be described in detail below. However, specific examples will be given in the description, but the present invention is not limited to these.
本発明のノルボルネン誘導体の開環重合体は、分子内に一般式（１）又は（２）で表される繰り返し単位を有することを特徴とする。 The ring-opening polymer of the norbornene derivative of the present invention is characterized by having a repeating unit represented by the general formula (1) or (2) in the molecule.
一般式（１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子、炭素数１〜２０の炭化水素基、置換シリル基、置換アミド基、置換アルコキシ基、置換アリーロキシ基、ハロゲン原子、または置換シリル基、周期表第１５族、１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基である。炭素数１〜２０の炭化水素基の具体例としては、メチル基、エチル基、ビニル基、ノルマルプロピル基、イソプロピル基、アリル基、ノルマルブチル基、イソブチル基、t−ブチル基、ペンチル基、ネオペンチル基、シクロペンチル基、ヘキシル基、シクロへキシル基、フェニル基、ヘプチル基、ベンジル基、２−メチルフェニル基、４−メチルフェニル基、オクチル基、２，６−ジメチルフェニル基、２−エチルフェニル基、ノニル基、クミル基、２−イソプロピルフェニル基、２，４，６−トリメチルフェニル基、２−エチル−６−メチルフェニル基、デシル基、ナフチル基、アダマンチル基、２−t−ブチルフェニル基、２，６−ジエチルフェニル基、２−メチル−６−イソプロピルフェニル基、ウンデシル基、２−エチル−６−イソプロピル基、２，６−ジエチル−４メチルフェニル基、ドデシル基、２，６−ジイソプロピルフェニル基、２−ビフェニル基、２−シクロへキシルフェニル基、トリデシル基、２，６−ジイソプロピル−４−メチルフェニル基、テトラデシル基、２，６−ジブチルフェニル基、１−アントラセニル基、ペンタデシル基、２，６−ジ−t−ブチル−４−メチルフェニル基、２−フェニル−６−イソプロピルフェニル基、ヘキサデシル基、２−ナフチルフェニル基、２−t−ブチル−６−フェニルフェニル基、ヘプタデシル基、２−t−ブチル−４−メチル−６−フェニルフェニル基、オクタデシル基、２，６−ジフェニルフェニル基、ノナデシル基、トリフェニルメチル基、４−メチル２，６−ジフェニルフェニル基、アラキジル基、２，６−ジパラトリルフェニル基等を挙げることができ、置換シリル基の具体例としては、トリメチルシリル基、ジメチルフェニルシリル基、トリイソプロピルシリル基、ジメチルメトキシシリル基、ジメチル−ｔ−ブチルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基等を挙げることができる。置換アミド基の具体的な例としては、ジメチルアミド基、ジエチルアミド基、ジイソプロピルアミド基などが挙げられる。置換アルコキシ基の具体的な例としては、メトキシ基、エトキシ基、イソプロポキシ基、t−ブトキシ基、トリメチルシリルメトキシ基などが挙げられる。置換アリーロキシ基の具体的な例としては、フェノキシ基、パラメチルフェノキシ基、パラメトキシフェノキシ基、２，６−ジメチルフェノキシ基、１−ナフトキシ基などが挙げられる。置換シリル基、周期表１５族，１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基の具体例としては、トリメチルシリルメチル基、ジメチルフェニルシリルメチル基、２−ジメチルアミノフェニル基、２−ジエチルアミノフェニル基、２−ジイソプロピルアミノフェニル基、２−ピリジル基、６−メチル−２−ピリジル基、２−ピリジルフェニル基、２−イミダゾリル基、２−シアノフェニル基、２−ジメチルホスフィノフェニル基、２−ジフェニルホスフィノフェニル基、トリフェニルホスホラニリデンメチル基、２−メトキシフェニル基、２−エトキシフェニル基、２−イソプロポキシフェニル基、２−フェノキシフェニル基、２−チオメチルフェニル基、メチルスルホニルメチル基、ｐ−トルエンスルホニルメチル基、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロフェニル基、２−クロロ−１−メチルエチル基等を挙げることができる。 In general formula (1), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group, a substituted amide group, a substituted alkoxy group, a substituted aryloxy group, or a halogen atom. Or a substituted silyl group, an atom of Groups 15 and 16 of the periodic table, or a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, normal propyl group, isopropyl group, allyl group, normal butyl group, isobutyl group, t-butyl group, pentyl group and neopentyl. Group, cyclopentyl group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group , Nonyl group, cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl group, 2-t-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-isopropylphenyl group, undecyl group, 2-ethyl-6-isopropyl Pyr group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, tridecyl group, 2,6-diisopropyl-4-methyl Phenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-di-t-butyl-4-methylphenyl group, 2-phenyl-6-isopropylphenyl group, hexadecyl group 2-naphthylphenyl group, 2-t-butyl-6-phenylphenyl group, heptadecyl group, 2-t-butyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl Group, triphenylmethyl group, 4-methyl 2,6-diphenylphenyl group, arachidyl group, 2,6-diparato Specific examples of the substituted silyl group include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenyl. A silyl group etc. can be mentioned. Specific examples of the substituted amide group include a dimethylamide group, a diethylamide group, and a diisopropylamide group. Specific examples of the substituted alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, and a trimethylsilylmethoxy group. Specific examples of the substituted aryloxy group include a phenoxy group, a paramethylphenoxy group, a paramethoxyphenoxy group, a 2,6-dimethylphenoxy group, and a 1-naphthoxy group. Specific examples of the substituted silyl group, the group 15 to 16 of the periodic table, or the hydrocarbon group having 1 to 20 carbon atoms including a halogen atom include a trimethylsilylmethyl group, a dimethylphenylsilylmethyl group, a 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group, 2-pyridyl group, 6-methyl-2-pyridyl group, 2-pyridylphenyl group, 2-imidazolyl group, 2-cyanophenyl group, 2-dimethylphosphinophenyl Group, 2-diphenylphosphinophenyl group, triphenylphosphoranylidenemethyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group, 2-phenoxyphenyl group, 2-thiomethylphenyl group, Methylsulfonylmethyl group, p-toluenesulfonylmethyl , It may be mentioned a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, a 2-chloro-1-methylethyl group and the like.
Ｅ１，Ｅ２の一方はシアノ基［−Ｃ≡Ｎ］、他方はエステル基［−Ｃ（Ｏ）ＯＲ３］である。 One of E 1 and E 2 is a cyano group [—C≡N], and the other is an ester group [—C (O) OR 3 ].
Ｒ３は水素原子、炭素数１〜２０の炭化水素基、置換シリル基、置換アミド基、置換アルコキシ基、置換アリーロキシ基、または置換シリル基、周期表第１５族、１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基である。炭素数１〜２０の炭化水素基の具体例としては、メチル基、エチル基、ビニル基、ノルマルプロピル基、イソプロピル基、アリル基、ノルマルブチル基、イソブチル基、t−ブチル基、ペンチル基、ネオペンチル基、シクロペンチル基、ヘキシル基、シクロへキシル基、フェニル基、ヘプチル基、ベンジル基、２−メチルフェニル基、４−メチルフェニル基、オクチル基、２，６−ジメチルフェニル基、２−エチルフェニル基、ノニル基、クミル基、２−イソプロピルフェニル基、２，４，６−トリメチルフェニル基、２−エチル−６−メチルフェニル基、デシル基、ナフチル基、アダマンチル基、２−t−ブチルフェニル基、２，６−ジエチルフェニル基、２−メチル−６−イソプロピルフェニル基、ウンデシル基、２−エチル−６−イソプロピル基、２，６−ジエチル−４メチルフェニル基、ドデシル基、２，６−ジイソプロピルフェニル基、２−ビフェニル基、２−シクロへキシルフェニル基、トリデシル基、２，６−ジイソプロピル−４−メチルフェニル基、テトラデシル基、２，６−ジブチルフェニル基、１−アントラセニル基、ペンタデシル基、２，６−ジ−t−ブチル−４−メチルフェニル基、２−フェニル−６−イソプロピルフェニル基、ヘキサデシル基、２−ナフチルフェニル基、２−t−ブチル−６−フェニルフェニル基、ヘプタデシル基、２−t−ブチル−４−メチル−６−フェニルフェニル基、オクタデシル基、２，６−ジフェニルフェニル基、ノナデシル基、トリフェニルメチル基、４−メチル２，６−ジフェニルフェニル基、アラキジル基、２，６−ジパラトリルフェニル基等を挙げることができ、置換シリル基の具体例としては、トリメチルシリル基、ジメチルフェニルシリル基、トリイソプロピルシリル基、ジメチルメトキシシリル基、ジメチル−ｔ−ブチルシリル基、ジフェニルメチルシリル基、トリフェニルシリル基等を挙げることができる。置換アミド基の具体的な例としては、ジメチルアミド基、ジエチルアミド基、ジイソプロピルアミド基などが挙げられる。置換アルコキシ基の具体的な例としては、メトキシ基、エトキシ基、イソプロポキシ基、t−ブトキシ基、トリメチルシリルメトキシ基などが挙げられる。置換アリーロキシ基の具体的な例としては、フェノキシ基、パラメチルフェノキシ基、パラメトキシフェノキシ基、２，６−ジメチルフェノキシ基、１−ナフトキシ基などが挙げられる。置換シリル基、周期表１５族，１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基の具体例としては、トリメチルシリルメチル基、ジメチルフェニルシリルメチル基、２−ジメチルアミノフェニル基、２−ジエチルアミノフェニル基、２−ジイソプロピルアミノフェニル基、２−ピリジル基、６−メチル−２−ピリジル基、２−ピリジルフェニル基、２−イミダゾリル基、２−シアノフェニル基、２−ジメチルホスフィノフェニル基、２−ジフェニルホスフィノフェニル基、トリフェニルホスホラニリデンメチル基、２−メトキシフェニル基、２−エトキシフェニル基、２−イソプロポキシフェニル基、２−フェノキシフェニル基、２−チオメチルフェニル基、メチルスルホニルメチル基、ｐ−トルエンスルホニルメチル基、トリフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロフェニル基、２−クロロ−１−メチルエチル基等を挙げることができる。一般式（２）中、Ｒ１〜Ｒ３、Ｅ１およびＥ２は一般式（１）と同じである。 R 3 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group, a substituted amide group, a substituted alkoxy group, a substituted aryloxy group, or a substituted silyl group, a group 15 or group 16 atom or a halogen atom in the periodic table It is a C1-C20 hydrocarbon group containing. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, normal propyl group, isopropyl group, allyl group, normal butyl group, isobutyl group, t-butyl group, pentyl group and neopentyl. Group, cyclopentyl group, hexyl group, cyclohexyl group, phenyl group, heptyl group, benzyl group, 2-methylphenyl group, 4-methylphenyl group, octyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group , Nonyl group, cumyl group, 2-isopropylphenyl group, 2,4,6-trimethylphenyl group, 2-ethyl-6-methylphenyl group, decyl group, naphthyl group, adamantyl group, 2-t-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-isopropylphenyl group, undecyl group, 2-ethyl-6-isopropyl Pyr group, 2,6-diethyl-4methylphenyl group, dodecyl group, 2,6-diisopropylphenyl group, 2-biphenyl group, 2-cyclohexylphenyl group, tridecyl group, 2,6-diisopropyl-4-methyl Phenyl group, tetradecyl group, 2,6-dibutylphenyl group, 1-anthracenyl group, pentadecyl group, 2,6-di-t-butyl-4-methylphenyl group, 2-phenyl-6-isopropylphenyl group, hexadecyl group 2-naphthylphenyl group, 2-t-butyl-6-phenylphenyl group, heptadecyl group, 2-t-butyl-4-methyl-6-phenylphenyl group, octadecyl group, 2,6-diphenylphenyl group, nonadecyl Group, triphenylmethyl group, 4-methyl 2,6-diphenylphenyl group, arachidyl group, 2,6-diparato Specific examples of the substituted silyl group include trimethylsilyl group, dimethylphenylsilyl group, triisopropylsilyl group, dimethylmethoxysilyl group, dimethyl-t-butylsilyl group, diphenylmethylsilyl group, and triphenyl. A silyl group etc. can be mentioned. Specific examples of the substituted amide group include a dimethylamide group, a diethylamide group, and a diisopropylamide group. Specific examples of the substituted alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, and a trimethylsilylmethoxy group. Specific examples of the substituted aryloxy group include a phenoxy group, a paramethylphenoxy group, a paramethoxyphenoxy group, a 2,6-dimethylphenoxy group, and a 1-naphthoxy group. Specific examples of the substituted silyl group, the group 15 to 16 of the periodic table, or the hydrocarbon group having 1 to 20 carbon atoms including a halogen atom include a trimethylsilylmethyl group, a dimethylphenylsilylmethyl group, a 2-dimethylaminophenyl group, 2-diethylaminophenyl group, 2-diisopropylaminophenyl group, 2-pyridyl group, 6-methyl-2-pyridyl group, 2-pyridylphenyl group, 2-imidazolyl group, 2-cyanophenyl group, 2-dimethylphosphinophenyl Group, 2-diphenylphosphinophenyl group, triphenylphosphoranylidenemethyl group, 2-methoxyphenyl group, 2-ethoxyphenyl group, 2-isopropoxyphenyl group, 2-phenoxyphenyl group, 2-thiomethylphenyl group, Methylsulfonylmethyl group, p-toluenesulfonylmethyl , It may be mentioned a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluorophenyl group, a 2-chloro-1-methylethyl group and the like. In general formula (2), R 1 to R 3 , E 1 and E 2 are the same as in general formula (1).
本発明のノルボルネン誘導体の開環重合体は一般式（３）又は（４）で表されるノルボルネン誘導体を、開環メタセシス重合触媒の存在下で開環メタセシス重合することにより製造することができる。 The ring-opening polymer of the norbornene derivative of the present invention can be produced by subjecting the norbornene derivative represented by the general formula (3) or (4) to ring-opening metathesis polymerization in the presence of a ring-opening metathesis polymerization catalyst.
一般式（３）、（４）中、Ｒ１〜Ｒ３、Ｅ１およびＥ２は一般式（１）と同じである。 In general formulas (3) and (4), R 1 to R 3 , E 1 and E 2 are the same as in general formula (1).
一般式（３）で表されるノルボルネン誘導体は、一般式（５） The norbornene derivative represented by the general formula (3) has the general formula (5)
で表されるノルボルナジエン誘導体と一般式（６）
Ｎ≡Ｃ−Ｃ（Ｏ）ＯＲ３ （６）
（一般式（６）中、Ｒ３は一般式（１）と同じである）
で表されるシアノギ酸エステルを遷移金属化合物存在下において反応させることにより製造することができる（式Ａ−１）。
A norbornadiene derivative represented by the general formula (6)
N≡C—C (O) OR 3 (6)
(In general formula (6), R 3 is the same as in general formula (1))
In the presence of a transition metal compound (formula A-1).
一般式（５）中のＲ１、Ｒ２は、一般式（１）と同じである。式Ａ−１中のＲ１〜Ｒ３、Ｅ１およびＥ２は一般式（１）と同じである。一般式（５）で表されるノルボルナジエン誘導体の具体例としては、２，５−ノルボルナジエン、２−メチル−２，５−ノルボルナジエン、２，３−ジメチル−２，５−ノルボルナジエン、２−エチル−２，５−ノルボルナジエン、２−プロピル−２，５−ノルボルナジエン、２−プロピル−２，５−ノルボルナジエン、２−t−ブトキシ−２，５−ノルボルナジエンなどを挙げることができる。 R 1 and R 2 in the general formula (5) are the same as those in the general formula (1). R 1 to R 3 , E 1 and E 2 in Formula A-1 are the same as those in General Formula (1). Specific examples of the norbornadiene derivative represented by the general formula (5) include 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2,3-dimethyl-2,5-norbornadiene, 2-ethyl-2. , 5-norbornadiene, 2-propyl-2,5-norbornadiene, 2-propyl-2,5-norbornadiene, 2-t-butoxy-2,5-norbornadiene, and the like.
一般式（６）で表されるシアノギ酸エステルの具体例としては、シアノギ酸メチル、シアノギ酸エチル、シアノギ酸ビニル、シアノギ酸ノルマルプロピル、シアノギ酸イソプロピル、シアノギ酸アリル、シアノギ酸ノルマルブチル、シアノギ酸イソブチル、シアノギ酸−t−ブチル、シアノギ酸ペンチル、シアノギ酸ネオペンチル、シアノギ酸シクロペンチル、シアノギ酸ヘキシル、シアノギ酸シクロへキシル、シアノギ酸フェニル、シアノギ酸ヘプチル、シアノギ酸ベンジル、シアノギ酸トリメチルシリルメチル、シアノギ酸ジメチルフェニルシリルメチル等を挙げることができる。 Specific examples of the cyanoformate represented by the general formula (6) include methyl cyanoformate, ethyl cyanoformate, vinyl cyanoformate, normal cyanoformate, isopropyl cyanoformate, allyl cyanoformate, normal butyl cyanoformate, and cyanoformate. Isobutyl, cyanoformate-t-butyl, pentyl cyanoformate, neopentyl cyanoformate, cyclopentyl cyanoformate, hexyl cyanoformate, cyclohexyl cyanoformate, phenyl cyanoformate, heptyl cyanoformate, benzyl cyanoformate, trimethylsilylmethyl cyanoformate, cyanoformate Examples thereof include dimethylphenylsilylmethyl.
ここで用いられる遷移金属化合物の具体例としては、ビス（１，５−シクロオクタジエン）ニッケル、テトラキス（トリフェニルホスフィン）ニッケル、テトラキス（トリフェニルホスフィン）パラジウム、テトラキス（メチルジフェニルホスフィン）パラジウム、テトラキス（トリエチルホスファイト）パラジウム、ビス（トリシクロヘキシルホスフィン）パラジウム、ビス（１，５−シクロオクタジエン）パラジウム、ビス（ジベンジリデンアセトン）パラジウム、ビス（１，２−ジフェニルホスフィノエタン）パラジウム、ビス（ジベンジリデンアセトン）白金、ビス（１，５−シクロオクタジエン）白金、テトラキス（トリフェニルホスフィン）白金、テトラキス（トリフェニルホスファイト）白金などを挙げることができる。 Specific examples of the transition metal compound used here include bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) palladium, tetrakis (methyldiphenylphosphine) palladium, tetrakis. (Triethylphosphite) palladium, bis (tricyclohexylphosphine) palladium, bis (1,5-cyclooctadiene) palladium, bis (dibenzylideneacetone) palladium, bis (1,2-diphenylphosphinoethane) palladium, bis ( Examples thereof include dibenzylideneacetone) platinum, bis (1,5-cyclooctadiene) platinum, tetrakis (triphenylphosphine) platinum, and tetrakis (triphenylphosphite) platinum.
式（Ａ−１）の反応に用いられる溶媒としては、ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサン、ジブチルエーテルなどのエーテル類、ベンゼン、トルエンなどの芳香族炭化水素類、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素類、シクロヘキサンなどの脂環式炭化水素類、ジクロロメタン、１，２−ジクロロエタンなどのハロゲン化炭化水素類、メタノール、エタノール、２−プロパノールなどのアルコール類、アセトニトリル、ベンゾニトリルなどのニトリル類、Ｎ，Ｎ−ジメチルホルムアミドなどのアミド類などが挙げられるが、好ましくは、ベンゼン、トルエンである。ノルボルナジエン誘導体とシアノギ酸エステルとの反応において、シアノギ酸エステルとノルボルナジエン誘導体との比はモル比で１：１〜１０００：１、好ましくは１：１〜５０：１である。遷移金属化合物とノルボルナジエン誘導体との比はモル比で１：１０００００〜１：１、好ましくは１：１００００〜１：１０である。式（Ａ−１）における反応温度は−７８〜１５０℃、好ましくは０〜１５０℃の範囲であり、反応時間は０．５〜１００時間、好ましくは１〜５０時間であるがこれらに限定されるものではない。 Examples of the solvent used in the reaction of the formula (A-1) include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dibutyl ether, aromatic hydrocarbons such as benzene and toluene, pentane, hexane, heptane, and the like. Aliphatic hydrocarbons such as cyclohexane, cycloaliphatic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, alcohols such as methanol, ethanol and 2-propanol, acetonitrile, benzonitrile, etc. Nitriles, amides such as N, N-dimethylformamide and the like can be mentioned, and benzene and toluene are preferable. In the reaction between the norbornadiene derivative and the cyanoformate, the molar ratio of the cyanoformate and the norbornadiene derivative is 1: 1 to 1000: 1, preferably 1: 1 to 50: 1. The ratio of the transition metal compound to the norbornadiene derivative is 1: 100000 to 1: 1, preferably 1: 10000 to 1:10 in molar ratio. The reaction temperature in the formula (A-1) is in the range of −78 to 150 ° C., preferably 0 to 150 ° C., and the reaction time is 0.5 to 100 hours, preferably 1 to 50 hours, but is not limited thereto. It is not something.
一般式（３）で表されるノルボルネン誘導体の具体的な例としては、５−ｅｘｏ−シアノ−６−ｅｘｏ−メトキシカルボニル−２−ノルボルネン、５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネン、５−ｅｘｏ−シアノ−６−ｅｘｏ−ｎ−プロポキシカルボニル−２−ノルボルネン、５−ｅｘｏ−シアノ−６−ｅｘｏ−イソプロポキシカルボニル−２−ノルボルネン、５−ｅｘｏ−シアノ−６−ｅｘｏ−ｎ−ブトキシカルボニル−２−ノルボルネン、５−ｅｘｏ−シアノ−６−ｅｘｏ−ベンジルオキシカルボニル−２−ノルボルネン、５−ｅｘｏ−シアノ−６−ｅｘｏ−ｎ−フェノキシカルボニル−２−ノルボルネンなどを挙げることができる。 Specific examples of the norbornene derivative represented by the general formula (3) include 5-exo-cyano-6-exo-methoxycarbonyl-2-norbornene and 5-exo-cyano-6-exo-ethoxycarbonyl-2. -Norbornene, 5-exo-cyano-6-exo-n-propoxycarbonyl-2-norbornene, 5-exo-cyano-6-exo-isopropoxycarbonyl-2-norbornene, 5-exo-cyano-6-exo- Examples include n-butoxycarbonyl-2-norbornene, 5-exo-cyano-6-exo-benzyloxycarbonyl-2-norbornene, 5-exo-cyano-6-exo-n-phenoxycarbonyl-2-norbornene. it can.
一般式（４）で表されるノルボルネン誘導体は一般式（３）で表されるノルボルネン誘導体とシクロペンタジエンとのＤｉｅｌｓ−Ａｌｄｅｒ反応により製造することができる（式Ａ−２）。 The norbornene derivative represented by the general formula (4) can be produced by a Diels-Alder reaction between the norbornene derivative represented by the general formula (3) and cyclopentadiene (formula A-2).
一般式（４）で表されるノルボルネン誘導体の具体的例としては、８−シアノ−９−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、８−シアノ−９−エトキシカルボニル−テトラシクロ〔４．４．０．１２，５．１７．１０〕−３−ドデセン、８−シアノ−９−ｎ−プロポキシカルボニル−テトラシクロ〔４．４．０．１２，５．１７．１０〕−３−ドデセン、８−シアノ−９−イソプロポキシカルボニル−テトラシクロ〔４．４．０．１２，５．１７．１０〕−３−ドデセン、８−シアノ−９−ｎ−ブトキシカルボニル−テトラシクロ〔４．４．０．１２，５．１７．１０〕−３−ドデセン、８−シアノ−９−フェノキシカルボニル−テトラシクロ〔４．４．０．１２，５．１７．１０〕−３−ドデセンなどを挙げることができる。 Specific examples of the norbornene derivative represented by the general formula (4) include 8-cyano-9-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7.10 ] -3-dodecene, 8-cyano-9-ethoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7.10 ] -3-dodecene, 8-cyano-9-n-propoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7.10 ] -3-dodecene, 8-cyano-9-isopropoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7.10 ] -3-dodecene, 8-cyano-9-n-butoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7.10 ] -3-dodecene, 8-cyano-9-phenoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7.10 ] -3-dodecene.
開環メタセシス重合触媒は、一般式（３）又は（４）で表されるノルボルネン誘導体を開環メタセシス重合可能なものであればよく、特に限定されない。 The ring-opening metathesis polymerization catalyst is not particularly limited as long as it is capable of ring-opening metathesis polymerization of the norbornene derivative represented by the general formula (3) or (4).
使用できる開環メタセシス重合触媒としては、遷移金属ハロゲン化物と有機リチウム化合物、有機アルミニウム化合物、有機スズ化合物などの助触媒の組み合わせからなる触媒、遷移金属カルベン錯体触媒などが挙げられる。 Examples of the ring-opening metathesis polymerization catalyst that can be used include a catalyst composed of a combination of a transition metal halide and a promoter such as an organolithium compound, an organoaluminum compound, and an organotin compound, and a transition metal carbene complex catalyst.
遷移金属ハロゲン化物の具体例としては、ＴｉＣｌ４、ＴｉＢｒ４等のチタンハロゲン化物、ＶＣｌ５、Ｖ（Ｏ）Ｃｌ３等のバナジウムハロゲン化物、ＭｏＣｌ３，ＭｏＢｒ３，ＭｏＣｌ５，ＭｏＣｌ２（Ｏ）２等のモリブデンハロゲン化物、ＷＣｌ４、ＷＣｌ５、ＷＣｌ６、ＷＣｌ４（Ｏ）、等のタングステンハロゲン化物等が挙げられる。 Specific examples of transition metal halides include titanium halides such as TiCl 4 and TiBr 4 , vanadium halides such as VCl 5 and V (O) Cl 3 , MoCl 3 , MoBr 3 , MoCl 5 , MoCl 2 (O). And molybdenum halides such as 2 and tungsten halides such as WCl 4 , WCl 5 , WCl 6 , and WCl 4 (O).
有機リチウム化合物の具体例としては、メチルリチウム、ｎ−ブチルリチウム、フェニルリチウムなどを挙げることができる。 Specific examples of the organic lithium compound include methyl lithium, n-butyl lithium, and phenyl lithium.
有機アルミニウム化合物の具体例としては、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、ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、エチルアルミニウムジクロリド、エチルアルミニウムセスキクロリド、メチルアルミノキサン等が挙げられる。有機スズ化合物の具体例としては、テトラメチルスズ、テトラエチルスズ、テトラブチルスズ、ジブチルジクロロスズなどを挙げることができる。 Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminoxane and the like. Specific examples of the organic tin compound include tetramethyltin, tetraethyltin, tetrabutyltin, and dibutyldichlorotin.
遷移金属カルベン錯体としては、モリブデンアルキリデン錯体、タングステンアルキリデン錯体、ルテニウムカルベン錯体、ルテニウムビニリデン錯体などが挙げられる。モリブデンアルキリデン錯体の具体例としては、Ｍｏ（Ｎ−２，６−ｉＰｒ２Ｃ６Ｈ３）（ＣＨ（ｔＢｕ）（ＯｔＢｕ）２、Ｍｏ（Ｎ−２，６−ｉＰｒ２Ｃ６Ｈ３）（ＣＨ（ｔＢｕ）（ＯＭｅ（ＣＦ３）２）２などを挙げることをできる。タングステンアルキリデン錯体の具体例としては、Ｗ（ＣＰｈ２）（ＣＯ）５、Ｗ（Ｎ−２，６−ｉＰｒ２Ｃ６Ｈ３）（ＣＨ（ｔＢｕ）（ＯｔＢｕ）２、Ｗ（Ｎ−２，６−ｉＰｒ２Ｃ６Ｈ３）（ＣＨ（ｔＢｕ）（ＯＭｅ（ＣＦ３）２）２などを挙げることをできる。ルテニウムカルベン錯体の具体例としては、ベンジリデンビス（トリシクロヘキシルホスフィン）ルテニウムジクロリド、ベンジリデン（１，３−ジメシチルイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、ベンジリデン（１，３−ジメシチル−４，５−ジヒドロイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、ベンジリデン（１，３−ジシクロヘキシルイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、ベンジリデンビス（１，３−ジメシチルイミダゾリジン−２−イリデン）ルテニウムジクロリド、ベンジリデンビス（１，３−ジイソプロピルイミダゾリジン−２−イリデン）ルテニウムジクロリド、ベンジリデンビス（１，３−ジシクロヘキシルイミダゾリジン−２−イリデン）ルテニウムジクロリドなどを挙げることができる。ルテニウムビニリデン錯体の具体例としては、（フェニルビニリデン）ビス（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（イソプロピルビニリデン）ビス（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（ｔｅｒｔ−ブチルビニリデン）ビス（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（ｔｅｒｔ−ブチルビニリデン）ビス（トリフェニルホスフィン）ルテニウムジクロリド、（ジメチルビニリデン）（１，３−ジメシチルイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（フェニルビニリデン）（１，３−ジメシチルイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（フェニルビニリデン）（１，３−ジシクロヘキシルイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド、（フェニルビニリデン）ビス（１，３−ジメシチルイミダゾリジン−２−イリデン）ルテニウムジクロリド、（フェニルビニリデン）ビス（１，３−ジイソプロピルイミダゾリジン−２−イリデン）ルテニウムジクロリド、（フェニルビニリデン）ビス（１，３−ジシクロヘキシルイミダゾリジン−２−イリデン）ルテニウムジクロリドなどを挙げることができる。好ましくは遷移金属アルキリデン錯体であり、より好ましくはルテニウムアルキリデン錯体である。 Examples of transition metal carbene complexes include molybdenum alkylidene complexes, tungsten alkylidene complexes, ruthenium carbene complexes, ruthenium vinylidene complexes, and the like. Specific examples of the molybdenum alkylidene complex include Mo (N-2,6-iPr 2 C 6 H 3 ) (CH (tBu) (OtBu) 2 , Mo (N-2,6-iPr 2 C 6 H 3 ) ( CH (tBu) (OMe (CF 3 ) 2 ) 2 etc. Specific examples of the tungsten alkylidene complex include W (CPh 2 ) (CO) 5 , W (N-2,6-iPr 2 C). 6 H 3 ) (CH (tBu) (OtBu) 2 , W (N-2,6-iPr 2 C 6 H 3 ) (CH (tBu) (OMe (CF 3 ) 2 ) 2 and the like. Specific examples of the ruthenium carbene complex include benzylidene bis (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexyl). Sylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5-dihydroimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dicyclohexylimidazolidin-2-ylidene) (tri Cyclohexylphosphine) ruthenium dichloride, benzylidenebis (1,3-dimesitylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropylimidazolidin-2-ylidene) ruthenium dichloride, benzylidenebis (1,3 -Dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, etc. Specific examples of the ruthenium vinylidene complex include (phenylvinylidene) bis (toluene). (Cyclohexylphosphine) ruthenium dichloride, (isopropylvinylidene) bis (tricyclohexylphosphine) ruthenium dichloride, (tert-butylvinylidene) bis (tricyclohexylphosphine) ruthenium dichloride, (tert-butylvinylidene) bis (triphenylphosphine) ruthenium dichloride, Dimethylvinylidene) (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (phenylvinylidene) (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) Ruthenium dichloride, (phenylvinylidene) (1,3-dicyclohexylimidazolidin-2-ylidene) (tricyclohexylphosphine) Tenium dichloride, (phenylvinylidene) bis (1,3-dimesityrylimidazolidine-2-ylidene) ruthenium dichloride, (phenylvinylidene) bis (1,3-diisopropylimidazolidin-2-ylidene) ruthenium dichloride, (phenyl) Vinylidene) bis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride. A transition metal alkylidene complex is preferable, and a ruthenium alkylidene complex is more preferable.
開環メタセシス重合触媒とノルボルネン誘導体との比はモル比で、１：５〜１：１，０００，０００、好ましくは、１：１０〜１：５００，０００である。 The ratio of the ring-opening metathesis polymerization catalyst to the norbornene derivative is a molar ratio of 1: 5 to 1: 1,000,000, preferably 1:10 to 1: 500,000.
開環メタセシス重合反応に用いる溶媒としては、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタンシクロヘキサンなどの脂肪族炭化水素、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、１，２−ジクロロエタン、クロロベンゼン、１，２−ジクロロベンゼンなどのハロゲン化炭化水素、ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサンなどのエーテル類、アセトン、エチルメチルケトン、シクロヘキサノンなどのケトン類、酢酸エチル、プロピオン酸エチルなどのエステル類、アセトニトリル、ベンゾニトリルなどの二トリル類、またはそれらの混合物が挙げられる。 Solvents used in the ring-opening metathesis polymerization reaction include aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptanecyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, 1,2-dichloroethane, Halogenated hydrocarbons such as chlorobenzene and 1,2-dichlorobenzene, ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane, ketones such as acetone, ethyl methyl ketone and cyclohexanone, ethyl acetate and ethyl propionate Examples include esters, nitriles such as acetonitrile and benzonitrile, or mixtures thereof.
反応温度は−７８〜２００℃、好ましくは０〜１５０℃の範囲であり、反応時間は０．５〜１００時間、好ましくは１〜５０時間であるがこれらに限定されるものではない。 The reaction temperature is in the range of −78 to 200 ° C., preferably 0 to 150 ° C., and the reaction time is 0.5 to 100 hours, preferably 1 to 50 hours, but is not limited thereto.
以下に、実施例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。反応はすべて不活性ガス雰囲気下で行い、反応に用いた溶媒はすべて予め公知の方法により精製、乾燥または脱酸素を行った。重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）および重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によって測定した。ＧＰＣ装置としてはＪＡＳＣＯ製 ＨＰＬＣシステムを用い、カラムとしては昭和電工製 Ｓｈｏｄｅｘ ＫＦ−８０６Ｌを用い、溶離液としてテトラヒドロフランを用いて測定し、ポリスチレン換算で算出した。化合物の同定は、１Ｈ、１３Ｃ、あるいは３１Ｐ ＮＭＲ（Ｖａｒｉａｎ社製 ＩＮＯＶＡ−６００およびＭｅｒｃｕｒｙ−３００ ＮＭＲ測定装置）を用いて行なった。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. All the reactions were carried out under an inert gas atmosphere, and all the solvents used for the reaction were purified, dried or deoxygenated in advance by a known method. The weight average molecular weight (Mw), the number average molecular weight (Mn) and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) were measured by gel permeation chromatography (GPC). A JSCO HPLC system was used as the GPC apparatus, Shodex KF-806L manufactured by Showa Denko was used as the column, and tetrahydrofuran was used as the eluent, and calculation was performed in terms of polystyrene. The compound was identified using 1 H, 13 C, or 31 P NMR (Varian INOVA-600 and Mercury-300 NMR measuring apparatus).
合成例１ （５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンの合成
テトラキス（トリフェニルホスフィン）パラジウム（０）（１．１６ｇ、１．０ｍｍｏｌ，１０ｍｏｌ％）のトルエン（１００ｍｌ）溶液に、室温でシアノギ酸エチル（０．９８ｍｌ，１０．０ｍｍｏｌ）及びノルボルナジエン（０．９２ｇ、１０．０ｍｍｏｌ）を加えた。１１０℃で２４時間反応させた後、１ｍｏｌ／Ｌ塩酸（５０ｍｌ）を加え反応を停止し、ジエチルエーテル（５０ｍｌ×２）で抽出を行った。無水硫酸マグネシウムにより乾燥した後、溶媒を留去すると淡黄色オイルが得られた。減圧蒸留を行うと５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンが無色オイルとして得られた（収率：６６％）。
１Ｈ ＮＭＲ（δ，ＣＤＣｌ３）６．２４（ｄｄ，１Ｈ，Ｃ＝ＣＨ），６．１５（ｄｄ，１Ｈ，Ｃ＝ＣＨ），４．２４（ｓ，２Ｈ，ＯＣＨ２），３．２６（ｂｒ，１Ｈ），３．２６（ｂｒ，１Ｈ），２．６８（ｄｄ，１Ｈ，ＣＨＣＮ），２．５７（ｄｄ，１Ｈ，ＣＨＣＯＯＥｔ），２．００（ｄ，１Ｈ），１．６６（ｄｔ，１Ｈ），１．３１（ｔ，３Ｈ，ＣＨ３），１３Ｃ ＮＭＲ（δ，ＣＤＣｌ３）１７１．８（ＣＯ），１３８．４（Ｃ＝ＣＨ），１３５．９（Ｃ＝ＣＨ）１２０．２（ＣＮ），６１．６（ＯＣＨ２），４７．６（橋頭位）４７．０（ＣＨＣＯＯＥｔ），４６．５（ＣＨ２），４５．０（橋頭位），３３．１（ＣＨＣＮ），１４．３（ＣＨ３）、
元素分析 計算値（Ｃ１１Ｈ１３ＮＯ２）Ｃ，６９．０９；Ｈ，６．８５；Ｎ，７．３２％，測定値 Ｃ，６９．０７；Ｈ，６．７４；Ｎ，７．１３％
Synthesis Example 1 (Synthesis of 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene) Tetrakis (triphenylphosphine) palladium (0) (1.16 g, 1.0 mmol, 10 mol%) in toluene (100 ml) To the mixture, ethyl cyanoformate (0.98 ml, 10.0 mmol) and norbornadiene (0.92 g, 10.0 mmol) were added at room temperature, followed by reaction at 110 ° C. for 24 hours, and then 1 mol / L hydrochloric acid (50 ml) was added. The reaction was stopped, extraction was performed with diethyl ether (50 ml × 2), and after drying with anhydrous magnesium sulfate, the solvent was distilled off to obtain a pale yellow oil. 6-exo-ethoxycarbonyl-2-norbornene was obtained as a colorless oil (yield: 66%).
1 H NMR (δ, CDCl 3 ) 6.24 (dd, 1H, C═CH), 6.15 (dd, 1H, C═CH), 4.24 (s, 2H, OCH 2 ), 3.26 (Br, 1H), 3.26 (br, 1H), 2.68 (dd, 1H, CHCN), 2.57 (dd, 1H, CHCOOEt), 2.00 (d, 1H), 1.66 ( dt, 1H), 1.31 (t, 3H, CH 3 ), 13 C NMR (δ, CDCl 3 ) 171.8 (CO), 138.4 (C═CH), 135.9 (C═CH) 120.2 (CN), 61.6 (OCH 2 ), 47.6 (bridge head position) 47.0 (CHCOOEt), 46.5 (CH 2 ), 45.0 (bridge head position), 33.1 (CHCN ), 14.3 (CH 3 ),
Analysis Calculated (C 11 H 13 NO 2) C, 69.09; H, 6.85; N, 7.32%, measured C, 69.07; H, 6.74; N, 7.13 %
実施例１ ５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンの開環重合体の製造
５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネン（４６ｍｇ、０．２４ｍｍｏｌ）をジクロロメタン（０．７５ｍｌ）に溶解させた。そこに、ベンジリデン（１，３−ジメシチル−４，５−ジヒドロイミダゾリジン−２−イリデン）（トリシクロヘキシルホスフィン）ルテニウムジクロリド（２．０ｍｇ、２．４μｍｏｌ）のジクロロメタン（０．２５ｍｌ）溶液を加え、室温で５時間反応させた。エチルビニルエーテル（１３μｌ、０．１４ｍｏｌ）を加え、１２時間攪拌し反応を停止した。反応溶液をメタノール（１００ｍｌ）に投入し、ポリマーを析出させ、ろ別、減圧乾燥を行うと収率９７％にて開環重合体が得られた。分子量は、Ｍｎが４６２００、Ｍｗが１００１００、Ｍｗ／Ｍｎが２．１７であった。
Example 1 Preparation of Ring-Opening Polymer of 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene (46 mg, 0.24 mmol) was prepared. Dissolved in dichloromethane (0.75 ml). Thereto was added a solution of benzylidene (1,3-dimesityl-4,5-dihydroimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (2.0 mg, 2.4 μmol) in dichloromethane (0.25 ml), The reaction was allowed to proceed for 5 hours at room temperature. Ethyl vinyl ether (13 μl, 0.14 mol) was added and the reaction was stopped by stirring for 12 hours. The reaction solution was poured into methanol (100 ml) to precipitate a polymer, which was filtered and dried under reduced pressure to obtain a ring-opening polymer with a yield of 97%. The molecular weight was 46200 for Mn, 100100 for Mw, and 2.17 for Mw / Mn.
実施例２ ５−ｅｘｏ−シアノ−６−ｅｘｏ−メトキシカルボニル−２−ノルボルネンの開環重合体の製造
５−ｅｘｏ−シアノ−６−ｅｘｏ−メトキシカルボニル−２−ノルボルネンの合成：シアノギ酸エチルに替えてシアノギ酸メチルを用いた以外は、合成例１と同様の方法で合成した（収率：７６％）。
Example 2 Preparation of a ring-opening polymer of 5-exo-cyano-6-exo-methoxycarbonyl-2-norbornene Synthesis of 5-exo-cyano-6-exo-methoxycarbonyl-2-norbornene: Replacement with ethyl cyanoformate This was synthesized in the same manner as in Synthesis Example 1 except that methyl cyanoformate was used (yield: 76%).
開環重合体の製造：５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンに替えて５−ｅｘｏ−シアノ−６−ｅｘｏ−メトキシカルボニル−２−ノルボルネンを用いた以外は実施例１と同様に反応を実施した。その結果、収率９９％にて開環重合体を得た。分子量は、Ｍｎが３９７００、Ｍｗが６０８００、Ｍｗ／Ｍｎが１．５３であった。 Production of ring-opening polymer: Example 1 except that 5-exo-cyano-6-exo-methoxycarbonyl-2-norbornene was used instead of 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene The reaction was carried out in the same manner as above. As a result, a ring-opening polymer was obtained with a yield of 99%. The molecular weight was 39700 for Mn, 60800 for Mw, and 1.53 for Mw / Mn.
実施例３ ５−ｅｘｏ−シアノ−６−ｅｘｏ−ノルマルプロポキシカルボニル−２−ノルボルネンの開環重合体の製造
５−ｅｘｏ−シアノ−６−ｅｘｏ−ノルマルプロポキシカルボニル−２−ノルボルネンの合成：シアノギ酸エチルに替えてシアノギ酸ノルマルプロピルを用いた以外は、合成例１と同様の方法で合成した（収率：７６％）。
Example 3 Preparation of ring-opening polymer of 5-exo-cyano-6-exo-normal propoxycarbonyl-2-norbornene Synthesis of 5-exo-cyano-6-exo-normal propoxycarbonyl-2-norbornene: ethyl cyanoformate The synthesis was performed in the same manner as in Synthesis Example 1 except that normal propyl formate was used (yield: 76%).
開環重合体の製造：５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンに替えて５−ｅｘｏ−シアノ−６−ｅｘｏ−ノルマルプロポキシカルボニル−２−ノルボルネンを用いた以外は実施例１と同様に反応を実施した。その結果、収率９３％で開環重合体を得た。分子量は、Ｍｎが５７４００、Ｍｗが１１８７００、Ｍｗ／Ｍｎが２．０７であった。 Production of ring-opening polymer: Examples except that 5-exo-cyano-6-exo-normal propoxycarbonyl-2-norbornene was used instead of 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene The reaction was carried out as in 1. As a result, a ring-opening polymer was obtained with a yield of 93%. The molecular weight was 57400 for Mn, 118700 for Mw, and 2.07 for Mw / Mn.
実施例４ ５−ｅｘｏ−シアノ−６−ｅｘｏ−イソプロポキシカルボニル−２−ノルボルネンの開環重合体の製造
５−ｅｘｏ−シアノ−６−ｅｘｏ−イソプロポキシカルボニル−２−ノルボルネンの合成：シアノギ酸エチルに替えてシアノギ酸イソプロピルを用いた以外は、合成例１と同様の方法で合成した（収率：６２％）。
Example 4 Preparation of a ring-opening polymer of 5-exo-cyano-6-exo-isopropoxycarbonyl-2-norbornene Synthesis of 5-exo-cyano-6-exo-isopropoxycarbonyl-2-norbornene: ethyl cyanoformate The synthesis was performed in the same manner as in Synthesis Example 1 except that isopropyl cyanoformate was used in place of (Yield: 62%).
開環重合体の製造：５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンに替えて５−ｅｘｏ−シアノ−６−ｅｘｏ−イソプロポキシカルボニル−２−ノルボルネンを用いた以外は実施例１と同様に反応を実施した。その結果、収率９９％で開環重合体を得た。分子量は、Ｍｎが８１７００、Ｍｗが１３０６００、Ｍｗ／Ｍｎが１．６０であった。 Production of ring-opening polymer: Examples except that 5-exo-cyano-6-exo-isopropoxycarbonyl-2-norbornene was used instead of 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene The reaction was carried out as in 1. As a result, a ring-opening polymer was obtained with a yield of 99%. The molecular weight was 81700 for Mn, 130600 for Mw, and 1.60 for Mw / Mn.
実施例５ ５−ｅｘｏ−シアノ−６−ｅｘｏ−ノルマルブトキシカルボニル−２−ノルボルネンの開環重合体の製造
５−ｅｘｏ−シアノ−６−ｅｘｏ−ノルマルブトキシカルボニル−２−ノルボルネンの合成：シアノギ酸エチルに替えてシアノギ酸ノルマルブチルを用いた以外は、合成例１と同様の方法で合成した（収率：６７％）。
Example 5 Preparation of ring-opening polymer of 5-exo-cyano-6-exo-normal butoxycarbonyl-2-norbornene Synthesis of 5-exo-cyano-6-exo-normal butoxycarbonyl-2-norbornene: ethyl cyanoformate The synthesis was performed in the same manner as in Synthesis Example 1 except that normal butyl cyanate was used (yield: 67%).
開環重合体の製造：５−ｅｘｏ−シアノ−６−ｅｘｏ−エトキシカルボニル−２−ノルボルネンに替えて５−ｅｘｏ−シアノ−６−ｅｘｏ−ノルマルブトキシカルボニル−２−ノルボルネンを用いた以外は実施例１と同様に反応を実施した。その結果、収率９１％で開環重合体を得た。分子量は、Ｍｎが４８４００、Ｍｗが１３４７００、Ｍｗ／Ｍｎが２．７９であった。 Production of ring-opening polymer: Examples except that 5-exo-cyano-6-exo-normal butoxycarbonyl-2-norbornene was used instead of 5-exo-cyano-6-exo-ethoxycarbonyl-2-norbornene The reaction was carried out as in 1. As a result, a ring-opening polymer was obtained with a yield of 91%. The molecular weight was 48400 for Mn, 134700 for Mw, and 2.79 for Mw / Mn.
本発明のノルボルネン誘導体の開環重合体は、耐熱性、透明性などに優れ、耐熱性光学材料として有用である。 The ring-opening polymer of the norbornene derivative of the present invention is excellent in heat resistance and transparency, and is useful as a heat resistant optical material.
Claims (5)
または、一般式（２）
Or general formula (2)
または、一般式（４）
Or general formula (4)
Ｎ≡Ｃ−Ｃ（Ｏ）ＯＲ３ （６）
（Ｒ３は、前記一般式（１）と同じである。）で表されるシアノギ酸エステルとを遷移金属化合物存在下において反応させることで製造した一般式（３）
N≡C—C (O) OR 3 (6)
(R 3 is the same as in the general formula (1).) The general formula (3) produced by reacting a cyanoformate ester represented by the transition metal compound.
または、一般式（４）
Or general formula (4)
Ｎ≡Ｃ−Ｃ（Ｏ）ＯＲ３ （６）
（Ｒ３は、水素原子、炭素数１〜２０の炭化水素基、置換シリル基、置換アミド基、置換アルコキシ基、置換アリーロキシ基、ハロゲン原子、または置換シリル基、周期表第１５族，１６族の原子もしくはハロゲン原子を含む炭素数１〜２０の炭化水素基である。）で表されるシアノギ酸エステルとを遷移金属化合物存在下において反応させることで製造した一般式（３）
N≡C—C (O) OR 3 (6)
(R 3 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group, a substituted amide group, a substituted alkoxy group, a substituted aryloxy group, a halogen atom, or a substituted silyl group, groups 15 and 16 of the periodic table. Or a cyanoformate ester represented by general formula (3) produced by reacting in the presence of a transition metal compound.
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| JPH11193323A (en) * | 1997-05-28 | 1999-07-21 | Mitsui Chem Inc | Production of hydrogenated ring-opening metathesis polymer of cycloolefin |
| JP2003128766A (en) * | 2001-10-29 | 2003-05-08 | Nippon Zeon Co Ltd | Method for producing ring-opened polymer and method for producing hydrogenated ring-opened polymer |
| JP2006321744A (en) * | 2005-05-18 | 2006-11-30 | Tosoh Corp | METHOD FOR PRODUCING SUBSTITUTED beta-CYANO ESTER |
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| JPH11193323A (en) * | 1997-05-28 | 1999-07-21 | Mitsui Chem Inc | Production of hydrogenated ring-opening metathesis polymer of cycloolefin |
| JP2003128766A (en) * | 2001-10-29 | 2003-05-08 | Nippon Zeon Co Ltd | Method for producing ring-opened polymer and method for producing hydrogenated ring-opened polymer |
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