JP2006028532A - Ring-opening metathesis polymerization method of cyclic olefin - Google Patents
Ring-opening metathesis polymerization method of cyclic olefin Download PDFInfo
- Publication number
- JP2006028532A JP2006028532A JP2005296676A JP2005296676A JP2006028532A JP 2006028532 A JP2006028532 A JP 2006028532A JP 2005296676 A JP2005296676 A JP 2005296676A JP 2005296676 A JP2005296676 A JP 2005296676A JP 2006028532 A JP2006028532 A JP 2006028532A
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- JP
- Japan
- Prior art keywords
- cyano
- ring
- opening metathesis
- metathesis polymerization
- dodecene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- -1 cyclic olefin Chemical class 0.000 title claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 19
- 125000001118 alkylidene group Chemical group 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 7
- 238000005649 metathesis reaction Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 5
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical group C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005865 alkene metathesis reaction Methods 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical class C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical class C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LAZHUUGOLCHESB-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(C)C(C)C1C=C2 LAZHUUGOLCHESB-UHFFFAOYSA-N 0.000 description 1
- GZMMEGIIXYXLHG-UHFFFAOYSA-N 2-(3-cyano-2-bicyclo[2.2.1]hept-5-enyl)acetic acid Chemical compound C1C2C=CC1C(CC(=O)O)C2C#N GZMMEGIIXYXLHG-UHFFFAOYSA-N 0.000 description 1
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- ZVIOPXFLYBAWKR-UHFFFAOYSA-N 2-(cyclohepten-1-yl)cycloheptene-1-carbonitrile Chemical class C1CCCCC(C#N)=C1C1=CCCCCC1 ZVIOPXFLYBAWKR-UHFFFAOYSA-N 0.000 description 1
- CBLSMVAUCYZVSK-UHFFFAOYSA-N 2-cyanobicyclo[2.2.1]hept-5-ene-3-carboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C#N CBLSMVAUCYZVSK-UHFFFAOYSA-N 0.000 description 1
- RSCIDCVEEKEQCR-UHFFFAOYSA-N 2-methylbicyclo[2.2.1]hept-5-ene-3-carbonitrile Chemical compound C1C2C=CC1C(C)C2C#N RSCIDCVEEKEQCR-UHFFFAOYSA-N 0.000 description 1
- 125000004924 2-naphthylethyl group Chemical group C1=C(C=CC2=CC=CC=C12)CC* 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- AKQHUJRZKBYZLC-UHFFFAOYSA-N tri(propan-2-yl)-prop-2-enylsilane Chemical compound CC(C)[Si](C(C)C)(C(C)C)CC=C AKQHUJRZKBYZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- SVGQCVJXVAMCPM-UHFFFAOYSA-N triethyl(prop-2-enyl)silane Chemical compound CC[Si](CC)(CC)CC=C SVGQCVJXVAMCPM-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、遷移金属アルキリデン錯体からなる開環メタセシス重合触媒を用いて特定の環状オレフィンをオレフィンまたはジエンを共存させることによって高い触媒効率で、かつ、広い分子量分布の共重合体を製造する開環メタセシス重合方法に関するものである。 The present invention relates to a ring-opening process for producing a copolymer having a high catalytic efficiency and a wide molecular weight distribution by using a ring-opening metathesis polymerization catalyst composed of a transition metal alkylidene complex to allow a specific cyclic olefin to coexist with an olefin or a diene. The present invention relates to a metathesis polymerization method.
環状オレフィンを開環メタセシス重合する触媒は Olefin Metathesis ( Kenneth J. Ivin ; 1983 Academic Press, London )(非特許文献1)に記載されている塩化タングステン、酸化塩化タングステン、塩化モリブデン、塩化チタンまたは塩化バナジウム等の周期表4〜8族の遷移金属の化合物と有機アルミニウムや有機スズ等のようなルイス酸等の助(または共)触媒の組合せからなる触媒系などが知られている。一方、これら従来のメタセシス触媒系とは異なり、環状オレフィンを上述のルイス酸を必要せずに開環メタセシス重合するタングステンまたはモリブデンのアルキリデン錯体触媒についてRichard R. Schrockら( Acc. Chem. Res. 1990, 23(5), 158 : Organometallics 1990, 9, 2262 ; J. Am. Chem Soc., 1990, 112,3875 )(非特許文献2、3)が報告している。これらの錯体触媒は従来のメタセシス触媒系では困難であった極性官能基を有する環状オレフィンの重合を可能にし、リビング反応でブロック共重合体の合成も可能にした。しかしながら、リビング反応である為、1分子のポリマーを得るためには、1分子の錯体を必要とし、触媒コストの観点から経済性が非常に低いという問題を有している。さらに、リビング反応で重合したポリマーは分子量分布が単分散(Mw/Mn=1)であるために分子量分布が広いポリマーに比べて高せん断応力下での粘度が高いなどの成形加工性が不良であるという問題がある。 Catalysts for ring-opening metathesis polymerization of cyclic olefins are tungsten chloride, tungsten oxide chloride, molybdenum chloride, titanium chloride or vanadium chloride described in Olefin Metathesis (Kenneth J. Ivin; 1983 Academic Press, London) (non-patent document 1). A catalyst system composed of a combination of a transition metal compound of Group 4 to 8 of the periodic table and the like, and an auxiliary (or co) catalyst such as Lewis acid such as organoaluminum or organotin is known. On the other hand, unlike these conventional metathesis catalyst systems, Richard R. Schrock et al. (Acc. Chem. Res. 1990) describe tungsten or molybdenum alkylidene complex catalysts for ring-opening metathesis polymerization of cyclic olefins without the need for the aforementioned Lewis acids. , 23 (5), 158: Organometallics 1990, 9, 2262; J. Am. Chem Soc., 1990, 112, 3875) (Non-Patent Documents 2 and 3). These complex catalysts made it possible to polymerize cyclic olefins having polar functional groups, which was difficult with conventional metathesis catalyst systems, and also made it possible to synthesize block copolymers by living reactions. However, since it is a living reaction, in order to obtain a polymer of one molecule, a complex of one molecule is required, and there is a problem that economic efficiency is very low from the viewpoint of catalyst cost. Furthermore, the polymer polymerized by the living reaction has a monodisperse molecular weight distribution (Mw / Mn = 1), so that it has poor molding processability such as a higher viscosity under high shear stress than a polymer with a wide molecular weight distribution. There is a problem that there is.
一方、四塩化チタン、五塩化モリブデン、六塩化タングステン等の金属塩化物とアルキルアルミ等の助触媒とからなる従来のメタセシス触媒系での開環メタセシス重合において、得られるポリマーの分子量をコントロールするために、重合反応系にオレフィン類を添加する方法が既に知られている(特開平3−220230、特開平3−121122、特開平5−132546、特開平5−105743)(特許文献1〜4)。 On the other hand, to control the molecular weight of the resulting polymer in ring-opening metathesis polymerization in a conventional metathesis catalyst system comprising a metal chloride such as titanium tetrachloride, molybdenum pentachloride, tungsten hexachloride and a cocatalyst such as alkylaluminum. In addition, methods for adding olefins to the polymerization reaction system are already known (JP-A-3-220230, JP-A-3-121122, JP-A-5-132546, JP-A-5-105743) (Patent Documents 1 to 4). .
これに対してアルキリデン錯体触媒系については、Macromolecules 1990, 23,3534(非特許文献4)に記載されているように、モリブデンのアルキリデン錯体を用いるノルボルネンの開環メタセシス重合に対してスチレンが非常に良い連鎖移動を起こすことが知られている。一方、1,3−ペンタジエンも連鎖移動性を有するが分子量分布から考察して、その効果は低く、さらに1−ペンテンのようなオレフィンは連鎖移動効果が見られないことが示されており、これは、ノルボルネンに比べてα−オレフィンの反応性が乏しいことが原因であると考えられる。
アルキリデン錯体触媒系は極性基を有する環状オレフィンを重合することが可能な触媒系であるが、その触媒効率は悪く、得られるポリマーの成形性が不良であるという問題があり、経済性に優れた高い触媒効率で成形性が良好なポリマーを製造することが望まれる。 The alkylidene complex catalyst system is a catalyst system capable of polymerizing a cyclic olefin having a polar group, but its catalytic efficiency is poor, and there is a problem that the resulting polymer has poor moldability and is excellent in economic efficiency. It is desired to produce a polymer with high catalyst efficiency and good moldability.
本発明の目的は開環メタセシス触媒を用い、環状オレフィンをメタセシス重合して高い触媒効率で広い分子量分布の共重合体を製造することができるメタセシス重合方法を提供することにある。 An object of the present invention is to provide a metathesis polymerization method capable of producing a copolymer having a wide molecular weight distribution with high catalyst efficiency by metathesis polymerization of a cyclic olefin using a ring-opening metathesis catalyst.
本発明のいま一つの目的は製品中の触媒残渣の低減を図ることができるメタセシス重合方法を提供することにある。 Another object of the present invention is to provide a metathesis polymerization method capable of reducing catalyst residues in a product.
本発明者らは、上記課題を解決すべく鋭意検討し本発明を完成した。 The present inventors have intensively studied to solve the above problems and have completed the present invention.
即ち本発明は、周期表第4〜8族の遷移金属アルキリデン錯体からなる開環メタセシス重合触媒を用いて、一般式〔1〕 That is, the present invention uses a ring-opening metathesis polymerization catalyst comprising a transition metal alkylidene complex of Groups 4 to 8 of the periodic table, and has the general formula [1]
(式中R1〜R4はそれぞれ同一であっても異なっていてもよく、水素、アルキル、アリール、アラルキル、アルコキシ、ハロゲン、またはハロゲン化アルキルから選ばれ、xは1〜3の整数を表す。)と一般式〔2〕
(Wherein R 1 to R 4 may be the same or different and are selected from hydrogen, alkyl, aryl, aralkyl, alkoxy, halogen, or alkyl halide, and x represents an integer of 1 to 3) And general formula [2]
(式中R5〜R8のうち少なくとも1つはニトリル、カルボキシル、またはアルコキシカルボニルから選ばれ、その他は水素、アルキル、アリール、アラルキル、アルコキシ、ハロゲン、またはハロゲン化アルキルから選ばれ、xは1〜3の整数を表す。)で表される環状オレフィンをオレフィンまたはジエン共存下で共重合することを特徴とする開環メタセシス重合方法である。
Wherein at least one of R 5 to R 8 is selected from nitrile, carboxyl, or alkoxycarbonyl, the other is selected from hydrogen, alkyl, aryl, aralkyl, alkoxy, halogen, or alkyl halide, and x is 1 The ring-opening metathesis polymerization method is characterized by copolymerizing the cyclic olefin represented by -3 in the presence of an olefin or a diene.
本発明によれば、遷移金属アルキリデン錯体からなる開環メタセシス重合触蝶を用いて環状オレフィンをメタセシス重合して高い触媒効率で、かつ、高せん断応力下での成形加工性を改善する広い分子量分布の共重合体を製造することができ、同時に製品中の触媒残渣の低減を図ることができる。 According to the present invention, a ring-opening metathesis polymerization catalyst comprising a transition metal alkylidene complex is used to metathesis-polymerize cyclic olefins to achieve high catalytic efficiency and a wide molecular weight distribution that improves molding processability under high shear stress. Can be produced, and at the same time, the catalyst residue in the product can be reduced.
本発明において周期表第4〜8族の遷移金属アルキリデン錯体の遷移金属としてはチタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、テクネチウム、レニウム、鉄、ルテニウム、オスミウムである。 In the present invention, transition metals of transition metal alkylidene complexes of Groups 4 to 8 of the periodic table are titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium. is there.
また、遷移金属アルキリデン錯体としては、一般式〔3〕で示されるような遷移金属錯体である。 The transition metal alkylidene complex is a transition metal complex represented by the general formula [3].
(Mは周期表第4〜8族から選ばれる遷移金属、CはMと二重結合で結合する炭素、R9、R10は水素、アルキル、アリール、アルケニル、アルコキシ、アルキルシリルを表し、X、Yは、ハロゲン、アルコキシ、アリールオキシ、アルキルアミド、アリールアミド、アルキルシリルを表し、QはMと窒素が二重結合で結合したイミドからなる配位子またはMと炭素が三重結合で結合したアルキリデンからなる配位子であり、Zは、トリアルキルホスフィン、トリアリールホスフィンなどのホスフィン類、エーテル類またはアミン類である。h、i、j、kは0または1〜2の整数である。)
一般式〔3〕の遷移金属アルキリデン錯体として、例えば、遷移金属をMとして表すと、M(N−2,6−C6H3−i−Pr2)(CH−t−Bu)(O−t−Bu)2、M(N−2,6−C6H3−i−Pr2)(CHCMe2Ph)(OCMe(CF3)2)2、M(N−2,6−C6H3Me2)(CHCHCMePh)(O−t−Bu)2(PMe3)、M(N−2,6−C6H3Me2)(CHCHCMePh)(OCMe2CF3)2(PMe3)、M(N−2,6−C6H3Me2)(CHCHCPh2)(OCMe(CF3)2)2(thf)、M(N−2,6−C6H3−i−Pr2)(CHCHCMePh)(OPh)2(PMe3)、MCl2(P(C6H5)3)2(CHCHC(C6H5)2)、MCl2(P(C6H11)3)2(CHCHC(C6H5)2)、M(O−t−Bu)2(P(C6H5)3)2(CHCHC(C6H5)2)、M[C(Me)C(Me)CHMe3](O−2,6−C6H3−i−Pr2)3Py、M[C(Ph)C(Ph)CHMe3](O−2,6−C6H3−i−Pr2)3Py、M(C−t−Bu)(CH−t−Bu)(O−2,6−C6H3−i−Pr2)2、M(C−t−Bu)(CH−t−Bu)(OCMe(CF3)2)2(式中のi−Prはイソプロピル、t−Buはtert−ブチル、Meはメチル、Phはフェニル、thfはテトラヒドロフラン、Pyはピリジンを示す。)等が挙げられる。また、これらの開環メタセシス触媒は単独または複数併用のどちらでも使用可能である。
(M is a transition metal selected from Groups 4 to 8 of the periodic table, C is carbon bonded to M by a double bond, R 9 and R 10 are hydrogen, alkyl, aryl, alkenyl, alkoxy, alkylsilyl, X , Y represents halogen, alkoxy, aryloxy, alkylamide, arylamide, alkylsilyl, Q is a ligand composed of an imide in which M and nitrogen are bonded by a double bond, or M and carbon are bonded by a triple bond. Z is a phosphines such as trialkylphosphine and triarylphosphine, ethers or amines, and h, i, j and k are 0 or an integer of 1 to 2. )
As the transition metal alkylidene complexes of the general formula [3], for example, to represent the transition metal as M, M (N-2,6- C 6 H 3 -i-Pr 2) (CH-t-Bu) (O- t-Bu) 2, M ( N-2,6-C 6 H 3 -i-Pr 2) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, M (N-2,6-C 6 H 3 Me 2 ) (CHCHCMePh) (Ot-Bu) 2 (PMe 3 ), M (N-2,6-C 6 H 3 Me 2 ) (CHCHCMePh) (OCMe 2 CF 3 ) 2 (PMe 3 ), M (N-2,6-C 6 H 3 Me 2) (CHCHCPh 2) (OCMe (CF 3) 2) 2 (thf), M (N-2,6-C 6 H 3 -i-Pr 2) (CHCHCMePh) (OPh) 2 ( PMe 3), MCl 2 (P (C 6 H 5) 3) 2 (CHCHC (C 6 H 5) 2), MCl 2 (P C 6 H 11) 3) 2 (CHCHC (C 6 H 5) 2), M (O-t-Bu) 2 (P (C 6 H 5) 3) 2 (CHCHC (C 6 H 5) 2), M [C (Me) C ( Me) CHMe 3] (O-2,6-C 6 H 3 -i-Pr 2) 3 Py, M [C (Ph) C (Ph) CHMe 3] (O-2 , 6-C 6 H 3 -i -Pr 2) 3 Py, M (C-t-Bu) (CH-t-Bu) (O-2,6-C 6 H 3 -i-Pr 2) 2, M (Ct-Bu) (CH-t-Bu) (OCMe (CF 3 ) 2 ) 2 (wherein i-Pr is isopropyl, t-Bu is tert-butyl, Me is methyl, Ph is phenyl, thf is tetrahydrofuran, Py is pyridine, and the like. These ring-opening metathesis catalysts can be used either alone or in combination.
本発明において用いられる一般式〔1〕及び一般式〔2〕の環状オレフィンとしてはxが0であるビシクロヘプトエンの誘導体、xが1であるテトラシクロドデセンの誘導体、xが2であるヘキサシクロヘプタデセンの誘導体、xが3であるオクタシクロドコセンの誘導体である。また、一般式〔1〕のR1〜R4はそれぞれ同一であっても異なっていてもよく、水素、アルキル、アリール、アラルキル、アルコキシ、ハロゲン、またはハロゲン化アルキルから選ばれる。さらに、一般式〔2〕のR5〜R8は、それらの少なくとも1つはニトリル、カルボキシル、またはアルコキシカルボニルから選ばれ、その他は水素、アルキル、アリール、アラルキル、アルコキシ、ハロゲン、またはハロゲン化アルキルから選ばる。ここで、R1〜R8のアルキルは炭素数1〜20のアルキルであり、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ターシャルブチルまたはシクロヘキシル等が挙げられ、アリールは炭素数6〜20アリールであり、例えば、フェニルまたはナフチル等が挙げられ、アラルキルは炭素数7〜20のアラルキルであり、例えば、ベンジル、フェネチル、フェニルイソプロピル、2−ナフチルメチル、2−ナフチルエチル、2−ナフチルイソプロピル等が挙げられ、アルコキシは炭素数1から20のアルコキシであり、例えば、メトキシ、エトキシ、メントキシ等が挙げられる。また、ハロゲンとしては塩素、ヨウ素、臭素、フッ素であり、ハロゲン化アルキルは炭素数1〜20のハロゲン化アルキルであり、例えば、フルオロメチル、クロロメチル、ブロモメチル、ジフルオロメチル、ジクロロメチル、ジブロモメチル、トリフルオロメチル、トリクロロメチル、トリブロモメチル等が挙げられる。また、R5〜R8のニトリル、カルボキシル、アルコキシカルボニルのうちアルコキシカルボニルは炭素数1〜20のアルコキシカルボニルであり、例えば、メトキシカルボニル、エトキシカルボニル、メントキシカルボニル等が挙げられる。 The cyclic olefins of the general formulas [1] and [2] used in the present invention include a bicycloheptene derivative in which x is 0, a tetracyclododecene derivative in which x is 1, and a hexa in which x is 2. A derivative of cycloheptadecene, a derivative of octacyclodocosene in which x is 3. Further, R 1 to R 4 in the general formula [1] may be the same or different and are selected from hydrogen, alkyl, aryl, aralkyl, alkoxy, halogen, or alkyl halide. Furthermore, at least one of R 5 to R 8 in the general formula [2] is selected from nitrile, carboxyl, or alkoxycarbonyl, and the others are hydrogen, alkyl, aryl, aralkyl, alkoxy, halogen, or alkyl halide. Choose from. Here, the alkyl of R 1 to R 8 is an alkyl having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, cyclohexyl, etc., and aryl has 6 to 20 carbon atoms. Aryl, for example, phenyl or naphthyl, and aralkyl is an aralkyl having 7 to 20 carbon atoms, such as benzyl, phenethyl, phenylisopropyl, 2-naphthylmethyl, 2-naphthylethyl, 2-naphthylisopropyl, etc. Alkoxy is an alkoxy having 1 to 20 carbon atoms, and examples thereof include methoxy, ethoxy, and menthoxy. The halogen is chlorine, iodine, bromine or fluorine, and the halogenated alkyl is a halogenated alkyl having 1 to 20 carbon atoms. For example, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, Examples thereof include trifluoromethyl, trichloromethyl, tribromomethyl and the like. Further, the nitrile R 5 to R 8, a carboxyl, alkoxycarbonyl of alkoxycarbonyl is alkoxycarbonyl having 1 to 20 carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl, menthoxy carbonyl, and the like.
一般式〔1〕及び〔2〕の具体例としては、5−シアノビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−5−メチルビシクロ[2.2.1]ヘプト−2−エン、5−ジシアノビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−メチルビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−メトキシビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−カルボキシメチルビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−カルボキシビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−シアノビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−トリフルオロメチルビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−フルオロビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−ジフルオロビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−フェニルビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−ベンジルビシクロ[2.2.1]ヘプト−2−エン、5−シアノ−6−シクロヘキシルビシクロ[2.2.1]ヘプト−2−エン等の、シアノビシクロヘプトエン類、8−シアノテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−8−メチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−ジシアノテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−メチルテトラシクロ[4.4.0.1.12.5.17.10]−3ドデセン、8−シアノ−9−メトキシテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−カルボキシメチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−カルボキシテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−シアノテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−トリフルオロメチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−フルオロテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−ジフルオロテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−フェニルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−ベンジルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−シアノ−9−シクロヘキシルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン等のシアノテトラシクロドデセン類、11−シアノヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−11−メチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−ジシアノヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−メチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−メトキシヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−カルボキシメチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−カルボキシヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−シアノヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−トリフルオロメチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−フルオロヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−ジフルオロヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−フェニルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−ベンジルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−シアノ−12−シクロヘキシルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン等のシアノヘキサシクロヘプタデセン類、14−シアノオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−14−メチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−ジシアノオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]‐5−ドコセン、14−シアノ−15−メチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15−メトキシオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15−カルボキシメチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15−カルボキシオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15.シアノオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15−トリフルオロメチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15−フルオロオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノー15−ジフルオロオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノー15−フェニルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5.ドコセン、14−シアノ−15−ベンジルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−シアノ−15−シクロヘキシルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン等のシアノオクタシクロドコセン類を挙げることができる。 Specific examples of the general formulas [1] and [2] include 5-cyanobicyclo [2.2.1] hept-2-ene and 5-cyano-5-methylbicyclo [2.2.1] hept-2. -Ene, 5-dicyanobicyclo [2.2.1] hept-2-ene, 5-cyano-6-methylbicyclo [2.2.1] hept-2-ene, 5-cyano-6-methoxybicyclo [ 2.2.1] Hept-2-ene, 5-cyano-6-carboxymethylbicyclo [2.2.1] hept-2-ene, 5-cyano-6-carboxybicyclo [2.2.1] hept 2-ene, 5-cyano-6-cyanobicyclo [2.2.1] hept-2-ene, 5-cyano-6-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5 -Cyano-6-fluorobicyclo [2.2.1] hept-2-ene 5-cyano-6-difluorobicyclo [2.2.1] hept-2-ene, 5-cyano-6-phenylbicyclo [2.2.1] hept-2-ene, 5-cyano-6-benzylbicyclo Cyanobicycloheptenes such as [2.2.1] hept-2-ene, 5-cyano-6-cyclohexylbicyclo [2.2.1] hept-2-ene, and 8-cyanotetracyclo [4. 4.0.1.1 2.5. 1 7.10 ] -3-dodecene, 8-cyano-8-methyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-dicyanotetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-methyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3dodecene, 8-cyano-9-methoxytetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-carboxymethyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-carboxytetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-cyanotetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-trifluoromethyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-fluorotetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-difluorotetracyclo [4.4.0.1.1.1 2.5 . 1 7.10] -3-dodecene, 8-cyano-9-phenyl-tetracyclo [4.4.0.1.1 2.5. 1 7.10 ] -3-dodecene, 8-cyano-9-benzyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyano-9-cyclohexyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10] -3-cyano-tetracyclododecene such as dodecene, 11 cyanohexadecanoic cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-11-methyl-hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-dicyano hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-methyl-hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-methoxy-hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-carboxymethyl hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-carboxymethyl hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-cyanohexadecanoic cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-trifluoromethyl hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-fluoro-hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-difluoro-hex cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-phenyl-hex cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-benzyl hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-cyano-12-cyclohexyl hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-cyano hexa cycloheptanone decene such as heptadecene, 14-cyano octa cyclo [8.8.0.1 2.9. 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-14-methyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-dicyanooctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-methyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-methoxyoctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-carboxymethyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-carboxyoctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15. Cyanooctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-trifluoromethyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-fluorooctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-difluorooctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-phenyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5. Dococene, 14-cyano-15-benzyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-cyano-15-cyclohexyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . Cyanooctacyclodocosene such as 0 12.17 ] -5-docosene.
更にはビシクロ[2.2.1]ヘプト−2−エン、5−メチルビシクロ[2.2.1]ヘプト−2−エン、5−エチルビシクロ[2.2.1]ヘプト−2−エン、5−カルボキシビシクロ[2.2.1]ヘプト−2−エン、5−カルボキシメチルビシクロ[2.2.1]ヘプト−2−エン、5−ベンジルビシクロ[2.2.1]ヘプト−2−エン、5−クロロビシクロ[2.2.1]ヘプト−2−エン、5−ブロモビシクロ[2.2.1]ヘプト−2−エン、5−メトキシビシクロ[2.2.1]ヘプト−2−エン、5−エトキシビシクロ[2.2.1]ヘプト−2−エン、5−メチル−6−メチルビシクロ[2.2.1]ヘプト−2−エン等のビシクロヘプトエン誘導体、テトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−メチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−エチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−カルボキシテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8.カルボキシメチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−ベンジルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−クロロテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−ブロモテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−メトキシテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−エトキシテトラシクロ[4.4.0.l.12.5.17.10]−3−ドデセン、8−メチル−9−メチルトキシテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−メチル−9−カルボキシメチルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン、8−フェニルテトラシクロ[4.4.0.1.12.5.17.10]−3−ドデセン等のテトラシクロドデセン誘導体、ヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−メチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−エチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−カルボキシヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−ベンジルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−カルボキシメチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−メトキシヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−エトキシヘキサシクロ[6.6.1,13.6.110.13.02.7.09.14]−4−ヘプタデセン、11−メチル−12−カルボキシメチルヘキサシクロ[6.6.1.13.6.110.13.02.7.09.14]−4−ヘプタデセン等のヘキサシクロヘプタデセン誘導体、オクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−メチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−エチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−カルボキシオクタシクロ[8.8.0.12.9.14.7.111.18.113.l6.03.8.012.17]−5−ドコセン、14−ベンジルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−カルボキシメチルオクタシクロ[8.8.0.12.9.14.7.111.l8.113.16.03.8.012.17]−5−ドコセン、14−メトキシオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−エトキシオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン、14−メチル−15−カルボキシメチルオクタシクロ[8.8.0.12.9.14.7.111.18.113.16.03.8.012.17]−5−ドコセン等のオクタシクロドコセン誘導体、または、モノ環状オレフィンとして、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテン等のシクロオレフィン類、ジシクロペンタジエン類等も挙げられる。 Furthermore, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] hept-2-ene, 5-benzylbicyclo [2.2.1] hept-2-ene Ene, 5-chlorobicyclo [2.2.1] hept-2-ene, 5-bromobicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2 -Bicycloheptene derivatives such as 5-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5-methyl-6-methylbicyclo [2.2.1] hept-2-ene, tetracyclo [4 4.0.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-carboxytetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8. Carboxymethyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-benzyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-bromotetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-methoxytetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-ethoxytetracyclo [4.4.0. l. 1 2.5 . 1 7.10 ] -3-dodecene, 8-methyl-9-methyltoxitetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-methyl-9-carboxymethyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] -3-dodecene, 8-phenyltetracyclo [4.4.0.1.1.1 2.5 . 1 7.10 ] tetracyclododecene derivatives such as 3-dodecene, hexacyclo [6.6.1.1 3.6 . 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-methyl-hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-ethylhexanoate cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-carboxy hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-benzyl hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-carboxymethyl hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-methoxy-hexamethylene cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-ethoxy hexa cyclo [6.6.1,1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, 11-methyl-12-carboxymethyl hexa cyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-hexa cycloheptanone decene derivatives such heptadecene, octacyclo [8.8.0.1 2.9. 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-methyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-ethyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-carboxyoctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.l6 . 0 3.8 . 0 12.17 ] -5-docosene, 14-benzyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-carboxymethyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.l8 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-methoxyoctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-ethoxyoctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . 0 12.17 ] -5-docosene, 14-methyl-15-carboxymethyloctacyclo [8.8.0.1 2.9 . 1 4.7 . 1 11.18 . 1 13.16 . 0 3.8 . Examples of octacyclodocosene derivatives such as 0 12.17 ] -5-docosene or monocyclic olefins include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene, and dicyclopentadiene.
さらに、本発明において上述の一般式〔1〕と〔2〕で表される環状オレフィンの共重合の比率としては、一般式〔1〕の環状オレフィンに対して一般式〔2〕の環状オレフィンが99:1〜1:99である。 Furthermore, in the present invention, the ratio of the copolymerization of the cyclic olefins represented by the above general formulas [1] and [2] is the cyclic olefin of the general formula [2] with respect to the cyclic olefin of the general formula [1]. 99: 1 to 1:99.
本発明において用いられるオレフィンとしては、例えば、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、オクテン等のα−オレフィンが挙げられ、さらに、ビニルトリメチルシラン、アリルトリメチルシラン、アリルトリエチルシラン、アリルトリイソプロピルシラン等のケイ素含有オレフィンが挙げられ、また、ジエンとしては、1、4−ペンタジエン、1、5−ヘキサジエン、1、6−ヘプタジエン等の非共役系ジエンが挙げられる。さらに、これらオレフィンまたはジエンはそれぞれ単独または2種類以上を併用しても良い。 Examples of the olefin used in the present invention include α-olefins such as ethylene, propylene, butene, pentene, hexene, octene, and further, vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane, and the like. Examples of the diene include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, and 1,6-heptadiene. Furthermore, these olefins or dienes may be used alone or in combination of two or more.
本発明において共存させるオレフィンまたはジエンの使用量は、オレフィンまたはジエンと一般式〔1〕及び一般式〔2〕で表される環状オレフィンのモル比が環状オレフィンに対して0.001〜0.5、好ましくは0.01〜0.2の範囲であり、オレフィンまたはジエンと一般式〔3〕で表される遷移金属アルキリデン錯体のモル比は、遷移金属アルキリデン錯体のアルキリデンの1当量に対して0.1〜1000、好ましくは1〜500の範囲である。 The amount of the olefin or diene used in the present invention is such that the molar ratio of the olefin or diene to the cyclic olefin represented by the general formula [1] and the general formula [2] is 0.001 to 0.5 with respect to the cyclic olefin. The molar ratio of the olefin or diene to the transition metal alkylidene complex represented by the general formula [3] is 0 with respect to 1 equivalent of the alkylidene of the transition metal alkylidene complex. .1 to 1000, preferably in the range of 1 to 500.
本発明の開環メタセシス重合において一般式〔1〕及び一般式〔2〕で表される環状オレフィンの使用量は、一般式〔3〕で表される遷移金属アルキリデン錯体に対してモル比で10〜10000であり、好ましくは50〜5000である。また、この重合には無溶媒でも溶媒を使用して良いが、特に使用する溶媒としては、テトラヒドロフラン、ジエチルエーテル、ジブチルエーテル、ジメトキシエタン、ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、デカリン等の脂肪族環状炭化水素、メチレンジクロライド、ジクロロエタン、ジクロロエチレン、テトラクロロエタン、クロロベンゼン、トリクロロベンゼン等のハロゲン化炭化水素等が挙げられ、これらの2種類以上を混合使用しても良い。 In the ring-opening metathesis polymerization of the present invention, the cyclic olefin represented by the general formula [1] and the general formula [2] is used in a molar ratio of 10 with respect to the transition metal alkylidene complex represented by the general formula [3]. It is -10000, Preferably it is 50-5000. In this polymerization, a solvent may be used even without a solvent. Particularly, the solvent to be used includes ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, dioxane, benzene, toluene, xylene, ethylbenzene and the like. Aromatic hydrocarbons, aliphatic hydrocarbons such as pentane, hexane, heptane, etc., cyclopentane, cyclohexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, decalin and other aliphatic cyclic hydrocarbons, methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, tri Examples thereof include halogenated hydrocarbons such as chlorobenzene, and two or more of these may be used in combination.
本発明における開環メタセシス重合で溶媒を使用する場合の環状オレフィンの濃度は、0.01〜100mol/Lの範囲であり、重合温度は、−30〜150℃で、好ましくは常温〜100℃である。また、重合時間は10分〜15時間の範囲で行う。さらに、重合反応を停止するためにアルデヒド類、ケトン類、アルコール類等を使用しても良い。 The concentration of the cyclic olefin when using a solvent in the ring-opening metathesis polymerization in the present invention is in the range of 0.01 to 100 mol / L, and the polymerization temperature is -30 to 150 ° C, preferably normal temperature to 100 ° C. is there. The polymerization time is in the range of 10 minutes to 15 hours. Furthermore, aldehydes, ketones, alcohols and the like may be used to stop the polymerization reaction.
溶液重合の場合、重合反応を停止した後、アルコール等の貧溶媒に加えてポリマーを沈殿させ、濾過または遠心分離等よってポリマーを回収、乾燥の後、開環メタセシスポリマーを得ることができる。また、懸濁重合の場合は貧溶媒に加えても、そのまま、濾過または遠心分離等によってポリマーを回収、乾燥の後、開環メタセシスポリマーを得ることができる。 In the case of solution polymerization, after stopping the polymerization reaction, the polymer is precipitated in addition to a poor solvent such as alcohol, the polymer is recovered by filtration or centrifugation, and dried, and then a ring-opening metathesis polymer can be obtained. In addition, in the case of suspension polymerization, a ring-opening metathesis polymer can be obtained after collecting and drying the polymer by filtration or centrifugation as it is, even if it is added to a poor solvent.
以下の実施例にて本発明を詳細に説明するが、本発明がこれによって限定されるものではない。 The present invention will be described in detail in the following examples, but the present invention is not limited thereto.
実施例において示されたポリマーの平均分子量については、得られた開環メタセシスポリマーをクロロホルム中に溶解し、GPC検出器として日本分光社製830−RI、カラムとしてShodex k−805,804,803,802.5を使用し、室温にて流速1.0ml/minの条件下で測定した。尚、測定値はポリスチレンスタンダードにて較正した値である。 Regarding the average molecular weight of the polymers shown in the Examples, the obtained ring-opening metathesis polymer was dissolved in chloroform, and 830-RI manufactured by JASCO Corporation as a GPC detector and Shodex k-805, 804, 803 as columns. 802.5 was used, and measurement was performed at room temperature under a flow rate of 1.0 ml / min. The measured value is a value calibrated with polystyrene standards.
実施例1
窒素下で100mlフラスコ中にて8−メチルテトラシクロ[4.4.0.12.5.17.10]−3−ドデセン(697mg,4.0mmol)と8−シアノテトラシクロ[4.4.0.12.5.17.10]−3−ドデセン(370mg,2.0mmol)を乾燥テトラヒドロフラン(30ml)に溶解し、更に1,5−ヘキサジエン(40mg,0.48mmol)を混合し、撹件下でW(N−2,6−C6H3−Me2)(CHCHCMePh)(O−t−Bu)2P(Me)3(10mg,0.015mmol)を加えて、室温で4時間反応行った。ベンズアルデヒド(20mg,0.18mmol)を加え、30分間撹件した後、ポリマー溶液を撹件下で200mlのメタノールに加え、沈澱させた。濾過、乾燥し、1.06gのポリマーを得た。得られたポリマーのGPC分析を行ったところクロマトグラフは単一のピークであり、その数平均分子量(Mn)は17,800で、分子量分布指数(Mw/Mn)は2.7であった。
Example 1
8-methyltetracyclo [4.4.0.1 2.5 . In a 100 ml flask under nitrogen. 1 7.10] -3-dodecene (697 mg, 4.0 mmol) and 8-cyano-tetracyclo [4.4.0.1 2.5. 1 7.10 ] -3-dodecene (370 mg, 2.0 mmol) was dissolved in dry tetrahydrofuran (30 ml), 1,5-hexadiene (40 mg, 0.48 mmol) was further mixed, and W (N-2 in addition to 6-C 6 H 3 -Me 2 ) (CHCHCMePh) (O-t-Bu) 2 P (Me) 3 (10mg, 0.015mmol), the reaction was carried out at room temperature for 4 hours. After adding benzaldehyde (20 mg, 0.18 mmol) and stirring for 30 minutes, the polymer solution was added to 200 ml of methanol under stirring to precipitate. Filtration and drying gave 1.06 g of polymer. When the GPC analysis of the obtained polymer was performed, the chromatograph was a single peak, the number average molecular weight (Mn) was 17,800, and the molecular weight distribution index (Mw / Mn) was 2.7.
実施例2
実施例1の1,5−ヘキサジエンに代わって1−ペンテンを80mg(1.14mmol)使用したこと以外は実施例1と同様に行った。ポリマー収量は1.06gであり、GPCは単一のピークであり、Mnは16,600、Mw/Mnは3.1であった。
Example 2
The same procedure as in Example 1 was carried out except that 80 mg (1.14 mmol) of 1-pentene was used instead of 1,5-hexadiene in Example 1. The polymer yield was 1.06 g, GPC was a single peak, Mn was 16,600, and Mw / Mn was 3.1.
比較例1
実施例1において1,5−ヘキサジエンを加えなかったこと以外は実施例1と同様に行った。ポリマー収量は0.78gであり、GPCは単一のピークであり、Mnは59,000、Mw/Mnは1.13であった。
Comparative Example 1
The same procedure as in Example 1 was performed except that 1,5-hexadiene was not added in Example 1. The polymer yield was 0.78 g, GPC was a single peak, Mn was 59,000, and Mw / Mn was 1.13.
Claims (1)
(式中R1〜R4はそれぞれ同一であっても異なっていてもよく、水素、アルキル、アリール、アラルキル、アルコキシ、ハロゲン、またはハロゲン化アルキルから選ばれ、xは1〜3の整数を表す。)と一般式〔2〕
(式中R5〜R8のうち少なくとも1つはニトリル、カルボキシル、またはアルコキシカルボニルから選ばれ、その他は水素、アルキル、アリール、アラルキル、アルコキシ、ハロゲン、またはハロゲン化アルキルから選ばれ、xは1〜3の整数を表す。)で表される環状オレフィンをオレフィンまたはジエン共存下で共重合することを特徴とする環状オレフィンの開環メタセシス重合方法。 Using a ring-opening metathesis polymerization catalyst comprising a transition metal alkylidene complex of Groups 4 to 8 of the periodic table, the general formula [1]
(Wherein R 1 to R 4 may be the same or different and are selected from hydrogen, alkyl, aryl, aralkyl, alkoxy, halogen, or alkyl halide, and x represents an integer of 1 to 3) And general formula [2]
Wherein at least one of R 5 to R 8 is selected from nitrile, carboxyl, or alkoxycarbonyl, the other is selected from hydrogen, alkyl, aryl, aralkyl, alkoxy, halogen, or alkyl halide, and x is 1 The ring-opening metathesis polymerization method of a cyclic olefin characterized by copolymerizing the cyclic olefin represented by -3 in the presence of an olefin or a diene.
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