JP2007063409A - Process for producing cycloolefin copolymer - Google Patents
Process for producing cycloolefin copolymer Download PDFInfo
- Publication number
- JP2007063409A JP2007063409A JP2005251303A JP2005251303A JP2007063409A JP 2007063409 A JP2007063409 A JP 2007063409A JP 2005251303 A JP2005251303 A JP 2005251303A JP 2005251303 A JP2005251303 A JP 2005251303A JP 2007063409 A JP2007063409 A JP 2007063409A
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- JP
- Japan
- Prior art keywords
- group
- cyclic olefin
- compound
- producing
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title abstract description 19
- 229920001577 copolymer Polymers 0.000 title abstract description 17
- -1 cycloolefin compound Chemical class 0.000 claims abstract description 334
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000004711 α-olefin Substances 0.000 claims abstract description 17
- 230000000737 periodic effect Effects 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 5
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 18
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 12
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical group 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 150000003623 transition metal compounds Chemical class 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- 125000005336 allyloxy group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052799 carbon Chemical group 0.000 claims description 3
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 3
- 239000004913 cyclooctene Substances 0.000 claims description 3
- 229910052696 pnictogen Inorganic materials 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 239000003054 catalyst Substances 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 238000007334 copolymerization reaction Methods 0.000 description 15
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 230000037048 polymerization activity Effects 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000007787 solid Substances 0.000 description 5
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 4
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 125000005808 2,4,6-trimethoxyphenyl group Chemical group [H][#6]-1=[#6](-[#8]C([H])([H])[H])-[#6](-*)=[#6](-[#8]C([H])([H])[H])-[#6]([H])=[#6]-1-[#8]C([H])([H])[H] 0.000 description 3
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical group COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KGCRXHYTNRMHCF-UHFFFAOYSA-N 6-methyl-2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(C)O1 KGCRXHYTNRMHCF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 238000012718 coordination polymerization Methods 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000003136 n-heptyl 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])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([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
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 2
- IPRROFRGPQGDOX-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trichlorotitanium Chemical group Cl[Ti](Cl)Cl.CC=1C(C)=C(C)[C-](C)C=1C IPRROFRGPQGDOX-UHFFFAOYSA-K 0.000 description 1
- UOYKBJNWNACIRX-UHFFFAOYSA-N 2,3,3-trifluorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(F)C2(F)F UOYKBJNWNACIRX-UHFFFAOYSA-N 0.000 description 1
- JPUKSAVXNUITKN-UHFFFAOYSA-N 2,3,3-trimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C)C2(C)C JPUKSAVXNUITKN-UHFFFAOYSA-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
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- LZAIJFHJQZYVLF-UHFFFAOYSA-N 5,5-dichlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)(Cl)CC1C=C2 LZAIJFHJQZYVLF-UHFFFAOYSA-N 0.000 description 1
- UDOJACSDSIHAAT-UHFFFAOYSA-N 5-benzylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CC2C1CC1=CC=CC=C1 UDOJACSDSIHAAT-UHFFFAOYSA-N 0.000 description 1
- PSCJIEZOAFAQRM-UHFFFAOYSA-N 5-chlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)CC1C=C2 PSCJIEZOAFAQRM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 1
- LFBHYIUTPVORTR-UHFFFAOYSA-N 5-fluorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(F)CC1C=C2 LFBHYIUTPVORTR-UHFFFAOYSA-N 0.000 description 1
- RCDOWRWNYHNLLA-UHFFFAOYSA-N 5-methoxybicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(OC)CC1C=C2 RCDOWRWNYHNLLA-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- AVFRNNALLLVPGJ-UHFFFAOYSA-N 7-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1C2C AVFRNNALLLVPGJ-UHFFFAOYSA-N 0.000 description 1
- RUSMDMDNFUYZTM-UHFFFAOYSA-N 8-chloroquinoline Chemical compound C1=CN=C2C(Cl)=CC=CC2=C1 RUSMDMDNFUYZTM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241000566113 Branta sandvicensis Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003931 anilides Chemical group 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-O methyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[NH+](C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-O 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RAYYZJTYTUPECK-UHFFFAOYSA-N n,n-diethyl-2,4-dinitroaniline Chemical compound CCN(CC)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RAYYZJTYTUPECK-UHFFFAOYSA-N 0.000 description 1
- LLXZODPVPXJXPD-UHFFFAOYSA-N n,n-dimethylbicyclo[2.2.1]hept-2-en-5-amine Chemical compound C1C2C(N(C)C)CC1C=C2 LLXZODPVPXJXPD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-O phenylphosphanium Chemical compound [PH3+]C1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-O 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Abstract
Description
本発明は、エチレン及び／又は炭素数３〜２０のα−オレフィンと環状オレフィン化合物からなる環状オレフィン系共重合体の製造方法に関するものである。さらに詳しくは、合成が容易でかつ高い重合活性と高い共重合性を有する錯体金属触媒系を用いて環状オレフィン系共重合体を効率よく製造する方法に関するものである。 The present invention relates to a method for producing a cyclic olefin copolymer comprising ethylene and / or an α-olefin having 3 to 20 carbon atoms and a cyclic olefin compound. More specifically, the present invention relates to a method for efficiently producing a cyclic olefin copolymer using a complex metal catalyst system that is easy to synthesize and has high polymerization activity and high copolymerizability.
エチレン及び／又は炭素数３〜２０のα−オレフィンと環状オレフィン化合物との共重合体は透明性、耐薬品性、耐水性等に優れ、近年では、環状オレフィン含量を高めることにより耐熱性を制御した光学用途素材として産業的応用が活発に行われている。また、その製造方法に関しても、（i）配位重合を利用したもの、（ii）開環メタセシス及び水素添加反応を組み合わせたものなど、種々の製造方法が提案されているが、錯体金属触媒系を用いる配位重合系が一段反応で済む点で工業的プロセスを簡便化できる利点がある。 Copolymers of ethylene and / or α-olefins having 3 to 20 carbon atoms and cyclic olefin compounds are excellent in transparency, chemical resistance, water resistance, etc. In recent years, heat resistance is controlled by increasing the cyclic olefin content. Industrial application as an optical material has been actively carried out. As for the production method, various production methods such as (i) using coordination polymerization and (ii) combining ring-opening metathesis and hydrogenation reaction have been proposed. There is an advantage that the industrial process can be simplified in that the coordination polymerization system using the saponification requires only one-step reaction.
錯体金属触媒系としては、例えば、ケイ素あるいは炭素原子等で架橋した２分子のシクロペンタジエニル骨格を有する遷移金属錯体とアルミノキサン化合物からなる、いわゆる架橋メタロセン触媒を用いる方法（例えば、特許文献１〜４参照）、また、アミド基等の供与性分子がシクロペンタジエン骨格と架橋した構造を有する、架橋型のハーフメタロセン化合物を用いて、オレフィン類と環状オレフィン化合物との共重合体を得る方法（例えば、特許文献５参照）が提案されている。 As a complex metal catalyst system, for example, a method using a so-called bridged metallocene catalyst comprising a transition metal complex having a bimolecular cyclopentadienyl skeleton bridged by silicon or a carbon atom and an aluminoxane compound (for example, Patent Documents 1 to 4), and a method of obtaining a copolymer of an olefin and a cyclic olefin compound using a crosslinked half metallocene compound having a structure in which a donor molecule such as an amide group is crosslinked with a cyclopentadiene skeleton (for example, , See Patent Document 5).
これらの製造方法は、全て架橋型のメタロセン触媒あるいは架橋型のハーフメタロセン触媒を用いるものであり、用いられる遷移金属化合物の合成はその合成経路が２〜５段階以上と多く、煩雑であり、個々の工程に技術を要することから触媒コストが高くなるという問題点がある。 All of these production methods use a bridged metallocene catalyst or a bridged half metallocene catalyst, and the synthesis of the transition metal compound used is complicated because there are many synthesis routes of 2 to 5 steps or more. Since this process requires technology, there is a problem that the catalyst cost increases.
一方、合成が容易な非架橋型のハーフメタロセン化合物とアルミノキサン化合物を用いてエチレン及び／又は炭素数３〜２０のα−オレフィンと環状オレフィン化合部物を共重合させる方法（例えば、特許文献６、非特許文献１参照）も提案されている。
例えば、１〜３個の置換基を有する１分子のシクロペンタジエニル基と炭化水素基あるいはジケトナト基を有するハーフメタロセン化合物とアルミノキサン化合物を用いる方法、また、１分子のインデニル基若しくは置換シクロペンタジエニル基と２個以上の置換基を有する１分子のアリロキシ基を有するハーフメタロセン化合物とアルミノキサン化合物を用いる方法である。しかし、どちらの場合も重合活性、及び得られる共重合体中の環状オレフィン化合物の取り込み量（共重合性）が充分ではない。
On the other hand, a method of copolymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms and a cyclic olefin compound using a non-crosslinked half metallocene compound and an aluminoxane compound that are easy to synthesize (for example, Patent Document 6, Non-patent document 1) has also been proposed.
For example, a method using one molecule of a cyclopentadienyl group having 1 to 3 substituents and a half metallocene compound having a hydrocarbon group or a diketonato group and an aluminoxane compound, or one molecule of an indenyl group or a substituted cyclopentadiene. In this method, a half metallocene compound and an aluminoxane compound having an aryl group and one molecule of an allyloxy group having two or more substituents are used. However, in either case, the polymerization activity and the amount of cyclic olefin compound incorporated in the resulting copolymer (copolymerizability) are not sufficient.
一方、非メタロセン化合物を用いる重合方法（例えば、特許文献７参照）も提案されている。これは、２個以上の置換基を有する１分子のアニリド基と２個以上の置換基を有する１分子のアリロキシ基を有する遷移金属化合物からなる錯体金属触媒系であるが、重合様式が開環メタセシス反応であり、エチレン及び／又は炭素数３〜２０のα−オレフィンと環状オレフィン化合物とを共重合し得る方法ではない。
従って、合成が容易でかつ高い重合活性と高い共重合性の両者を満足させる環状オレフィン共重合体の製造方法の開発が望まれている。
On the other hand, a polymerization method using a nonmetallocene compound (see, for example, Patent Document 7) has also been proposed. This is a complex metal catalyst system consisting of a transition metal compound having one molecule of an anilide group having two or more substituents and one molecule of an allyloxy group having two or more substituents. It is a metathesis reaction and is not a method in which ethylene and / or an α-olefin having 3 to 20 carbon atoms and a cyclic olefin compound can be copolymerized.
Therefore, development of a method for producing a cyclic olefin copolymer that is easy to synthesize and satisfies both high polymerization activity and high copolymerizability is desired.
本発明は工業的に用いる上でより簡単に合成でき、高い重合活性と高い共重合性を有する錯体金属触媒系を用いたエチレン及び／又は炭素数３〜２０のα−オレフィンと環状オレフィン化合物からなる環状オレフィン系共重合体の製造方法を見出すことを目的とする。 The present invention can be synthesized more easily for industrial use, from ethylene and / or a C3-C20 α-olefin and a cyclic olefin compound using a complex metal catalyst system having high polymerization activity and high copolymerizability. It aims at finding the manufacturing method of the cyclic olefin type copolymer which becomes.
本発明は、合成の容易な、シクロペンタジエニル骨格を含む配位子１分子と少なくとも１つの特定の骨格を有するアニオン性配位子１分子が周期律表４族の金属に配位した遷移金属化合物と活性化剤からなる錯体金属触媒系が、エチレン及び／又は炭素数３〜２０のα−オレフィンと環状オレフィン化合物の共重合に対して、高い重合活性を有しかつその共重合性に極めて優れるという驚くべき事実に基づいてなされたものである。
すなわち、本発明は、下記（１）〜（４）の環状オレフィン系共重合体の製造方法である。
The present invention provides a transition in which one molecule of a ligand containing a cyclopentadienyl skeleton and one molecule of an anionic ligand having at least one specific skeleton are coordinated to a metal of Group 4 of the periodic table. A complex metal catalyst system comprising a metal compound and an activator has a high polymerization activity for copolymerization of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a cyclic olefin compound, and the copolymerizability thereof. It is based on the surprising fact that it is extremely good.
That is, this invention is a manufacturing method of the cyclic olefin type copolymer of following (1)-(4).
（１）下記一般式（１）で表される遷移金属化合物（Ａ）及び有機アルミニウムオキシ化合物又は有機ホウ素化合物から選ばれる１種以上の活性化剤（Ｂ）からなる重合触媒の存在下、エチレン及び／又は炭素数３〜２０のα−オレフィンと少なくとも１種類の環状オレフィン化合物との共重合を行うことを特徴とする環状オレフィン系共重合体の製造方法。 (1) Ethylene in the presence of a polymerization catalyst comprising a transition metal compound (A) represented by the following general formula (1) and one or more activators (B) selected from organic aluminum oxy compounds or organic boron compounds And / or copolymerizing an α-olefin having 3 to 20 carbon atoms and at least one cyclic olefin compound.
（式中、Ｍは周期律表４族の遷移金属を表す。Ｌは周期律表１５族の元素が配位原子となる１価のアニオン性配位子を表す。Ｘは水素、ハロゲン又は炭素数１〜２０のアルキル基、アルコキシ基、アリール基、アリロキシ基、アラルキル基を表す。Ｌ又はＸは、各々独立に、同一であっても良いし異なっていても良い。ｍは１〜３の整数を表す。Ｒ１〜Ｒ５は各々同じでも異なっていても良く、水素、ハロゲン又は炭素数１〜２０のアルキル基、アルコキシ基、アリール基、アリロキシ基からなり、任意の２つ又は３つが縮合し環を形成していても良い。環には共役２重結合を含んだ芳香族性を有するものも含む。） (In the formula, M represents a transition metal of Group 4 of the periodic table. L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table serves as a coordination atom. X represents hydrogen, halogen, or carbon. Represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or an aralkyl group of formulas 1 to 20. L or X may be the same or different from each other, and m is 1 to 3; Each of R 1 to R 5 may be the same or different and is composed of hydrogen, halogen or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, or an allyloxy group, and any two or three of them are (It may be condensed to form a ring. The ring includes those having aromaticity including a conjugated double bond.)
（２）前記遷移金属化合物（Ａ）の一般式（１）におけるＬが下記一般式（２）で表される１価のアニオン性配位子であることを特徴とする上記（１）に記載の環状オレフィン系共重合体の製造方法 (2) In the above (1), L in the general formula (1) of the transition metal compound (A) is a monovalent anionic ligand represented by the following general formula (2) Method for producing cyclic olefin copolymer of
（式中、Ｙは周期律表の１５族元素、Ｚは周期律表の１４族又は１５族又は１６族から選ばれる一種類の元素を表す。Ｒは水素、炭素数１〜２０のアルキル基、アルコキシ基、アミド基、アリール基、アラルキル基、シリル基、アルキルアミド基、アルキルシリル基、アリールアミド基、シリルアミド基、ホスフィノアミド基、及びホスフィド基を表す。Ｒは、各々独立して互いに同一でも異なっていても良い。ｎはＺの価数に応じた１〜３の整数を表す。またＲは各々が互いに結合して環を形成しても良く、また請求項１に示すシクロペンタジエニル基と結合していても良い。）
（３）前記環状オレフィン化合物が下記一般式（３）で表される化合物であることを特徴とする上記（１）又は（２）に記載の環状オレフィン系共重合体の製造方法。
(In the formula, Y represents a group 15 element of the periodic table, Z represents one element selected from group 14, 15 or 16 of the periodic table. R represents hydrogen and an alkyl group having 1 to 20 carbon atoms. Represents an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an alkylamide group, an alkylsilyl group, an arylamide group, a silylamide group, a phosphinoamide group, and a phosphide group. N represents an integer of 1 to 3 depending on the valence of Z. R may be bonded to each other to form a ring, and the cyclopentadienyl shown in claim 1 It may be bonded to a group.)
(3) The method for producing a cyclic olefin copolymer according to (1) or (2), wherein the cyclic olefin compound is a compound represented by the following general formula (3).
（式中、Ｒ６〜Ｒ１７は各々独立して互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、ハロゲンで置換されていてもよい炭化水素基、酸素を含む置換基または窒素原子を含む置換基を示し、Ｒ１４〜Ｒ１７は互いに結合して単環又は多環を形成していてよく、かつその単環または多環が二重結合を有していてもよく、またＲ１４とＲ１５とでアルキリデン基を形成していてもよい。ｎは０〜２の整数を表す。）
（４）前記環状オレフィン化合物が、シクロペンテン、シクロヘキセン、シクロヘプテン及びシクロオクテンからなる群より選ばれる少なくとも１種であることを特徴とすることを特徴とする上記（１）又は（２）に記載の環状オレフィン系共重合体の製造方法。
(Wherein R 6 to R 17 may each independently be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with halogen, a substituent containing oxygen, or a nitrogen atom. R 14 to R 17 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R 14 And R 15 may form an alkylidene group, and n represents an integer of 0 to 2.)
(4) The cyclic olefin compound according to (1) or (2) above, wherein the cyclic olefin compound is at least one selected from the group consisting of cyclopentene, cyclohexene, cycloheptene and cyclooctene. A method for producing an olefin copolymer.
本発明の環状オレフィン系共重合体の製造方法によれば、高い重合活性と高い共重合性を有する錯体金属触媒系、及び該錯体金属触媒系を用いることによって、エチレン及び／又は炭素数３〜２０のα−オレフィンと少なくとも１つの環状オレフィン化合物とから環状オレフィン系共重合体を工業的により簡単且つ効率的に合成することできる。 According to the method for producing a cyclic olefin copolymer of the present invention, by using a complex metal catalyst system having high polymerization activity and high copolymerizability, and the complex metal catalyst system, ethylene and / or carbon atoms of 3 to 3 are used. A cyclic olefin copolymer can be synthesized industrially more easily and efficiently from 20 α-olefins and at least one cyclic olefin compound.
以下、本発明に関わる環状オレフィン系共重合体の製造方法について詳細に説明する。
本発明で用いられるエチレン及び／又は炭素数３〜２０のα−オレフィンと少なくとも１つの環状オレフィン化合物とを共重合する錯体金属触媒系の前記一般式（１）で表される遷移金属化合物（Ａ）について説明する。
Hereafter, the manufacturing method of the cyclic olefin type copolymer in connection with this invention is demonstrated in detail.
Transition metal compound (A) represented by the above general formula (1) of a complex metal catalyst system for copolymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms and at least one cyclic olefin compound used in the present invention. ).
式中、Ｍは周期律表の４族の遷移金属を表す。Ｌは周期律表の１５族の元素が配位原子となる１価のアニオン性配位子を表す。Ｘは水素、ハロゲン又は炭素数１〜２０のアルキル基、アルコキシ基、アリール基、アリロキシ基、アラルキル基を表す。Ｌ又はＸは、各々独立に、同一であっても良いし異なっていても良い。ｍは１〜３の整数を表す。Ｒ１〜Ｒ５は各々同じでも異なっていても良く、水素、ハロゲン又は炭素数１〜２０のアルキル基、アルコキシ基、アリール基、アリロキシ基からなり、任意の２つ又は３つが縮合し環を形成していても良い。環には共役２重結合を含んだ芳香族性を有するものも含む。 In the formula, M represents a group 4 transition metal in the periodic table. L represents a monovalent anionic ligand in which the group 15 element of the periodic table is a coordination atom. X represents hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or an aralkyl group. L or X may be independently the same or different. m represents an integer of 1 to 3. R 1 to R 5 may be the same as or different from each other, and each of R 1 to R 5 is composed of hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, or an aryloxy group, and any two or three of them are condensed to form a ring. It may be formed. The ring includes those having aromaticity including a conjugated double bond.
殊に、Ｌは前記一般式（２）で表される１価のアニオン性配位子である。式中、Ｙは周期律表の１５族原子、Ｚは周期律表の１４族または１５族原子を表す。Ｒは各々独立に、同一であっても良いし異なっていても良く、水素、炭素数１〜２０のアルキル基、アルコキシ基、アミド基、アリール基、アラルキル基、シリル基、アルキルアミド基、アルキルシリル基、アリールアミド基、シリルアミド基、ホスフィノアミド基、ホスフィド基を表す。ｎはＺの価数に応じた１〜３の整数である。またＲは各々が互いに結合して環を形成しても良く、またシクロペンタジエニル基と結合していても良い。 In particular, L is a monovalent anionic ligand represented by the general formula (2). In the formula, Y represents a group 15 atom in the periodic table, and Z represents a group 14 or group 15 atom in the periodic table. R may independently be the same or different, and may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an alkylamide group, an alkyl group. Represents a silyl group, an arylamide group, a silylamide group, a phosphinoamide group, and a phosphide group. n is an integer of 1 to 3 corresponding to the valence of Z. R may be bonded to each other to form a ring, or may be bonded to a cyclopentadienyl group.
アルキル基、アルコキシ基、アリール基、アリロキシ基、アラルキル基、及びアルキルアミド基、アルキルシリル基、アリールアミド基のアルキル、アリール、アリロキシ部分の具体例としては、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｓｅｃ−ブチル、ｎ−ペンチル、イソペンチル、１−メチルブチル、２−メチルブチル、１，２−ジメチルプロピル、ネオペンチル、シクロペンチル、ｎ−ヘキシル、イソヘキシル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチル、１，１−ジメチルブチル、２，２−ジメチルブチル、３，３−ジメチルブチル、１，２−ジメチルブチル、１，３−ジメチルブチル、１，１−エチルメチルプロピル、１−エチルブチル、２−エチルブチル、シクロヘキシル、ｎ−ヘプチル、イソヘプチル、４−メチルヘキシル、３−メチルヘキシル、２−メチルヘキシル、１−メチルヘキシル、１，１−ジメチルペンチル、２，２−ジメチルペンチル、３，３−ジメチルペンチル、４，４−ジメチルペンチル、１，２−ジメチルペンチル、１，３−ジメチルペンチル、１，４−ジメチルペンチル、１−エチルペンチル、１−プロピルブチル、２−エチルペンチル、３−エチルペンチル、１，１−エチルメチルブチル、１，１−ジエチルプロピル、２，３−ジメチルペンチル、２，４−ジメチルペンチル、３，４−ジメチルペンチル、１−エチル−２−メチルブチル、１−エチル−３−メチルブチル、４−メチルシクロヘキシル、３−メチルシクロヘキシル、シクロヘプチル、１，１，２−トリメチルブチル、１，１，３−トリメチルブチル、２，２，１−トリメチルブチル、２，２，３−チルメチルブチル、３，３，１−トリメチルブチル、３，３，２−トリメチルブチル、１，１，２，２−テトラメチルプロピル、ｎ−オクチル、１−メチルヘプチル、２−メチルヘプチル、３−メチルヘプチル、４−メチルヘプチル、５−メチルヘプチル、イソオクチル、１−エチルヘキシル、２−エチルヘキシル、３−エチルヘキシル、４−エチルヘキシル、１，１−ジメチルヘキシル、２，２−ジメチルヘキシル、３，３−ジメチルヘキシル、４，４−ジメチルヘキシル、５，５−ジメチルヘキシル、１，２−ジメチルヘキシル、１，３−ジメチルヘキシル、１，４−ジメチルヘキシル、１，５−ジメチルヘキシル、２，３−ジメチルヘキシル、２，４−ジメチルヘキシル、３，４−ジメチルヘキシル、２，５−ジメチルヘキシル、３，５−ジメチルヘキシル、１，１−メチルエチルペンチル、１−エチル−２−メチルペンチル、１−エチル−３−メチルペンチル、１−エチル−４−メチルペンチル、２−エチル−１−メチルペンチル、２，２−エチルメチルペンチル、３，３−エチルメチルペンチル、２−エチル−３−メチルペンチル、２−エチル−４−メチルペンチル、３−エチル−４−メチルペンチル、３−エチル−２−メチルペンチル、１，１−ジエチルブチル、２，２−ジエチルブチル、１，２−ジエチルブチル、１，１−メチルプロピルブチル、２−メチル−１−プロピルブチル、３−メチル−１−プロピルブチル、４−エチルシクロヘキシル、３−エチルシクロヘキシル、３，４−ジメチルシクロヘキシル、１，１，２−トリメチルペンチル、１，１，３−トリメチルペンチル、１，１，４−トリメチルペンチル、２，２，１−トリメチルペンチル、２，２，３−トリメチルペンチル、２，２，４−トリメチルペンチル、３，３，１−トリメチルペンチル、３，３，２−トリメチルペンチル、３，３，４−トリメチルペンチル、１，２，３−トリメチルペンチル、１，２，４−トリメチルペンチル、１，３，４−トリメチルペンチル、１，２，３−トリメチルペンチル、１，２，４−トリメチルペンチル、１，３，４−トリメチルペンチル、１，１，２，２−テトラメチルブチル、１，１，３，３−テトラメチルブチル、１，１，２，３−テトラメチルブチル、２，２，１，３−テトラメチルブチル、１−エチル−１，２−ジメチルブチル、２−エチル−１，２−ジメチルブチル、１−エチル−２，３−ジメチルブチル、ｎ−ノニル、イソノニル、１−メチルオクチル、２−メチルオクチル、３−メチルオクチル、４−メチルオクチル、５−メチルオクチル、６−メチルオクチル、１−エチルヘプチル、２−エチルヘプチル、３−エチルヘプチル、４−エチルヘプチル、５−エチルヘプチル、１，１−ジメチルヘプチル、２，２−ジメチルヘプチル、３，３−ジメチルヘプチル、４，４−ジメチルヘプチル、５，５−ジメチルヘプチル、６，６−ジメチルヘプチル、１，２−ジメチルヘプチル、１，３−ジメチルヘプチル、１，４−ジメチルヘプチル、１，５−ジメチルヘプチル、１，６−ジメチルヘプチル、２，３−ジメチルヘプチル、２，４−ジメチルヘプチル、２，５−ジメチルヘプチル、２，６−ジメチルヘプチル、３，４−ジメチルヘプチル、３，５−ジメチルヘプチル、３，６−ジメチルヘプチル、４，５−ジメチルヘプチル、４，６−ジメチルヘプチル、５，６−ジメチルヘプチル、１，１，２−トリメチルヘキシル、１，１，３−トリメチルヘキシル、１，１，４−トリメチルヘキシル、１，１，５−トリメチルヘキシル、２，２，１−トリメチルヘキシル、２，２，３−トリメチルヘキシル、２，２，４−トリメチルヘキシル、２，２，５−トリメチルヘキシル、３，３，１−トリメチルヘキシル、３，３，２−トリメチルヘキシル、３，３，４−トリメチルヘキシル、３，３，５−トリメチルヘキシル、４，４，１−トリメチルヘキシル、４，４，２−トリメチルヘキシル、４，４，３−トリメチルヘキシル、４，４，５−トリメチルヘキシル、５，５，１−トリメチルヘキシル、５，５，２−トリメチルヘキシル、５，５，３−トリメチルヘキシル、５，５，４−トリメチルヘキシル、１，２，３−トリメチルヘキシル、２，３，４−トリメチルヘキシル、３，４，５−トリメチルヘキシル、１，３，４−トリメチルヘキシル、１，４，５−トリメチルヘキシル、２，４，５−トリメチルヘキシル、１，２，５−トリメチルヘキシル、１，２，４−トリメチルヘキシル、１，１−エチルメチルヘキシル、２，２−エチルメチルヘキシル、３，３−エチルメチルヘキシル、４，４−エチルメチルヘキシル、５，５−エチルメチルヘキシル、１−エチル−２−メチルヘキシル、１−エチル−３−メチルヘキシル、１−エチル−４−メチルヘキシル、１−エチル−５−メチルヘキシル、２−エチル−１−メチルヘキシル、３−エチル−１−メチルヘキシル、３−エチル−２−メチルヘキシル、１，１−ジエチルペンチル、２，２−ジエチルペンチル、３，３−ジエチルペンチル、１，２−ジエチルペンチル、１，３−ジエチルペンチル、２，３−ジエチルペンチル、１，１−メチルプロピルペンチル，２，２−メチルプロピルペンチル，１−メチル−２−プロピルペンチル、ｎ−デシル、イソデシル、１−メチルノニル、２−メチルノニル、３−メチルノニル、４−メチルノニル、５−メチルノニル、６−メチルノニル、７−メチルノニル、１−エチルオクチル、２−エチルオクチル、３−エチルオクチル、４−エチルオクチル、５−エチルオクチル、６−エチルオクチル、１，１−ジメチルオクチル、２，２−ジメチルオクチル、３，３−ジメチルオクチル、４，４−ジメチルオクチル、５，５−ジメチルオクチル、６，６−ジメチルオクチル、７，７−ジメチルオクチル、１，２−ジメチルオクチル、１，３−ジメチルオクチル、１，４−ジメチルオクチル、１，５−ジメチルオクチル、１，６−ジメチルオクチル、１，７−ジメチルオクチル、２，３−ジメチルオクチル、２，４−ジメチルオクチル、２，５−ジメチルオクチル、２，６−ジメチルオクチル、２，７−ジメチルオクチル、３，４−ジメチルオクチル、３，５−ジメチルオクチル、３，６−ジメチルオクチル、３，７−ジメチルオクチル、４，５−ジメチルオクチル、４，６−ジメチルオクチル、４，７−ジメチルオクチル、５，６−ジメチルオクチル、５，７−ジメチルオクチル、ｎ−ウンデシル、ｎ−ドデシル、フェニル、ベンジル、ｐ−トリル、ｍ−トリル、キシリル、メシチリル、２，６−ジメチルフェニル、２，４，６−トリメチルフェニル、２，６−ジメトキシフェニル、２，４，６−トリメトキシフェニル、２，６−ジイソプロピルフェニル、２，４，６−トリイソプロピルフェニル、ナフチル、２−メトキシフェニル、２−イソプロポキシフェニル、２−ｔ−ブトキシフェニル、２，６−ジ−ｔ−ブチルフェニル、２−メチルフェニル、２−イソプロピルフェニル、２−ｔ−ブチルフェニル、２−メチル−６−イソプロピルフェニル、２−メチル−６−ｔ−ブチルフェニル、トリメチルシリルメチレン、ビストリメチルシリルメチンなどが挙げられる。 Specific examples of alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, and alkylamide group, alkylsilyl group, alkylamide of arylamide group, aryl, aryloxy moiety include methyl, ethyl, propyl, isopropyl, n- Butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2- Methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,1-ethylmethylpropyl 1-ethylbutyl, 2-ethylbutyl, siku Hexyl, n-heptyl, isoheptyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4 , 4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1-ethylpentyl, 1-propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1 -Ethylmethylbutyl, 1,1-diethylpropyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 4 -Methylcyclohexyl, 3-methylcyclohexyl, cycloheptyl, 1,1,2-trimethylbutene 1,1,3-trimethylbutyl, 2,2,1-trimethylbutyl, 2,2,3-tylmethylbutyl, 3,3,1-trimethylbutyl, 3,3,2-trimethylbutyl, 1, 1,2,2-tetramethylpropyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, isooctyl, 1-ethylhexyl, 2-ethylhexyl, 3 -Ethylhexyl, 4-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, , 3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4 -Dimethylhexyl, 3,4-dimethylhexyl, 2,5-dimethylhexyl, 3,5-dimethylhexyl, 1,1-methylethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4- Methylpentyl, 3-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 1,1-diethylbutyl, 2,2-diethylbutyl, 1,2-diethylbutyl, 1,1-methylpropylbutyl, 2-methyl-1-propylbutyl, 3-methyl-1-propylbutyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 3, -Dimethylcyclohexyl, 1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,1,4-trimethylpentyl, 2,2,1-trimethylpentyl, 2,2,3-trimethylpentyl, 2 , 2,4-trimethylpentyl, 3,3,1-trimethylpentyl, 3,3,2-trimethylpentyl, 3,3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4- Trimethylpentyl, 1,3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4-trimethylpentyl, 1,3,4-trimethylpentyl, 1,1,2,2-tetramethylbutyl 1,1,3,3-tetramethylbutyl, 1,1,2,3-tetramethylbutyl, 2,2,1,3-tetramethylbutyl, 1-ethyl-1 2-dimethylbutyl, 2-ethyl-1,2-dimethylbutyl, 1-ethyl-2,3-dimethylbutyl, n-nonyl, isononyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4- Methyloctyl, 5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, 1,1-dimethylheptyl, 2,2-dimethyl Heptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 5,5-dimethylheptyl, 6,6-dimethylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, 1,4-dimethylheptyl 1,5-dimethylheptyl, 1,6-dimethylheptyl, 2,3-dimethylheptyl, 2,4-dimethylhept Butyl, 2,5-dimethylheptyl, 2,6-dimethylheptyl, 3,4-dimethylheptyl, 3,5-dimethylheptyl, 3,6-dimethylheptyl, 4,5-dimethylheptyl, 4,6-dimethylheptyl 5,6-dimethylheptyl, 1,1,2-trimethylhexyl, 1,1,3-trimethylhexyl, 1,1,4-trimethylhexyl, 1,1,5-trimethylhexyl, 2,2,1- Trimethylhexyl, 2,2,3-trimethylhexyl, 2,2,4-trimethylhexyl, 2,2,5-trimethylhexyl, 3,3,1-trimethylhexyl, 3,3,2-trimethylhexyl, 3, 3,4-trimethylhexyl, 3,3,5-trimethylhexyl, 4,4,1-trimethylhexyl, 4,4,2-trimethylhexyl, 4 4,3-trimethylhexyl, 4,4,5-trimethylhexyl, 5,5,1-trimethylhexyl, 5,5,2-trimethylhexyl, 5,5,3-trimethylhexyl, 5,5,4-trimethyl Hexyl, 1,2,3-trimethylhexyl, 2,3,4-trimethylhexyl, 3,4,5-trimethylhexyl, 1,3,4-trimethylhexyl, 1,4,5-trimethylhexyl, 2,4 , 5-trimethylhexyl, 1,2,5-trimethylhexyl, 1,2,4-trimethylhexyl, 1,1-ethylmethylhexyl, 2,2-ethylmethylhexyl, 3,3-ethylmethylhexyl, 4, 4-ethylmethylhexyl, 5,5-ethylmethylhexyl, 1-ethyl-2-methylhexyl, 1-ethyl-3-methylhexyl, 1-ethyl 4-methylhexyl, 1-ethyl-5-methylhexyl, 2-ethyl-1-methylhexyl, 3-ethyl-1-methylhexyl, 3-ethyl-2-methylhexyl, 1,1-diethylpentyl, 2,2-diethylpentyl, 3,3-diethylpentyl, 1,2-diethylpentyl, 1,3-diethylpentyl, 2,3-diethylpentyl, 1,1-methylpropylpentyl, 2,2-methylpropylpentyl , 1-methyl-2-propylpentyl, n-decyl, isodecyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 1-ethyloctyl, 2 -Ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyl Octyl, 1,1-dimethyloctyl, 2,2-dimethyloctyl, 3,3-dimethyloctyl, 4,4-dimethyloctyl, 5,5-dimethyloctyl, 6,6-dimethyloctyl, 7,7-dimethyloctyl 1,2-dimethyloctyl, 1,3-dimethyloctyl, 1,4-dimethyloctyl, 1,5-dimethyloctyl, 1,6-dimethyloctyl, 1,7-dimethyloctyl, 2,3-dimethyloctyl, 2,4-dimethyloctyl, 2,5-dimethyloctyl, 2,6-dimethyloctyl, 2,7-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 3, , 7-dimethyloctyl, 4,5-dimethyloctyl, 4,6-dimethyloctyl, 4,7-dimethyloctyl, 5,6 Dimethyloctyl, 5,7-dimethyloctyl, n-undecyl, n-dodecyl, phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 2-t -Butoxyphenyl, 2,6-di-t-butylphenyl, 2-methylphenyl, 2-isopropylphenyl, 2-t-butylphenyl, 2-methyl-6-isopropylphenyl, 2-methyl-6-t-butyl Examples include phenyl, trimethylsilylmethylene, bistrimethylsilylmethine and the like.
好ましくはメチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｓｅｃ−ブチル、ｎ−ペンチル、イソペンチル、１−メチルブチル、２−メチルブチル、１，２−ジメチルプロピル、ネオペンチル、シクロペンチル、ｎ−ヘキシル、イソヘキシル、１−メチルペンチル、２−メチルペンチル、１，１−ジメチルブチル、２，２−ジメチルブチル、１，２−ジメチルブチル、１，３−ジメチルブチル、１，１−エチルメチルプロピル、１−エチルブチル、２−エチルブチル、シクロヘキシル、ｎ−ヘプチル、イソヘプチル、２−メチルヘキシル、１−メチルヘキシル、１，１−ジメチルペンチル、２，２−ジメチルペンチル、３，３−ジメチルペンチル、１，２−ジメチルペンチル、１，３−ジメチルペンチル、１，４−ジメチルペンチル、１−エチルペンチル、１−プロピルブチル、２−エチルペンチル、３−エチルペンチル、１，１−エチルメチルブチル、１，１−ジエチルプロピル、２，３−ジメチルペンチル、２，４−ジメチルペンチル、１−エチル−２−メチルブチル、１−エチル−３−メチルブチル、４−メチルシクロヘキシル、３−メチルシクロヘキシル、１，１，２−トリメチルブチル、１，１，３−トリメチルブチル、２，２，１−トリメチルブチル、２，２，３−チルメチルブチル、３，３，１−トリメチルブチル、３，３，２−トリメチルブチル、１，１，２，２−テトラメチルプロピル、ｎ−オクチル、１−メチルヘプチル、２−メチルヘプチル、３−メチルヘプチル、１−エチルヘキシル、２−エチルヘキシル、１，１−ジメチルヘキシル、２，２−ジメチルヘキシル、３，３−ジメチルヘキシル、１，２−ジメチルヘキシル、１，３−ジメチルヘキシル、１，４−ジメチルヘキシル、１，５−ジメチルヘキシル、２，３−ジメチルヘキシル、２，４−ジメチルヘキシル、３，４−ジメチルヘキシル、２，５−ジメチルヘキシル、１，１−メチルエチルペンチル、１−エチル−２−メチルペンチル、１−エチル−３−メチルペンチル、１−エチル−４−メチルペンチル、２−エチル−１−メチルペンチル、２，２−エチルメチルペンチル、３，３−エチルメチルペンチル、２−エチル−３−メチルペンチル、２−エチル−４−メチルペンチル、３−エチル−４−メチルペンチル、３−エチル−２−メチルペンチル、１，１−ジエチルブチル、２，２−ジエチルブチル、１，２−ジエチルブチル、１，１−メチルプロピルブチル、２−メチル−１−プロピルブチル、３メチル−１−プロピルブチル、４−エチルシクロヘキシル、３−エチルシクロヘキシル、３，４−ジメチルシクロヘキシル、１，１，２−トリメチルペンチル、１，１，３−トリメチルペンチル、１，１，４−トリメチルペンチル、２，２，１−トリメチルペンチル、２，２，３−トリメチルペンチル、２，２，４−トリメチルペンチル、３，３，１−トリメチルペンチル、３，３，２−トリメチルペンチル、３，３，４−トリメチルペンチル、１，２，３−トリメチルペンチル、１，２，４−トリメチルペンチル、１，３，４−トリメチルペンチル、１，２，３−トリメチルペンチル、１，２，４−トリメチルペンチル、１，３，４−トリメチルペンチル、１，１，２，２−テトラメチルブチル、１，１，３，３−テトラメチルブチル、１，１，２，３−テトラメチルブチル、２，２，１，３−テトラメチルブチル、１−エチル−１，２−ジメチルブチル、２−エチル−１，２−ジメチルブチル、１−エチル−２，３−ジメチルブチル、フェニル、ベンジル、ｐ−トリル、ｍ−トリル、キシリル、メシチリル、２，６−ジメチルフェニル、２，４，６−トリメチルフェニル、２，６−ジメトキシフェニル、２，４，６−トリメトキシフェニル、２，６−ジイソプロピルフェニル、２，４，６−トリイソプロピルフェニル、ナフチル、２−メトキシフェニル、２−イソプロポキシフェニル、２−ｔ−ブトキシフェニル、２，６−ジ−ｔ−ブチルフェニル、２−メチルフェニル、２−イソプロピルフェニル、２−ｔ−ブチルフェニル、２−メチル−６−イソプロピルフェニル、２−メチル−６−ｔ−ブチルフェニル、トリメチルシリルメチレン、ビストリメチルシリルメチンなどが挙げられる。 Preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, cyclopentyl, n -Hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,1-ethylmethylpropyl 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, 2-methylhexyl, 1-methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 1, 2-dimethylpentyl, 1,3-dimethylpentyl, , 4-dimethylpentyl, 1-ethylpentyl, 1-propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-ethylmethylbutyl, 1,1-diethylpropyl, 2,3-dimethylpentyl, 2, 4-dimethylpentyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 4-methylcyclohexyl, 3-methylcyclohexyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 2 , 2,1-trimethylbutyl, 2,2,3-tilmethylbutyl, 3,3,1-trimethylbutyl, 3,3,2-trimethylbutyl, 1,1,2,2-tetramethylpropyl, n- Octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,1-di Tilhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl 2,4-dimethylhexyl, 3,4-dimethylhexyl, 2,5-dimethylhexyl, 1,1-methylethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1- Ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 1,1-diethylbutyl, 2,2-diethylbutyl 1,2-diethylbutyl, 1,1-methylpropylbutyl, 2-methyl-1-propylbutyl, 3methyl-1-propylbutyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 3,4-dimethylcyclohexyl, 1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,1,4-trimethylpentyl, 2,2,1-trimethylpentyl, 2,2,3-trimethylpentyl, 2,2,4 -Trimethylpentyl, 3,3,1-trimethylpentyl, 3,3,2-trimethylpentyl, 3,3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4-trimethylpentyl, 1 , 3,4-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4-trimethylpentyl, 1,3,4-tri Tilpentyl, 1,1,2,2-tetramethylbutyl, 1,1,3,3-tetramethylbutyl, 1,1,2,3-tetramethylbutyl, 2,2,1,3-tetramethylbutyl, 1-ethyl-1,2-dimethylbutyl, 2-ethyl-1,2-dimethylbutyl, 1-ethyl-2,3-dimethylbutyl, phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesitylyl, 2 , 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl 2-methoxyphenyl, 2-isopropoxyphenyl, 2-t-butoxyphenyl, 2,6-di-t-butylphenyl, 2-methylphenyl, 2- Isopropyl phenyl, 2-t-butylphenyl, 2-methyl-6-isopropylphenyl, 2-methyl -6-t-butylphenyl, trimethylsilyl methylene, bis trimethylsilyl methine.
前記、一般式（１）で表される具体的な遷移金属化合物（Ａ）として、例えば、ＣｐＴｉ（ｔ−Ｂｕ２Ｃ＝Ｎ）Ｃｌ２、Ｃｐ＊Ｔｉ（ｔ−Ｂｕ２Ｃ＝Ｎ）Ｃｌ２、１，３-Ｍｅ２ＣｐＴｉ（ｔ−Ｂｕ２Ｃ＝Ｎ）Ｃｌ２及び１，３-Ｍｅ２ＣｐＴｉ（(Ｍｅ３Ｓｉ)(ｔ−Ｂｕ)Ｃ＝Ｎ）Ｃｌ２等を例示することが出来る。これらは単独で用いても良いし、組み合わせて用いても良い。ここで、Ｃｐはシクロペンタジエニル基を、Ｃｐ＊はη５−ペンタメチルシクロペンタジエニル基を表す。 Examples of the specific transition metal compound (A) represented by the general formula (1) include CpTi (t-Bu 2 C═N) Cl 2 and Cp * Ti (t-Bu 2 C═N) Cl. 2, 1,3-Me 2 CpTi ( t-Bu 2 C = N) Cl 2 and 1,3-Me 2 CpTi ((Me 3 Si) (t-Bu) C = N) be exemplified Cl 2, etc. I can do it. These may be used alone or in combination. Here, Cp represents a cyclopentadienyl group, and Cp * represents an η 5 -pentamethylcyclopentadienyl group.
本発明で用いることのできる有機アルミニウムオキシ化合物としては下記一般式（４）、（５）、（６）および（７）で示される有機アルミニウムオキシ化合物のうち少なくとも１つの化合物があげられる。 Examples of the organoaluminum oxy compound that can be used in the present invention include at least one compound among the organoaluminum oxy compounds represented by the following general formulas (4), (5), (6), and (7).
これら有機アルミニウムオキシ化合物の具体例としては、メチルアルミノキサン、エチルアルミノキサン、プロピルアルミノキサン、ブチルアルミノキサン、イソブチルアルミノキサン、メチルエチルアルミノキサン、メチルブチルアルミノキサン、メチルイソブチルアルミノキサン等が挙げられる。特に、メチルアルミノキサン、イソブチルアルミノキサン、メチルイソブチルアルミノキサンが好適に使用できる。これらは２種以上組み合わせて用いてもよい。
また、これら有機アルミニウムオキシ化合物には、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等の有機アルミニウム化合物を含んでいてもよい。
また、本発明で用いることのできる有機ホウ素化合物としては下記一般式（８）または（９）で示される有機ホウ素化合物のうち少なくとも１つの化合物があげられる。
Specific examples of these organoaluminum oxy compounds include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. In particular, methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane can be preferably used. Two or more of these may be used in combination.
These organoaluminum oxy compounds may contain organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum.
Moreover, as an organic boron compound which can be used by this invention, at least 1 compound is mention | raise | lifted among the organic boron compounds shown by following General formula (8) or (9).
前記一般式（８）および（９）の炭化水素基の具体例としてはフェニル、ベンジル、ｐ−トリル、ｍ−トリル、キシリル、メシチリル、２，６−ジメチルフェニル，２，４，６−トリメチルフェニル，２，６−ジメトキシフェニル，２，４，６−トリメトキシフェニル，２，６−ジイソプロピルフェニル，２，４，６−トリイソプロピルフェニル、ナフチル、ｏ−イソプロポキシフェニル、ペンタフルオロフェニル、ペンタフルオロベンジル、テトラフルオロフェニル、テトラフルオロトリル等があげられる。 Specific examples of the hydrocarbon groups of the general formulas (8) and (9) include phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl. 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, o-isopropoxyphenyl, pentafluorophenyl, pentafluorobenzyl , Tetrafluorophenyl, tetrafluorotolyl and the like.
また、前記一般式（９）中のＱの具体例としてはピリジニウム、２，４−ジニトロ−Ｎ，Ｎ−ジエチルアニリニウム、ｐ−ニトロアニリニウム、２，５−ジクロロアニリン、ｐ−ニトロ−Ｎ，Ｎ−ジメチルアニリニウム，キノリニウム、Ｎ，Ｎ−ジメチルアニリニウム，メチルジフェニルアンモニウム、Ｎ，Ｎ−ジエチルアニリニウム、８−クロロキノリニウム、トリメチルアンモニウム、トリプロピルアンモニウム、トリエチルアンモニウム、トリブチルアンモニウム、トリフェニルホスホニウム、アンモニウム、トリフェニルメチル、ナトリウム、リチウム、カリウム、セシウム、カルシウム、マグネシウム等があげられる。 Specific examples of Q in the general formula (9) include pyridinium, 2,4-dinitro-N, N-diethylanilinium, p-nitroanilinium, 2,5-dichloroaniline, p-nitro-N. , N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, methyldiphenylammonium, N, N-diethylanilinium, 8-chloroquinolinium, trimethylammonium, tripropylammonium, triethylammonium, tributylammonium, tri Examples include phenylphosphonium, ammonium, triphenylmethyl, sodium, lithium, potassium, cesium, calcium, magnesium and the like.
これら有機ホウ素化合物の具体例としては、トリメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリエチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。これらは２種以上組み合わせて用いてもよい。最も好ましくはトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートが挙げられる。 Specific examples of these organic boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl). ) Borate and the like. Two or more of these may be used in combination. Most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.
本発明において使用するのに好適な触媒は（Ａ）遷移金属化合物および（Ｂ）アルキルアルミニウムオキシ化合物または有機ホウ素化合物から選ばれる１種以上の活性化剤を任意の順序でかつ任意の好適な方法で組み合わせることによって製造される。
前記（Ａ）成分と（Ｂ）成分の触媒組成比（モル比）は、好ましくは（Ａ）：（Ｂ）＝１：０．０１〜１：１００００であり、更に好ましくは１：１００〜１：３０００である。
Suitable catalysts for use in the present invention are (A) transition metal compounds and (B) one or more activators selected from alkylaluminumoxy compounds or organoboron compounds in any order and in any suitable process. Manufactured by combining with.
The catalyst composition ratio (molar ratio) between the component (A) and the component (B) is preferably (A) :( B) = 1: 0.01 to 1: 10000, more preferably 1: 100 to 1. : 3000.
触媒調製はあらかじめ、窒素、アルゴン等の不活性ガス雰囲気下、好適な溶媒中で混合することにより行ってもよいし、（Ａ），（Ｂ）それぞれの成分を別々にモノマーが共存するリアクター内に打ち込んで、リアクター内において調製してもよい。触媒調製に好適な溶媒はヘキサン、シクロヘキサン等のアルカンをはじめとする炭化水素系溶媒とトルエン、ベンゼン、エチルベンゼン等の芳香族系の溶媒があげられる。またこれらの溶媒は前処理において水分等を除去しておくことが好ましい。触媒の調製温度としては、−２０℃〜１５０℃が最適である。 The catalyst may be prepared in advance by mixing it in a suitable solvent under an inert gas atmosphere such as nitrogen or argon, or in a reactor in which each component (A) and (B) is separately present in the monomer. And may be prepared in the reactor. Suitable solvents for preparing the catalyst include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene. Moreover, it is preferable to remove water and the like from these solvents in the pretreatment. The optimum catalyst preparation temperature is -20 ° C to 150 ° C.
本発明で使用できる炭素数３〜２０のα−オレフィンとしては、例えば、プロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−ヘプテン、１−オクテン、１−デセン等をあげることができる。
また、本発明で使用できる環状オレフィン化合物としては、下記一般式（３）で表すことができる化合物、若しくはシクロペンテン、又はシクロヘキセン、又はシクロヘプテン、又はシクロオクテン等をあげることができる。
Examples of the α-olefin having 3 to 20 carbon atoms that can be used in the present invention include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, and 1-decene. I can give you.
Examples of the cyclic olefin compound that can be used in the present invention include a compound represented by the following general formula (3), cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like.
（式中、Ｒ６〜Ｒ１７は各々独立して互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、ハロゲンで置換されていてもよい炭化水素基、酸素を含む置換基または窒素原子を含む置換基を示し、Ｒ１４〜Ｒ１７は互いに結合して単環または多環を形成していてよく、かつその単環または多環が二重結合を有していてもよい。またＲ１４とＲ１５とでアルキリデン基を形成していてもよい。ｎは０〜２の整数を示す。） (Wherein R 6 to R 17 may each independently be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with halogen, a substituent containing oxygen, or a nitrogen atom. represents a substituent containing, R 14 to R 17 may form a monocyclic or polycyclic bonded to each other, and the monocyclic or polycyclic ring may have a double bond. the R 14 And R 15 may form an alkylidene group, and n represents an integer of 0 to 2.)
前記一般式（３）のハロゲン原子、ハロゲンで置換されていてもよい炭化水素基としては具体的には、例えば、フッ素、塩素、臭素、ヨウ素等のハロゲン基、クロロメチル基、ブロモメチル基、クロロエチル基等の炭素数１〜２０のハロゲン置換アルキル基、炭素数１〜２０のハロゲン非置換アルキル基等を挙げることができる。
また、前記一般式（３）の酸素を含む置換基として具体的には、メトキシ基、エトキシ基、プロポキシ基、フェノキシ基等の炭素数１〜２０のアルコキシ基、メトキシカルボニル基、エトキシカルボニル基等の炭素数１〜２０のアルコキシカルボニル基等を挙げることができる。
さらに、前記一般式（３）の窒素原子を含む置換基としては具体的には、例えば、ジメチルアミノ基、ジエチルアミノ基等の炭素数１〜２０のアルキルアミノ基やシアノ基等を挙げることができる。
Specific examples of the halogen atom of the general formula (3) and the hydrocarbon group which may be substituted with halogen include, for example, halogen groups such as fluorine, chlorine, bromine and iodine, chloromethyl group, bromomethyl group and chloroethyl. Examples thereof include a halogen-substituted alkyl group having 1 to 20 carbon atoms such as a group and a halogen-unsubstituted alkyl group having 1 to 20 carbon atoms.
Specific examples of the oxygen-containing substituent represented by the general formula (3) include methoxy group, ethoxy group, propoxy group, phenoxy group and other C1-C20 alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group and the like. And an alkoxycarbonyl group having 1 to 20 carbon atoms.
Furthermore, specific examples of the substituent containing a nitrogen atom in the general formula (3) include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group. .
前記一般式（３）で表される環状オレフィン化合物の具体例としては、ビシクロ［２．２．１］ヘプト−２−エン（以下ノルボルネンと称する）、５−メチルノルボルネン、５−エチルノルボルネン、５−プロピルノルボルネン、５，６−ジメチルノルボルネン、１−メチルノルボルネン、７−メチルノルボルネン、５，５，６−トリメチルノルボルネン、５−フェニルノルボルネン、５−ベンジルノルボルネン、５−エチリデンノルボルネン、５−ビニルノルボルネン、５−クロロノルボルネン、５−シアノノルボルネン、５−フルオロノルボルネン、５，５−ジクロロノルボルネン、５，５，６−トリフルオロノルボルネン、５−メトキシノルボルネン、５−ジメチルアミノノルボルネン、５，５，６−トリフルオロ−６−メチルノルボルネン、トリシクロ［４．３．０．１２.５］−３−デセン、トリシクロ［４．４．０．１２.５］−３−ウンデセン、テトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−メチルテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−エチルテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−プロピルテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−ブチルテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−イソブチルテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−エチリデンテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−クロロテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−シアノテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−フルオロテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８，８−ジクロロテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−メトキシテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８−ジメチルアミノテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８，８，９−トリフルオロテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、８，８，９−トリフルオロ−９−メチルテトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセン、ペンタシクロ［６．５．１．１３.６．０２.７．０９.１３］−４−ペンタデセン、ペンタシクロ［６．６．１．１３.６．０２.７．０９.１４］−４−ヘキサデセン、ヘキサシクロ［６．６．１．１３.６．１１０.１３．０２.７．０９.１４］−４−ヘプタデセン等が例示される。これらの環状オレフィン化合物は１種単独または２種以上組み合わせて用いることが出来る。これらの環状オレフィン化合物のなかで、ノルボルネン、トリシクロ［４．３．０．１２.５］−３−デセン、トリシクロ［４．４．０．１２.５］−３−ウンデセン、テトラシクロ［４．４．０．１２.５．１７.１０］−３−ドデセンが好ましく、特にノルボルネンが好ましい。 Specific examples of the cyclic olefin compound represented by the general formula (3) include bicyclo [2.2.1] hept-2-ene (hereinafter referred to as norbornene), 5-methylnorbornene, 5-ethylnorbornene, 5 -Propyl norbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 5-chloronorbornene, 5-cyanonorbornene, 5-fluoronorbornene, 5,5-dichloronorbornene, 5,5,6-trifluoronorbornene, 5-methoxynorbornene, 5-dimethylaminonorbornene, 5,5,6-tri Fluoro-6-methylnorbo Nene, tricyclo [4.3.0.1 2.5] -3- decene, tricyclo [4.4.0.1 2.5] -3- undecene, tetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-propyltetracyclo [4.4.0.1 2.5 . 1 7.10] -3-dodecene, 8-butyl tetracyclo [4.4.0.1 2.5. 1 7.10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyanotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-fluorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8,8-dichlorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-methoxytetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-dimethylaminotetracyclo [4.4.0.1 2.5 . 1 7.10] -3-dodecene, 8,8,9- trifluoro-tetracyclo [4.4.0.1 2.5. 1 7.10 ] -3-dodecene, 8,8,9-trifluoro-9-methyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, pentacyclo [6.5.1.1 3.6 . 0 2.7 . 0 9.13 ] -4-pentadecene, pentacyclo [6.6.1.1 3.6 . 0 2.7 . 0 9.14 ] -4-hexadecene, hexacyclo [6.6.1.1 3.6 . 1 10.13 . 0 2.7 . 0 9.14 ] -4-heptadecene and the like. These cyclic olefin compounds can be used singly or in combination of two or more. Among these cyclic olefin compounds, norbornene, tricyclo [4.3.0.1 2.5]-3-decene, tricyclo [4.4.0.1 2.5]-3-undecene, tetracyclo [4 4.0.1 2.5 . 1 7.10 ] -3-dodecene is preferred, and norbornene is particularly preferred.
本発明の共重合方法は、モノマー類と錯体金属触媒系の存在下、減圧、大気圧、加圧のいずれかの条件のもと、バルク、溶液、スラリーのいずれの方法でも行うことができる。
共重合を行うのに好適な温度範囲としては−３０℃〜２６０℃であり、好ましくは０℃〜２００℃である。また、共重合においては、窒素、アルゴン等の不活性ガス雰囲気下で行ってもよいし、エチレン雰囲気下で行ってもよい、またエチレン及び／又は炭素数３〜２０のα−オレフィン類と上記の不活性ガスの混合雰囲気下でもかまわない。さらに、分子量調節のために上記のガスに加えて、水素を共存させてもかまわない。また、触媒成分をアルミナ、塩化マグネシウム、シリカのような好適な担体に担持させて用いてもかまわない。また所望ならば、共重合に際して溶媒を用いることも出来る。共重合に用いるのに好適な溶媒としては、ヘキサン、シクロヘキサン等のアルカンをはじめとする炭化水素系溶媒とトルエン、ベンゼン、エチルベンゼン等の芳香族系の溶媒があげられる。
The copolymerization method of the present invention can be carried out in any of bulk, solution, and slurry under the conditions of reduced pressure, atmospheric pressure, and increased pressure in the presence of monomers and a complex metal catalyst system.
The temperature range suitable for carrying out the copolymerization is -30 ° C to 260 ° C, preferably 0 ° C to 200 ° C. The copolymerization may be performed in an inert gas atmosphere such as nitrogen or argon, or may be performed in an ethylene atmosphere, and ethylene and / or an α-olefin having 3 to 20 carbon atoms and the above-mentioned It may be in a mixed atmosphere of inert gas. Furthermore, hydrogen may be coexisted in addition to the above gas for molecular weight adjustment. Further, the catalyst component may be used by being supported on a suitable carrier such as alumina, magnesium chloride, or silica. If desired, a solvent can be used in the copolymerization. Suitable solvents for copolymerization include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene, and ethylbenzene.
共重合における好適な触媒量は［（生成ポリマー重量）ｋｇ］／［触媒（Ａ）成分１ｍｏｌ］＝１０ｋｇ／１ｍｏｌ〜１００００００ｋｇ／１ｍｏｌ程度のポリマーを与える量である。本発明における共重合後のポリマーの分離方法としては、例えば共重合液にアセトンまたは酸もしくはアルカリを混合したアルコール等の貧溶媒となる極性溶媒を加えて共重合体を沈澱させて回収する方法、反応液を撹拌下、熱湯中に投入後、溶媒と共に蒸留回収する方法、または直接反応液を加熱して溶媒を留去する方法等を挙げることができる。
本発明の環状オレフィン系共重合体の製造方法において、α−オレフィン系モノマー由来の繰り返し単位及び環状オレフィン系モノマー由来の繰り返し単位は各々２種類以上の成分から構成されていてもよく、三元あるいは四元以上の共重合体の製造も可能である。
本発明の環状オレフィン系共重合体の製造方法において、上記モノマー以外にも必要に応じて、スチレンのような芳香族ビニル化合物を共重合モノマーとして共重合することも可能である。
A suitable amount of catalyst in the copolymerization is an amount giving [(product polymer weight) kg] / [catalyst (A) component 1 mol] = 10 kg / 1 mol to 1000000 kg / 1 mol of polymer. As a method for separating a polymer after copolymerization in the present invention, for example, a method of adding a polar solvent that becomes a poor solvent such as acetone or an alcohol mixed with an acid or an alkali to the copolymer solution to precipitate and recover the copolymer, Examples thereof include a method in which the reaction solution is stirred into hot water and then distilled and recovered together with the solvent, or a method in which the solvent is distilled off by directly heating the reaction solution.
In the method for producing a cyclic olefin copolymer of the present invention, the repeating unit derived from an α-olefin monomer and the repeating unit derived from a cyclic olefin monomer may each be composed of two or more components, Quaternary or higher copolymers can also be produced.
In the method for producing a cyclic olefin copolymer of the present invention, an aromatic vinyl compound such as styrene can be copolymerized as a copolymerization monomer, if necessary, in addition to the above monomers.
本発明の環状オレフィン系共重合体の製造方法において、環状オレフィン系共重合体中の組成は、エチレン及び／又は炭素数３〜２０のα−オレフィン類１〜９９ｍｏｌ％に対し、環状オレフィン類９９〜１ｍｏｌ％の範囲で共重合できる。好ましくはエチレン及び／又は炭素数３〜２０のα−オレフィン類１０〜７５ｍｏｌ％に対し、環状オレフィン類９０〜２５ｍｏｌ％である。 In the method for producing a cyclic olefin copolymer of the present invention, the composition in the cyclic olefin copolymer is cyclic olefins 99 with respect to 1 to 99 mol% of ethylene and / or α-olefins having 3 to 20 carbon atoms. Copolymerization is possible in the range of ˜1 mol%. The cyclic olefins are preferably 90 to 25 mol% with respect to ethylene and / or 10 to 75 mol% of the α-olefin having 3 to 20 carbon atoms.
以下実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。錯体金属触媒は、J.Am.Chem.Soc., 122, 5499(2000)及びMacromolecules, 31, 7588(1998)を参考に調製した。
重合活性は重合終了後に得られたポリマー量から求めた。ポリマー中のノルボルネン含有量はMacromolecules, 33, 8931(2000)、シクロペンテン含有量はMacromolecules, 35, 9999(2002)、及びシクロヘキセン含有量はJ.Am.Chem.Soc., 127, 4582(2005) に従い、１３Ｃ−ＮＭＲスペクトルを用いて行った。ＮＭＲ測定はｄ６−ベンゼン／１，２，４−トリクロロベンゼン（１／１ｖｏｌ比）溶液中で行った。ポリマーのガラス転移温度（Ｔｇ）の測定は示差走査熱量計（ＤＳＣ）を用い、窒素雰囲気下２０℃／分の昇温速度で求めた。ポリマーの分子量はＧＰＣ法により１４０℃において、ｏ−ジクロルベンゼンを測定溶媒として、ＲＩにより検出し、ポリスチレン換算により求めた。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The complex metal catalyst was prepared with reference to J. Am. Chem. Soc., 122, 5499 (2000) and Macromolecules, 31, 7588 (1998).
The polymerization activity was determined from the amount of polymer obtained after completion of the polymerization. The norbornene content in the polymer is Macromolecules, 33, 8931 (2000), the cyclopentene content is Macromolecules, 35, 9999 (2002), and the cyclohexene content is according to J. Am. Chem. Soc., 127, 4582 (2005). , 13 C-NMR spectrum was used. NMR measurement was performed in a d 6 -benzene / 1,2,4-trichlorobenzene (1/1 vol ratio) solution. The glass transition temperature (Tg) of the polymer was measured using a differential scanning calorimeter (DSC) at a rate of temperature increase of 20 ° C./min in a nitrogen atmosphere. The molecular weight of the polymer was determined by the GPC method at 140 ° C., detected by RI using o-dichlorobenzene as a measurement solvent, and converted into polystyrene.
［参考例１］
ＣｐＴｉ（ｔ−Ｂｕ２Ｃ＝Ｎ）Ｃｌ２（以下、金属錯体−１）の合成
ＣｐＴｉＣｌ３（１．０ｇ，４．５５ｍｍｏｌ）を含むトルエン溶液（３０ｍｌ）中に、−７８℃でｔ−Ｂｕ２Ｃ＝ＮＬｉ（０．６７ｇ，４．５５ｍｍｏｌ）トルエン溶液（２０ｍｌ）を３０分間かけて滴下した。得られた反応溶液を、攪拌しつつゆっくりと室温まで上昇させ、終夜攪拌した。反応液をろ過した後、濃縮し、次いで−３０℃においてヘキサンより再結晶することにより、目的錯体を６０％の収率で得た。
ＮＭＲの測定結果は次の通りであった。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ６．１２（ｓ，３Ｈ），１．０４（ｓ，１８Ｈ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）：δ２０４．１（Ｃ＝Ｎ），１１７．１（Ｃｐ），４６．７１（ＣＣＨ３），３０．１６（Ｂｕ）．
[Reference Example 1]
CpTi (t-Bu 2 C = N) Cl 2 ( hereinafter, metal complexes -1) Synthesis CpTiCl 3 (1.0 g, 4.55 mmol) in toluene solution (30ml) containing, t-Bu at -78 ° C. 2 C = NLi (0.67 g, 4.55 mmol) in toluene (20 ml) was added dropwise over 30 minutes. The resulting reaction solution was slowly raised to room temperature while stirring and stirred overnight. The reaction solution was filtered, concentrated, and then recrystallized from hexane at −30 ° C. to obtain the target complex in a yield of 60%.
NMR measurement results were as follows.
1 H-NMR (CDCl 3 ): δ 6.12 (s, 3H), 1.04 (s, 18H)
13 C-NMR (CDCl 3 ): δ 204.1 (C═N), 117.1 (Cp), 46.71 (CCH 3 ), 30.16 (Bu).
［実施例１］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ３を真空下で除いて使用した。）を導入した。次いで、Ｎａ上で蒸留し脱水脱酸素処理したノルボルネンのトルエン溶液（濃度：２．５ｍｏｌ／ｌ）を１０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−１を０．０１μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝９．０×１０４ｋｇ／ｍｏｌ・Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝３．２×１０５（Ｍｗ／Ｍｎ＝２．０９）であった。ＤＳＣ測定より、Ｔｇ＝１４６℃であった。１３Ｃ−ＮＭＲから共重合体中のノルボルネン含有量は５８．８ｍｏｌ％と見積もられた。
[Example 1]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that the solvent toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 10 ml of a toluene solution (concentration: 2.5 mol / l) of norbornene distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 0.01 μmol of metal complex-1 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. The copolymerization activity of the polymer was = 9.0 × 10 4 kg / mol · Ti · h. From the GPC measurement, it was Mn = 3.2 × 10 5 (Mw / Mn = 2.09). It was Tg = 146 degreeC from DSC measurement. From 13 C-NMR, the norbornene content in the copolymer was estimated to be 58.8 mol%.
［実施例２］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ３を真空下で除いて使用した。）を導入した。次いで、Ｎａ上で蒸留し脱水脱酸素処理したノルボルネンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を１０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−１を０．０１μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝８．６×１０４ｋｇ／ｍｏｌ・Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝３．４×１０５（Ｍｗ／Ｍｎ＝２．００）であった。ＤＳＣ測定より、Ｔｇ＝１６７℃であった。１３Ｃ−ＮＭＲから共重合体中のノルボルネン含有量は６５．８ｍｏｌ％と見積もられた。
[Example 2]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that the solvent toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 10 ml of a toluene solution (concentration: 5.0 mol / l) of norbornene distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 0.01 μmol of metal complex-1 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity was 8.6 × 10 4 kg / mol · Ti · h. From the GPC measurement, it was Mn = 3.4 × 10 5 (Mw / Mn = 2.00). From DSC measurement, it was Tg = 167 degreeC. From 13 C-NMR, the norbornene content in the copolymer was estimated to be 65.8 mol%.
［実施例３］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ３を真空下で除いて使用した。）を導入した。次いで、Ｎａ上で蒸留し脱水脱酸素処理したシクロペンテンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を１０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−１を１．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝９０６ｋｇ／ｍｏｌ・Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝１．８×１０５（Ｍｗ／Ｍｎ＝２．０１）であった。１３Ｃ−ＮＭＲから共重合体中のシクロペンテン含有量は４３．１ｍｏｌ％と見積もられた。
[Example 3]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that the solvent toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 10 ml of a toluene solution (concentration: 5.0 mol / l) of cyclopentene distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 1.0 μmol of metal complex-1 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 906 kg / mol · Ti · h. From GPC measurement, it was Mn = 1.8 × 10 5 (Mw / Mn = 2.01). From 13 C-NMR, the cyclopentene content in the copolymer was estimated to be 43.1 mol%.
［実施例４］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ３を真空下で除いて使用した。）を導入した。次いで、Ｎａ上で蒸留し脱水脱酸素処理したシクロヘキセンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を１０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−１を１．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝１９４０ｋｇ／ｍｏｌ・Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝０．５×１０５（Ｍｗ／Ｍｎ＝１．８３）であった。１３Ｃ−ＮＭＲから共重合体中のシクロヘキセン含有量は０．３ｍｏｌ％と見積もられた。
[Example 4]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that the solvent toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 10 ml of a toluene solution (concentration: 5.0 mol / l) of cyclohexene distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 1.0 μmol of metal complex-1 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 1940 kg / mol · Ti · h. From GPC measurement, it was Mn = 0.5 × 10 5 (Mw / Mn = 1.83). From 13 C-NMR, the cyclohexene content in the copolymer was estimated to be 0.3 mol%.
［参考例２］
Ｃｐ＊Ｔｉ（２，６−ｉＰｒ２ＰｈＯ）Ｃｌ２（以下、金属錯体−２）の合成
Ｃｐ＊ＴｉＣｌ３（１．５５ｇ，５．３５ｍｍｏｌ）を含むトルエン溶液（２５ｍｌ）中に、−２５℃でＬｉＯ−２，６−ｉＰｒ２Ｐｈ（０．９９ｇ，５．３８ｍｍｏｌ）トルエン溶液（１５ｍｌ）を３０分間かけて滴下した。得られた反応溶液を、攪拌しつつゆっくりと室温まで上昇させ、終夜攪拌した。反応液をろ過した後、濃縮し、次いで−３０℃においてジクロロメタン／ヘキサンより再結晶することにより、目的錯体を６０％の収率で得た。
ＮＭＲの測定結果は次の通りであった。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ６．９９〜７．１５（ｍ，３Ｈ），３．４４（ｍ，２Ｈ），１．９５（ｓ，１５Ｈ），１．３１（ｄ，１２Ｈ）．
[Reference Example 2]
Synthesis of Cp * Ti (2,6- i Pr 2 PhO) Cl 2 (hereinafter referred to as metal complex-2) In a toluene solution (25 ml) containing Cp * TiCl 3 (1.55 g, 5.35 mmol), −25 LiO-2,6- i Pr 2 Ph (0.99 g, 5.38 mmol) in toluene (15 ml) was added dropwise at 30 ° C. over 30 minutes. The resulting reaction solution was slowly raised to room temperature while stirring and stirred overnight. The reaction solution was filtered, concentrated, and then recrystallized from dichloromethane / hexane at −30 ° C. to obtain the target complex in a yield of 60%.
NMR measurement results were as follows.
1 H-NMR (CDCl 3 ): δ 6.9-7.15 (m, 3H), 3.44 (m, 2H), 1.95 (s, 15H), 1.31 (d, 12H).
［比較例１］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ３を真空下で除いて使用した。）を導入した。次いで、Ｎａ上で蒸留し脱水脱酸素処理したノルボルネンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を１０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−２を５．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝２３８ｋｇ／ｍｏｌ・Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝５．３×１０４（Ｍｗ／Ｍｎ＝１．６３）であった。ＤＳＣ測定より、Ｔｇ＝８３℃であった。１３Ｃ−ＮＭＲから共重合体中のノルボルネン含有量は３７．５ｍｏｌ％と見積もられた。
[Comparative Example 1]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that the solvent toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 10 ml of a toluene solution (concentration: 5.0 mol / l) of norbornene distilled over Na and dehydrated and deoxygenated was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 5.0 μmol of metal complex-2 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 238 kg / mol · Ti · h. From the GPC measurement, it was Mn = 5.3 × 10 4 (Mw / Mn = 1.63). It was Tg = 83 degreeC from DSC measurement. From 13 C-NMR, the norbornene content in the copolymer was estimated to be 37.5 mol%.
本発明の製造方法を用いると、高い重合活性と高い共重合性を達成でき効率的に環状オレフィン系共重合体が得られる事が判る。
本発明を好ましい実施態様に関連して説明してきたが、当業者が容易に理解されるように本発明の原理及び範囲を逸脱することなく改変及び変更を実施し得ることを理解すべきである。従って、前記改変は本発明の範囲内で実施され得る。
It can be seen that when the production method of the present invention is used, high polymerization activity and high copolymerizability can be achieved, and a cyclic olefin copolymer can be obtained efficiently.
Although the invention has been described with reference to preferred embodiments, it is to be understood that modifications and changes can be made without departing from the principles and scope of the invention as will be readily appreciated by those skilled in the art. . Accordingly, such modifications can be implemented within the scope of the present invention.
本発明の方法によって、透明性、熱安定性に優れた新規な環状オレフィン系共重合体を工業的に効率良く製造することが可能となった。 According to the method of the present invention, it has become possible to industrially efficiently produce a novel cyclic olefin copolymer excellent in transparency and thermal stability.
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| WO2015178144A1 (en) * | 2014-05-23 | 2015-11-26 | ポリプラスチックス株式会社 | Method for producing cyclic olefin copolymer |
| JP2018150273A (en) * | 2017-03-13 | 2018-09-27 | 三井化学株式会社 | Transition metal compound, olefin polymerization catalyst, and olefin polymer production method |
| JP2021073223A (en) * | 2021-01-18 | 2021-05-13 | 三井化学株式会社 | Manufacturing method of transition metal compound, olefin polymerization catalyst, and olefin polymer |
| JPWO2022024549A1 (en) * | 2020-07-31 | 2022-02-03 |
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| WO2015178144A1 (en) * | 2014-05-23 | 2015-11-26 | ポリプラスチックス株式会社 | Method for producing cyclic olefin copolymer |
| JP2015221874A (en) * | 2014-05-23 | 2015-12-10 | ポリプラスチックス株式会社 | Method for producing cyclic olefin copolymer |
| JP2018150273A (en) * | 2017-03-13 | 2018-09-27 | 三井化学株式会社 | Transition metal compound, olefin polymerization catalyst, and olefin polymer production method |
| JPWO2022024549A1 (en) * | 2020-07-31 | 2022-02-03 | ||
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| JP7175426B2 (en) | 2020-07-31 | 2022-11-18 | ポリプラスチックス株式会社 | Method for producing cyclic olefin copolymer |
| JP2021073223A (en) * | 2021-01-18 | 2021-05-13 | 三井化学株式会社 | Manufacturing method of transition metal compound, olefin polymerization catalyst, and olefin polymer |
| JP6997887B2 (en) | 2021-01-18 | 2022-01-18 | 三井化学株式会社 | Methods for Producing Transition Metal Compounds, Catalysts for Olefin Polymerization, and Olefin Polymers |
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