WO2022070959A1 - 環状オレフィン共重合体の製造方法 - Google Patents
環状オレフィン共重合体の製造方法 Download PDFInfo
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- WO2022070959A1 WO2022070959A1 PCT/JP2021/034140 JP2021034140W WO2022070959A1 WO 2022070959 A1 WO2022070959 A1 WO 2022070959A1 JP 2021034140 W JP2021034140 W JP 2021034140W WO 2022070959 A1 WO2022070959 A1 WO 2022070959A1
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- WIPO (PCT)
- Prior art keywords
- group
- cyclic olefin
- olefin copolymer
- substituted
- carbon atoms
- Prior art date
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 59
- 239000004713 Cyclic olefin copolymer Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 52
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 51
- 125000005843 halogen group Chemical group 0.000 claims abstract description 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005977 Ethylene Substances 0.000 claims abstract description 42
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 33
- 125000001424 substituent group Chemical group 0.000 claims abstract description 32
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- -1 borate compound Chemical class 0.000 claims description 68
- 238000006116 polymerization reaction Methods 0.000 claims description 63
- 125000004432 carbon atom Chemical group C* 0.000 claims description 59
- 239000002904 solvent Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 150000002430 hydrocarbons Chemical group 0.000 claims description 15
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000001905 inorganic group Chemical group 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 33
- 239000003446 ligand Substances 0.000 abstract description 33
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 150000008040 ionic compounds Chemical class 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- WLTSXAIICPDFKI-UHFFFAOYSA-N 3-dodecene Chemical compound CCCCCCCCC=CCC WLTSXAIICPDFKI-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003426 co-catalyst Substances 0.000 description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- 150000002848 norbornenes Chemical class 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 101150096839 Fcmr gene Proteins 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 238000002360 preparation method Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 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 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- ROMPPAWVATWIKR-UHFFFAOYSA-N 4-[3-(4-chlorophenyl)-1,2,4-oxadiazol-5-yl]butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2C=CC(Cl)=CC=2)=N1 ROMPPAWVATWIKR-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 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
- 239000000460 chlorine Substances 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000008096 xylene Substances 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- LCSLWNXVIDKVGD-KQQUZDAGSA-N (3e,7e)-deca-3,7-diene Chemical compound CC\C=C\CC\C=C\CC LCSLWNXVIDKVGD-KQQUZDAGSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
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- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- GDGDLBOVIAWEAD-UHFFFAOYSA-N 2,4-ditert-butyl-6-(3,5-ditert-butyl-2-hydroxyphenyl)phenol Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC(C=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O GDGDLBOVIAWEAD-UHFFFAOYSA-N 0.000 description 1
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- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
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- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
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- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- XUFPYLQWLKKGDQ-UHFFFAOYSA-N 4,4a,9,9a-tetrahydro-1,4-methano-1h-fluorene Chemical compound C12CC3=CC=CC=C3C1C1C=CC2C1 XUFPYLQWLKKGDQ-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- BSFWGXOMEGLIPL-UHFFFAOYSA-N 4-prop-1-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=CC)C2 BSFWGXOMEGLIPL-UHFFFAOYSA-N 0.000 description 1
- JGLIHSMBVDZMSA-UHFFFAOYSA-N 5-(cyclohexen-1-yl)bicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CCCCC1 JGLIHSMBVDZMSA-UHFFFAOYSA-N 0.000 description 1
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 description 1
- DGBJYYFKBCUCNY-UHFFFAOYSA-N 5-cyclopentylbicyclo[2.2.1]hept-2-ene Chemical compound C1CCCC1C1C(C=C2)CC2C1 DGBJYYFKBCUCNY-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
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-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
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- GOLQZWYZZWIBCA-UHFFFAOYSA-N 5-octylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCC)CC1C=C2 GOLQZWYZZWIBCA-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- KGCRXHYTNRMHCF-UHFFFAOYSA-N 6-methyl-2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(C)O1 KGCRXHYTNRMHCF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HFYDURKIHZTKOL-UHFFFAOYSA-N CC(C)C(C(C)C)[AlH]C Chemical compound CC(C)C(C(C)C)[AlH]C HFYDURKIHZTKOL-UHFFFAOYSA-N 0.000 description 1
- YDNAWKQOSYKOSA-UHFFFAOYSA-N CCC(C)[Zn]C(C)CC Chemical compound CCC(C)[Zn]C(C)CC YDNAWKQOSYKOSA-UHFFFAOYSA-N 0.000 description 1
- JUCGLXJRZMNKAH-UHFFFAOYSA-N CCCCCCCC[Zn]CCCCCCCC Chemical compound CCCCCCCC[Zn]CCCCCCCC JUCGLXJRZMNKAH-UHFFFAOYSA-N 0.000 description 1
- DJYPUWSOJVBRTK-UHFFFAOYSA-N CCCCCCC[Zn]CCCCCCC Chemical compound CCCCCCC[Zn]CCCCCCC DJYPUWSOJVBRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- LSUIGMCLAKWIED-UHFFFAOYSA-M [Cl-].CC(C)C[Zn+] Chemical compound [Cl-].CC(C)C[Zn+] LSUIGMCLAKWIED-UHFFFAOYSA-M 0.000 description 1
- GTIVDIGFCBZLEE-UHFFFAOYSA-M [Cl-].CC[Zn+] Chemical compound [Cl-].CC[Zn+] GTIVDIGFCBZLEE-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 1
- UUDFOWYDKXNYTK-UHFFFAOYSA-N di(butan-2-yl)alumane Chemical compound CCC(C)[AlH]C(C)CC UUDFOWYDKXNYTK-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 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
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- DZZKHRZZALRSLB-UHFFFAOYSA-N hexylaluminum Chemical compound CCCCCC[Al] DZZKHRZZALRSLB-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical group C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- MNBIQZQDQOPSKO-UHFFFAOYSA-N pentadeca-1,3,5,10-tetraene Chemical compound CCCCC=CCCCC=CC=CC=C MNBIQZQDQOPSKO-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PMTPAGVGEXGVNI-UHFFFAOYSA-N tetracyclo[10.2.1.02,11.04,9]pentadeca-2,4,6,13-tetraene Chemical compound C12=CC3=CC=CCC3CC2C2CC1C=C2 PMTPAGVGEXGVNI-UHFFFAOYSA-N 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- OUZWXMBUAMCJMH-UHFFFAOYSA-N tetradeca-1,3,5,10-tetraene Chemical compound CCCC=CCCCC=CC=CC=C OUZWXMBUAMCJMH-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- SDTYFWAQLSIEBH-UHFFFAOYSA-N undec-3-ene Chemical compound CCCCCCCC=CCC SDTYFWAQLSIEBH-UHFFFAOYSA-N 0.000 description 1
- LMISWUPDWKMCIH-UHFFFAOYSA-N undeca-3,7-diene Chemical compound CCCC=CCCC=CCC LMISWUPDWKMCIH-UHFFFAOYSA-N 0.000 description 1
- AZGPUOZQDCSPRB-UHFFFAOYSA-N undeca-3,8-diene Chemical compound CCC=CCCCC=CCC AZGPUOZQDCSPRB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000051 zinc hydride Inorganic materials 0.000 description 1
- ABIAVOPWHAWUGT-UHFFFAOYSA-N zinc;2-methanidylpropane Chemical compound [Zn+2].CC(C)[CH2-].CC(C)[CH2-] ABIAVOPWHAWUGT-UHFFFAOYSA-N 0.000 description 1
- NMLXKNNXODLJIN-UHFFFAOYSA-M zinc;carbanide;chloride Chemical compound [CH3-].[Zn+]Cl NMLXKNNXODLJIN-UHFFFAOYSA-M 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
- 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
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
Definitions
- the present invention relates to a method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene.
- Cyclic olefin homopolymers and cyclic olefin copolymers have low hygroscopicity and high transparency, and are used in various applications including the field of optical materials such as optical disk substrates, optical films, and optical fibers.
- As a typical cyclic olefin copolymer there is a copolymer of cyclic olefin and ethylene, which is widely used as a transparent resin. Since the glass transition temperature of the copolymer of cyclic olefin and ethylene can be changed according to the copolymer composition of cyclic olefin and ethylene, the coweight in which the glass transition temperature (Tg) is adjusted in a wide temperature range. Coagulation can be produced (see, eg, Non-Patent Document 1).
- Non-Patent Document 1 there is a problem that a copolymer of cyclic olefin and ethylene cannot be produced in high yield.
- a highly active catalyst As a countermeasure against this problem, it is conceivable to carry out polymerization using a highly active catalyst.
- polymerization is carried out using a highly active catalyst for the purpose of increasing the production efficiency of the cyclic olefin copolymer, polyethylene-like impurities may be easily generated.
- the cyclic olefin copolymer contains polyethylene-like impurities, turbidity occurs when the cyclic olefin copolymer is dissolved in a solvent.
- the cyclic olefin copolymer contains polyethylene-like impurities, there is a concern that the transparency of the cyclic olefin copolymer may decrease. Further, when polyethylene-like impurities are generated, in a general production process for producing a cyclic olefin copolymer, a process of filtering and removing insoluble polyethylene-like impurities is required, which increases the production cost.
- the present invention has been made in view of the above problems, and the cyclic olefin copolymer is made efficient by copolymerizing a norbornene monomer and a monomer containing ethylene while suppressing the formation of polyethylene-like impurities. It is an object of the present invention to provide a method for producing a cyclic olefin copolymer that can be produced well.
- the present inventors have substituted the norbornene monomer and the monomer containing ethylene with an alkyl group which may be substituted with a halogen atom or a trialkylsilyl group, and the cyclos satisfy specific conditions for the substituent.
- a method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene At least, the norbornene monomer and ethylene are charged into the polymerization vessel as monomers, and Including polymerizing the monomers in the polymerization vessel in the presence of a metallocene catalyst,
- the metallocene catalyst has the following formula (a1): (In the formula (a1), M is Ti, Zr, or Hf, and R a1 to R a5 are alkyl groups or trialkylsilyl groups which may be the same or different, and may be substituted with a hydrogen atom or a halogen atom, respectively.
- At least one of R a1 to R a5 is an alkyl group or a trialkylsilyl group which may be substituted with a halogen atom.
- R a1 to R a5 is an alkyl group which may be substituted with a halogen atom or a trialkylsilyl group
- an alkyl group which may be substituted with a halogen atom or a trialkylsilyl group is 1 or more and 10 or less.
- R a1 to R a5 When two or more of R a1 to R a5 are alkyl groups or trialkylsilyl groups which may be substituted with halogen atoms, the total number of carbon atoms and silicon atoms for each of R a1 to R a5 is totaled.
- R a1 to R a5 contains an alkyl group or a trimethylsilyl group which may be substituted with a halogen atom having 2 or more and 4 or less carbon atoms
- R a1 to R Only one of a5 is an alkyl group or a trimethylsilyl group which may be substituted with a halogen atom having 2 or more and 4 or less carbon atoms.
- Two adjacent groups on the 5-membered ring of R a1 to R a5 may be bonded to each other to form a hydrocarbon ring, and X may contain a heteroatom from 1 to 1 carbon atom.
- 20 organic substituents or halogen atoms L is the following formula (a1a): It is a group represented by In the formula (a1a), Ra6 and Ra7 may be independently the same or different from each other, and may contain a hydrogen atom, a heteroatom, an organic substituent having 1 to 20 carbon atoms, or an inorganic group. It is a substituent, and the two groups Ra 6 and Ra 7 may be bonded to each other to form a ring.
- a production method which is a compound represented by.
- the DSC curve obtained by measuring the cyclic olefin copolymer sample with a differential scanning calorimeter under the conditions of a nitrogen atmosphere and a heating rate of 20 ° C./min according to the method described in JIS K7121 is obtained.
- a cyclic olefin copolymer capable of efficiently producing a cyclic olefin copolymer by copolymerizing a norbornene monomer and a monomer containing ethylene while suppressing the generation of polyethylene-like impurities.
- a manufacturing method can be provided.
- a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene is produced.
- the manufacturing method is At least, the norbornene monomer and ethylene are charged into the polymerization vessel as monomers, and It comprises polymerizing the monomers in the polymerization vessel in the presence of a metallocene catalyst.
- charging the norbornene monomer and ethylene as monomers into the polymerization vessel is also referred to as a charging step.
- polymerizing the monomer in the polymerization vessel in the presence of a metallocene catalyst is also referred to as a polymerization step.
- the monomer in the polymerization vessel is polymerized in the presence of a metallocene catalyst.
- the metallocene catalyst will be described in detail later.
- the norbornene monomer and ethylene are charged into the polymerization vessel as monomers.
- the polymerization vessel may be charged with a norbornene monomer and a monomer other than ethylene as long as the object of the present invention is not impaired.
- the total of the ratio of the constituent units derived from the norbornene monomer and the ratio of the constituent units derived from ethylene in the cyclic olefin copolymer is typically 80% by mass or more with respect to all the constituent units. It is preferably 95% by mass or more, more preferably 95% by mass or more. 98% by mass or more is more preferable.
- the norbornene monomer and other monomers other than ethylene are not particularly limited as long as they can be copolymerized with the norbornene monomer and ethylene.
- Typical examples of such other monomers include ⁇ -olefins.
- the ⁇ -olefin may be substituted with at least one substituent such as a halogen atom.
- ⁇ -olefin C3 to C12 ⁇ -olefins are preferable.
- the ⁇ -olefins C3 to C12 are not particularly limited, and are, for example, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1.
- 1-hexene, 1-octene, and 1-decene are preferable.
- the method of charging ethylene into the polymerization solution is not particularly limited as long as a desired amount of ethylene can be charged in the polymerization container.
- ethylene is charged into the polymerization vessel so that the charging pressure of ethylene in the polymerization vessel is 0.5 MPa or more.
- the ethylene charging pressure is preferably 0.55 MPa or more, more preferably 0.6 MPa or more.
- Increasing the ethylene charging pressure can reduce the amount of catalyst used per produced polymer.
- the ethylene charging pressure is, for example, preferably 10 MPa or less, more preferably 5 MPa or less, still more preferably 3 MPa or less.
- a solvent may be charged in the polymerization vessel together with the norbornene monomer and ethylene.
- the solvent is not particularly limited as long as it is a solvent that does not inhibit the polymerization reaction.
- Preferred solvents include hydrocarbon solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, and halogenated hydrocarbon solvents, which are excellent in handleability, thermal stability, and chemical stability. Solvents are preferred, and aliphatic hydrocarbon solvents are more preferred.
- preferable solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, and decahydronaphthalene (decalin), and benzene, toluene, and xylene.
- aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, and decahydronaphthalene (decalin), and benzene, toluene, and xylene.
- aromatic hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and halogenated hydrocarbon solvents such as
- the lower limit of the concentration of the norbornene monomer is preferably, for example, 0.5% by mass or more, and more preferably 10% by mass or more.
- the upper limit for example, 50% by mass or less is preferable, and 35% by mass or less is more preferable.
- norbornene monomer examples include norbornene and substituted norbornene, and norbornene is preferable.
- the norbornene monomer can be used alone or in combination of two or more.
- the substituted norbornene is not particularly limited, and examples of the substituent contained in the substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include compounds represented by the following general formula (I).
- R 1 to R 12 may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
- R 9 and R 10 and R 11 and R 12 may be integrated to form a divalent hydrocarbon group.
- R 9 or R 10 and R 11 or R 12 may form a ring with each other.
- n indicates 0 or a positive integer.
- R 1 to R 12 in the general formula (I) may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
- R 1 to R 8 include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having 1 to 20 carbon atoms, and the like, which may be different from each other. , Partially different, or all may be the same.
- R 9 to R 12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group and a trill.
- Substituent or unsubstituted aromatic hydrocarbon groups such as groups, ethylphenyl groups, isopropylphenyl groups, naphthyl groups, anthryl groups; benzyl groups, phenethyl groups, and other alkyl groups substituted with aryl groups such as aralkyl groups. They can be different, partially different, or all identical.
- R 9 and R 10 or R 11 and R 12 are integrated to form a divalent hydrocarbon group
- a divalent hydrocarbon group include, for example, an alkylidene group such as an ethylidene group, a propyridene group, and an isopropylidene group. Can be mentioned.
- the formed ring may be a monocyclic ring, a polycyclic ring, or a polycyclic ring having a crosslink. , It may be a ring having a double bond, or it may be a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.
- substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo [2.2.1] hepta-2-ene and 5,5-dimethyl-bicyclo [2.2.1] hepta-. 2-ene, 5-ethyl-bicyclo [2.2.1] hepta-2-ene, 5-butyl-bicyclo [2.2.1] hepta-2-ene, 5-ethylidene-bicyclo [2.2.
- Cyclic olefin of the ring Tetracyclo [4.4.0.1 2,5 . 17 and 10 ]
- Dodeca-3-ene also simply referred to as tetracyclododecene
- 8-methyltetracyclo 4.4.0.1 2,5 . 17 and 10
- Dodeca-3-ene, 8-ethyltetracyclo 4.4.0.1 2,5 . 1 7 , 10]
- Tetradeca-4,9,11,13-tetraene also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene
- tetracyclo 8.4.1, 4,7 . 0 1,10 1 .
- Pentadeca-5,10,12,14-tetraene also referred to as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene
- pentacyclo [6.6.1. 1 3, 6 . 0 2,7 . 09,14 ] -4-hexadecene
- pentacyclo [6.5.1.1 3,6 . 0 2,7 . 09,13 ] -4-pentadecene
- alkyl-substituted norbornene eg, bicyclo [2.2.1] hepta-2-ene substituted with one or more alkyl groups
- alkylidene-substituted norbornene eg, bicyclo substituted with one or more alkylidene groups
- [2.2.1] hepta-2-ene) is preferred, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene). ) Is particularly preferable.
- the monomers in the polymerization vessel are polymerized in the presence of a metallocene catalyst that meets predetermined requirements.
- the temperature at the time of polymerization is not particularly limited. Since the yield of the cyclic olefin copolymer is good, the temperature at the time of polymerization is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, still more preferably 60 ° C. or higher. 70 ° C. or higher is particularly preferable.
- the temperature at the time of polymerization may be 80 ° C. or higher.
- the upper limit of the temperature at the time of polymerization is not particularly limited, and the upper limit of the temperature at the time of polymerization may be, for example, 200 ° C. or lower, 140 ° C. or lower, or 120 ° C. or lower.
- a metallocene catalyst a metallocene compound represented by the following formula (a1) is used.
- L is a group represented by the following formula (a1a).
- M is Ti, Zr, or Hf, and Ti is particularly preferable in terms of easy acquisition and production of a metallocene catalyst, activity of the catalyst, and the like.
- Ra1 to Ra5 are independently the same or different, and are an alkyl group or a trialkylsilyl group which may be substituted with a hydrogen atom or a halogen atom. At least one of R a1 to R a5 is an alkyl group or a trialkylsilyl group which may be substituted with a halogen atom. When only one of R a1 to R a5 is an alkyl group which may be substituted with a halogen atom or a trialkylsilyl group, an alkyl group which may be substituted with a halogen atom or a trialkylsilyl group.
- the total number of carbon atoms and the number of silicon atoms is 1 or more and 10 or less.
- R a1 to R a5 are alkyl groups or trialkylsilyl groups which may be substituted with halogen atoms, the total number of carbon atoms and silicon atoms for each of R a1 to R a5 is totaled.
- R a1 to R a5 contains an alkyl group or a trimethylsilyl group which may be substituted with a halogen atom having 2 or more and 4 or less carbon atoms
- R a1 to R Only one of a5 is an alkyl group or a trimethylsilyl group which may be substituted with a halogen atom having 2 or more and 4 or less carbon atoms.
- Two adjacent groups on the 5-membered ring of R a1 to R a5 may be bonded to each other to form a hydrocarbon ring.
- the total value of the number of carbon atoms and the number of silicon atoms for each of R a1 to R a5 is the number of carbon atoms and the number of silicon atoms of R a1 , the number of carbon atoms and the number of silicon atoms of R a2 , and R a3 . It is the total value of the number of carbon atoms and the number of silicon atoms of R a4 , the number of carbon atoms and the number of silicon atoms of Ra4, and the number of carbon atoms and the number of silicon atoms of Ra5 .
- the number of carbon atoms of the alkyl group which may be substituted with halogen atoms as R a1 to R a5 is 1 or more and 10 or less, preferably 1 or more and 4 or less.
- the alkyl group which may be substituted with a halogen atom as R a1 to R a5 may be linear or branched chain.
- the alkyl group as R a1 to R a5 may be substituted with a halogen atom.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and the halogen atom is preferably a fluorine atom.
- R a1 to R a5 are unsubstituted alkyl groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-. Examples thereof include a butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
- alkyl group substituted with the halogen atom as R a1 to R a5 are fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl. The group is mentioned.
- the total number of carbon atoms and the number of silicon atoms of the trialkylsilyl group as R a1 to R a5 is 4 or more and 10 or less, preferably 4 or more and 7 or less, and 4 is more preferable.
- Preferred specific examples of the trialkylsilyl group as R a1 to R a5 include a trimethylsilyl group, a dimethyl (ethyl) silyl group, and a triethylsilyl group.
- a trimethylsilyl group and a triethylsilyl group are preferable, and a trimethylsilyl group is particularly preferable.
- Ra1 to Ra5 are hydrogen atoms or methyl groups, and one of Ra1 to Ra5 is a trialkylsilyl group. Is preferable.
- Table 1 shows the total value of the number of carbon atoms and the number of silicon atoms for each of R a1 to R a5 .
- the abbreviations in Table 1 are as follows.
- At least one of Ra1 to Ra5 is an alkyl group or a trialkylsilyl group which may be substituted with a halogen atom.
- an unsubstituted alkyl group which is an electron donating group and a trialkylsilyl group are preferable.
- the substituted cyclopentadiene is used in the metallocene compound represented by the formula (a1). The coordination strength of the ligand derived from the above to the central metal M is increased.
- the ligand derived from the substituted cyclopentadiene may be substituted with an alkyl group or a trialkylsilyl group so as to satisfy the above-mentioned predetermined conditions regarding the number of carbon atoms and the number of silicon atoms.
- the group represented by the formula (a1a) is rotated to obtain a stable arrangement, and a sufficiently wide reaction field is formed in the vicinity of the central metal M of the metallocene compound represented by the formula (a1). Secured.
- the structure and number of substituents bonded to the cyclopentadiene ring so as to satisfy the above-mentioned carbon atom number and silicon atom number for Ra1 to Ra5 . Is restricted. This also ensures a stable arrangement by rotating the group represented by the formula (a1a), and secures a sufficiently wide reaction field in the vicinity of the central metal M of the metallocene compound represented by the formula (a1). Will be done.
- X is an organic substituent or a halogen atom having 1 to 20 carbon atoms which may contain a heteroatom.
- the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom when the organic substituent contains a hetero atom, the type of the hetero atom is not particularly limited as long as the object of the present invention is not impaired.
- the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, a halogen atom and the like.
- the organic substituent is not particularly limited as long as it is a group that does not inhibit the reaction for producing the metallocene compound represented by the above formula (a1).
- an alkyl group having 1 to 20 carbon atoms an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, and ⁇ -.
- Examples thereof include a mono-substituted amino group substituted with 20 hydrocarbon groups and a di-substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
- an alkyl group having 1 to 6 carbon atoms an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aliphatic acyl having 2 to 6 carbon atoms.
- a group, a benzoyl group, a phenyl group, a benzyl group, a phenethyl group, and a trialkylsilyl group having 3 to 10 carbon atoms are preferable.
- Isobutyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, phenyl group, trimethylsilyl group, and tert-butyldimethylsilyl group are more preferable.
- a halogen atom is preferable, a chlorine atom and a bromine atom are more preferable, and a chlorine atom is particularly preferable.
- Ra6 and Ra7 may be independently the same or different from each other, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substance. It is a substituent.
- the two groups R a6 and R a7 may be bonded to each other to form a ring.
- Specific examples and preferred examples of organic substituents having 1 to 20 carbon atoms which may contain heteroatoms as R a6 and R a7 may contain heteroatoms as R a1 to R a5 . The same applies to specific examples and preferred examples of good organic substituents having 1 to 20 carbon atoms.
- a mono-substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms and a di-substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms are also preferable as the organic substituent.
- a suitable example of the hydrocarbon group having 1 to 20 carbon atoms bonded to the nitrogen atom is R a1 to.
- Preferred examples of organic substituents for R a5 include hydrocarbon groups.
- the inorganic substituents of R a6 and R a7 in the formula (a1a) are not particularly limited as long as they do not inhibit the reaction for producing the metallocene compound represented by the above formula (a1).
- Specific examples of the inorganic substituent include a halogen atom, a nitro group, an unsubstituted amino group, a cyano group and the like.
- Preferred examples of the group represented by the formula (a1a) include the groups represented by L1 to L5 below, and the group represented by L1 is more preferable.
- the ligand derived from the substituted cyclopentadiene in the formula (a1) is the ligands 1 to 28 described in Table 1 above.
- examples thereof include metallocene compounds in which the two Xs in the formula (a1) are both halogen atoms and the group represented by the formula (a1a) is a group represented by L1.
- Ti is preferable as the central metal M.
- the ligand derived from the substituted cyclopentadiene in the formula (a1) has high catalytic activity and can efficiently generate a cyclic olefin copolymer even when the polymerization reaction is carried out for a long time.
- the ligand 1, the ligand 5 to the ligand 8, the ligand 15, or the ligand 24 shown in Table 1, and the two Xs in the formula (a1) are both halogen atoms, and the formula ( A metallocene compound in which the group represented by a1a) is the group represented by L1 and the central metal M is Ti is preferable.
- the ligand derived from the substituted cyclopentadiene in the formula (a1) is more preferably the ligand 5, the ligand 8, the ligand 15, or the ligand 24 shown in Table 1. It is more preferably the position 15 or the ligand 24.
- the ligand derived from the substituted cyclopentadiene in the formula (a1) is any one of the ligands 20 to 23 shown in Table 1.
- the two Xs of the formula (a1) are both halogen atoms, the group represented by the formula (a1a) is the group represented by L1, and the metallocene compound in which the central metal M is Ti is preferable.
- the ligand derived from the substituted cyclopentadiene in the formula (a1) is more preferably the ligand 20 or the ligand 23 shown in Table 1.
- the monomer in the polymerization vessel is polymerized in the presence of the above-mentioned metallocene catalyst.
- the polymerization of the monomer is preferably carried out in the presence of the above-mentioned metallocene catalyst and co-catalyst.
- a compound generally used as a co-catalyst in the polymerization of olefins can be used without particular limitation.
- the co-catalyst include aluminoxane and ionic compounds. From the viewpoint that the polymerization reaction easily proceeds, the polymerization of the monomer is particularly preferably carried out using at least one of aluminoxane and a borate compound as an ionic compound as a co-catalyst.
- a metallocene catalyst and at least one of an aluminoxane and a borate compound.
- the metallocene catalyst is preferably mixed with aluminoxane and / or an ionic compound to form a catalyst composition.
- the ionic compound is a compound that produces a cationic transition metal compound by reaction with a metallocene catalyst.
- the catalyst composition is preferably prepared using a solution of a metallocene catalyst.
- the solvent contained in the metallocene catalyst solution is not particularly limited.
- Preferred solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), and mineral oil, and benzene, toluene, and xylene.
- aromatic hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and halogenated hydrocarbon solvents such as chlorobenzene.
- the amount of the solvent used is not particularly limited as long as the catalyst composition having the desired performance can be produced.
- the concentrations of the metallocene catalyst, aluminoxane, and the ionic compound are preferably 0.00000001 to 100 mol / L, more preferably 0.00000005 to 50 mol / L, and particularly preferably 0.0000001 to 20 mol / L.
- a quantity of solvent is used.
- the number of moles of the transition metal element in the metallocene catalyst is Ma
- the number of moles of aluminum in the aluminoxane is M b1
- the number of moles of the ionic compound is M b2 .
- the liquid containing the raw material of the catalyst composition is mixed so that the value of (M b1 + M b2 ) / Ma is preferably 1 to 200,000, more preferably 5 to 100,000, and particularly preferably 10 to 80,000. It is preferable to be.
- the temperature at which the liquid containing the raw material of the catalyst composition is mixed is not particularly limited, but is preferably -100 to 100 ° C, more preferably -50 to 50 ° C.
- the mixing of the metallocene catalyst solution for preparing the catalyst composition with the aluminoxane and / or the ionic compound may be carried out in a device separate from the polymerization vessel before the polymerization, and the polymerization is carried out in the polymerization vessel. It may be done before or during polymerization.
- aluminoxan As the alkynexane, various aluminoxanes conventionally used as co-catalysts and the like in the polymerization of various olefins can be used without particular limitation.
- the aluminoxane is an organic aluminoxane.
- one type of aluminoxane may be used alone, or two or more types may be used in combination.
- an alkylaluminoxane is preferably used as the aluminoxane.
- the alkylaluminoxane include compounds represented by the following formulas (b1-1) or (b1-2).
- the alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by reacting trialkylaluminum with water.
- R represents an alkyl group having 1 to 4 carbon atoms
- n represents an integer of 0 to 40, preferably 2 to 30).
- alkylaluminoxane examples include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of methylaluminoxane is replaced with another alkyl group.
- modified methylaluminoxane for example, as the substituted alkyl group, a modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group is preferable, and in particular, a modified methylaluminoxane is preferable.
- a modified methylaluminoxane in which a part of the methyl group is replaced with an isobutyl group is more preferable.
- the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxan, butylaluminoxane, isobutylaluminoxan, methylethylaluminoxan, methylbutylaluminoxan, methylisobutylaluminoxan and the like, and among them, methylaluminoxane and methylisobutylaluminoxan are preferable.
- Alkyl aluminoxane can be prepared by a known method. Further, as the alkylaluminoxane, a commercially available product may be used. Examples of commercially available alkylaluminoxane products include MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Toso Finechem Co., Ltd.), methylaluminoxane solution (manufactured by Albemarle Corporation), and the like. .. It is more preferable to use an alkylaluminoxane other than solid MAO because it is easy to suppress the formation of polyethylene-like impurities.
- the ionic compound is a compound that produces a cationic transition metal compound by reacting with a metallocene catalyst.
- ionic compounds include tetrakis (pentafluorophenyl) borate anions, amine cations having active protons such as dimethylphenylammonium cations ((CH 3 ) 2 N (C 6 H 5 ) H + ), (C 6 H). 5 )
- Ionic compounds containing ions such as trisubstituted carbonium cations such as 3C + , carborane cations, metal carborane cations, and ferrosenium cations with transition metals can be used.
- a suitable example of an ionic compound is borate.
- Preferred specific examples of borate are tetrakis (pentafluorophenyl) trityl borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-methyldinormaldecyl.
- Examples thereof include N-methyldialkylammonium tetrakis (pentafluorophenyl) borate such as ammonium tetrakis (pentafluorophenyl) borate.
- the aluminoxane or a plurality of phenolic hydroxyl groups are placed in the polymerization vessel before the metallocene catalyst or the catalyst composition containing the metallocene catalyst is added. It is preferable to have one or more selected from aromatic compounds having one or a plurality of halogen atoms on the aromatic ring and hindered phenol. In the above aromatic compound having a phenolic hydroxyl group and a halogen atom, the phenolic hydroxyl group and the halogen atom are bonded on the same aromatic ring which may be a monocyclic ring or a fused ring.
- Hindered phenols are phenols having a bulky substituent at at least one of the two adjacent positions of the phenolic hydroxyl group.
- the bulky substituent include an alkyl group other than the methyl group such as an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl tree, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and an alkoxy group. , Aryloxy group, substituted amino group, alkylthio group, arylthio group and the like.
- hindered phenol examples include, for example, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-.
- BHT 2,6-di-tert-butyl-p-cresol
- Hindered phenol contributes to the increase in yield of the cyclic olefin copolymer by reacting with the alkylaluminum compound in the polymerization system.
- hindered phenol is preferably used with alkylaluminum.
- the hindered phenol may be used by mixing with alkylaluminum in the polymerization machine. A mixture obtained by mixing alkylaluminum and hindered phenol before polymerization may be introduced into the polymerization machine.
- Aluminoxane is as described in the method for producing the catalyst composition.
- the amount used is preferably 1 to 1,000,000 mol as the number of moles of aluminum in the aluminoxane with respect to 1 mol of the metallocene catalyst. More preferably, 10 to 100,000 mol.
- the polymerization is carried out in the presence of a metallocene catalyst, aluminoxane and hindered phenol, or in the presence of a metallocene catalyst, an ionic compound and hindered phenol.
- the alkyl metal compound may be added to the catalyst composition or may be supplied to the polymerization vessel separately from the catalyst composition.
- the alkyl metal compound it is preferable to use at least one of an alkyl aluminum compound having at least one alkyl group bonded to an Al atom and an alkyl zinc compound having at least one alkyl group bonded to a Zn atom.
- the norbornene monomer and the monomer containing ethylene can be copolymerized while suppressing the formation of polyethylene-like impurities and the excessive increase in molecular weight.
- the cyclic olefin copolymer can be efficiently produced.
- the alkyl metal compound may be used alone or in combination of two or more.
- alkylaluminum compound a compound conventionally used for polymerization of olefins and the like can be used without particular limitation.
- alkylaluminum compound examples include compounds represented by the following general formula (II).
- R 01 is an alkyl group having 1 to 15 carbon atoms
- X is a halogen atom or a hydrogen atom
- z1 is an integer of 1 to 3).
- the number of carbon atoms of the alkyl group as R 01 is 1 to 15, and 1 to 8 is more preferable, and 2 to 8 is further preferable, from the viewpoint that the desired effect can be easily obtained.
- Preferred specific examples of the alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-. Examples include octyl groups.
- alkylaluminum compound examples include trimethylaluminum, triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trin-pentylaluminum, and trin-.
- Trialkylaluminum such as hexylaluminum, trin-heptylaluminum, trin-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride; dimethylaluminum hydride, diethylaluminum hydride, din-propyldimethyl Aluminum hydride, diisopropyldimethylaluminum hydride, din-butylaluminum hydride, diisobutylaluminum hydride, disec-butylaluminum hydride, din-pentyl aluminum hydride, din-hexyl aluminum hydride, din-heptyl aluminum hydride, din- Dialkylaluminum hydrides such as octylaluminum hydride; examples include dialkylaluminum alkoxides such as dimethylaluminum meth
- alkyl zinc compound a compound conventionally used for polymerization of olefins and the like can be used without particular limitation.
- alkyl zinc compound examples include compounds represented by the following general formula (III).
- R 02 is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z2 is an integer of 1 to 3).
- the number of carbon atoms of the alkyl group as R 02 is 1 to 15, and 1 to 8 is more preferable, and 2 to 8 is further preferable, from the viewpoint that a desired effect can be easily obtained.
- Preferred specific examples of the alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-. Examples include octyl groups.
- alkyl zinc compound examples include dimethyl zinc, diethyl zinc, din-propyl zinc, diisopropyl zinc, din-butyl zinc, diisobutyl zinc, disec-butyl zinc, din-pentyl zinc, and din-hexyl zinc.
- Dialkyl zinc such as di-n-heptyl zinc, di-n-octyl zinc
- alkyl zinc halides such as methyl zinc chloride, ethyl zinc chloride, isobutyl zinc chloride
- alkyl zinc hydride such as methyl zinc hydride, ethyl zinc hydride, isobutyl zinc hydride and the like.
- alkyl metal compounds one or more selected from the group consisting of trialkylaluminum, dialkylaluminum hydride, and dialkylzinc is preferable, and trialkylaluminum and / or dialkylaluminum hydride is more preferable.
- the amount of the alkyl metal compound used together with the metallocene catalyst is preferably 1 to 500,000 mol, more preferably 10 to 50,000 mol, as the total number of moles of aluminum and zinc with respect to 1 mol of the metallocene catalyst.
- the polymerization conditions are not particularly limited as long as the cyclic olefin copolymer having desired physical properties can be obtained, and known conditions can be used.
- the amount of the catalyst composition used is derived from the amount of the metallocene compound used in its preparation.
- the amount of the catalyst composition used is preferably 0.000000001 to 0.005 mol, more preferably 0.00000001 to 0.0005 mol, based on 1 mol of the norbornene monomer, as the mass of the metallocene compound used for the preparation thereof. preferable.
- the polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is reached or the molecular weight of the polymer is increased to a desired degree.
- the polymerization time varies depending on the temperature, the composition of the catalyst, and the composition of the monomer, but is typically 0.01 hours to 120 hours, preferably 0.1 hours to 80 hours, and 0.2 hours to 0.2 hours. 10 hours is more preferred.
- the catalyst composition is continuously added to the polymerization vessel.
- the cyclic olefin copolymer can be continuously produced, and the production cost of the cyclic olefin copolymer can be reduced.
- a cyclic olefin copolymer can be efficiently produced by copolymerizing a norbornene monomer and a monomer containing ethylene to suppress the formation of polyethylene-like impurities.
- the glass transition temperature of the obtained cyclic olefin copolymer is not particularly limited, but from the viewpoint of processability, for example, it is preferably 185 ° C. or lower, more preferably 160 ° C. or lower, further preferably 130 ° C. or lower, still more preferably 120 ° C. or lower. It is preferable, and 100 ° C. or lower is particularly preferable.
- a sample of the cyclic olefin copolymer produced by the above method was measured by a differential scanning calorimeter (DSC) under a nitrogen atmosphere and a heating rate of 20 ° C./min according to the method described in JIS K7121.
- DSC differential scanning calorimeter
- the obtained DSC curve does not have a peak of melting point (melting enthalpy) derived from polyethylene-like impurities. This means that polyethylene-like impurities in the cyclic olefin copolymer are absent or very few.
- the peak of the melting point derived from the polyethylene-like impurities on the DSC curve is generally detected in the range of 100 ° C to 140 ° C. Ru.
- the cyclic olefin copolymer produced by the above method has a low content of polyethylene-like impurities and is excellent in transparency. Therefore, the cyclic olefin copolymer produced by the above method is required to have a high degree of transparency in terms of optical function and aesthetics, and is an optical film or an optical sheet, or a film or sheet for a packaging material. It is particularly preferably used as a material for the above.
- Examples 1 to 18 and Comparative Examples 1 to 5 In the production of the cyclic olefin resin composition, in Examples 1 to 18, as the metallocene catalyst, the compound represented by the above formula (a1), M is Ti, X is a chlorine atom, and R is. Compounds in which a6 and Ra7 are tert-butyl groups and have the ligands numbered in Table 3 were used. The number of the ligand shown in Table 3 is the number of the ligand shown in Table 1. In Comparative Examples 1 to 5, as the metallocene catalyst, the compound represented by the above formula (a1), M is Ti, X is a chlorine atom, and R a6 and R a7 are tert-butyl groups. Yes, the compounds having the ligands with the numbers shown in Table 2 were used. The number of the ligand shown in Table 3 is the number of the ligand shown in Table 2.
- CC1 6.5% by mass (as the content of Al atom)
- MMAO-3A toluene solution [(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] Methylisobutylaluminoxane represented by n Solution, manufactured by Toso Finechem Co., Ltd., still containing 6 mol% trimethylaluminum with respect to total Al
- CC2 40.6% by mass (as the content of Al atom)
- Solid MAO toluene solution (average particle size d (0.5) 5.6 ⁇ m (measurement dispersion medium: toluene), slurry concentration 12.2 wt%, Toso Finechem Made by Co., Ltd.)
- CC3 N-Methyldialkylammonium tetrakis (pentafluorophenyl) borate (al
- the polymerization solution was put into a mixed solvent of 300 mL of acetone, 200 mL of methanol or isopropyl alcohol, and 5 mL of hydrochloric acid to precipitate the copolymer.
- the copolymer was recovered by suction filtration, washed with acetone and methanol, and vacuum dried at 110 ° C. for 12 hours to obtain a copolymer of norbornene and ethylene.
- Table 3 shows the copolymer yield (kg) per 1 g of the catalyst, which is calculated from the amount of the catalyst used and the amount of the copolymer obtained.
- Tg ⁇ Glass transition temperature (Tg)> The Tg of the cyclic olefin copolymer was measured by the DSC method (method described in JIS K7121).
- DSC device Differential scanning calorimetry (DSC-Q1000 manufactured by TA Instrument) Measurement atmosphere: Nitrogen temperature rise condition: 20 ° C / min
- the calorific value (mJ / mg) was calculated from the peak area of the melting point derived from the polyethylene-like impurities observed in the range of 100 ° C to 140 ° C. The larger the calculated calorific value, the higher the content of polyethylene-like impurities.
- ND in Table 3 indicates that the peak of the melting point derived from the polyethylene-like impurity is not detected on the DSC curve.
- a norbornene monomer and ethylene are used while suppressing the formation of polyethylene-like impurities by using a metallocene catalyst having a predetermined structure and having a ligand that satisfies a specific requirement. It can be seen that the cyclic olefin copolymer can be efficiently produced by copolymerizing the monomers containing the above. Further, according to the comparison between Example 3 and Examples 4 to 6, when a metallocene catalyst having a predetermined structure and an alkyl metal compound such as an alkylaluminum compound or an alkylzinc compound are used in combination, the copolymer weight is used.
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Abstract
Description
代表的な環状オレフィン共重合体として、透明樹脂として広く使用される、環状オレフィンとエチレンとの共重合体がある。環状オレフィンとエチレンとの共重合体は、そのガラス転移温度を環状オレフィンとエチレンとの共重合組成に応じて変えることが可能なため、広い温度領域でガラス転移温度(Tg)を調整した共重合体を製造することができる(例えば、非特許文献1を参照)。
しかしながら、環状オレフィン共重合体の製造効率を高める目的で、活性の高い触媒を用いて重合を行うと、ポリエチレン様の不純物が生成しやすい場合がある。環状オレフィン共重合体にポリエチレン様の不純物が含まれると、環状オレフィン共重合体を溶媒に溶解させた場合に濁りが生じる。このような現象からも理解できる通り、環状オレフィン共重合体にポリエチレン様の不純物が含まれると、環状オレフィン共重合体の透明性の低下が懸念される。さらに、ポリエチレン様の不純物が生成すると、環状オレフィン共重合体を製造する一般的な製造プロセスにおいて、不溶なポリエチレン様の不純物をろ過・除去するという製造コストの増大を招くプロセスが必要である。
少なくとも、ノルボルネン単量体と、エチレンとをモノマーとして重合容器内に仕込むことと、
重合容器内のモノマーをメタロセン触媒の存在下に重合させることと、を含み、
メタロセン触媒が、下記式(a1):
Ra1~Ra5は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基であり、
Ra1~Ra5のうちの少なくとも1つはハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基であり、
Ra1~Ra5のうちの1つのみがハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基である場合、ハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基の炭素原子数及びケイ素原子数の合計が1以上10以下であり、
Ra1~Ra5のうちの2つ以上がハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基である場合、Ra1~Ra5それぞれについての炭素原子数及びケイ素原子数を合計した値が2以上5以下であって、且つ、Ra1~Ra5が炭素原子数2以上4以下のハロゲン原子で置換されていてもよいアルキル基、又はトリメチルシリル基を含む場合、Ra1~Ra5のうちの1つのみが炭素原子数2以上4以下のハロゲン原子で置換されていてもよいアルキル基、又はトリメチルシリル基であり、
Ra1~Ra5のうちの5員環上で隣接する2つの基は相互に結合して炭化水素環を形成してもよく、Xは、ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基、又はハロゲン原子であり、
Lは下記式(a1a):
式(a1a)中、Ra6、及びRa7は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基、又は無機置換基であり、Ra6、及びRa7の2つの基は相互に結合して環を形成してもよい。)
で表される化合物である、製造方法。
環状オレフィン共重合体の製造方法では、ノルボルネン単量体由来の構成単位とエチレン由来の構成単位とを含む環状オレフィン共重合体を製造する。
当該製造方法は、
少なくとも、ノルボルネン単量体と、エチレンとをモノマーとして重合容器内に仕込むことと、
重合容器内のモノマーを、メタロセン触媒の存在下に重合させることと、を含む。
以下、ノルボルネン単量体と、エチレンとをモノマーとして重合容器内に仕込むことを仕込み工程とも称する。また、重合容器内のモノマーを、メタロセン触媒の存在下に重合させることを重合工程とも称する。
仕込み工程では、ノルボルネン単量体と、エチレンとをモノマーとして重合容器内に仕込む。重合容器には、本発明の目的を阻害しない範囲で、ノルボルネン単量体、及びエチレン以外の他の単量体が仕込まれてもよい。環状オレフィン共重合体における、ノルボルネン単量体に由来する構成単位の比率と、エチレンに由来する構成単位の比率との合計は、典型的には、全構成単位に対して、80質量%以上が好ましく、95質量%以上がより好ましく。98質量%以上がさらに好ましい。
ノルボルネン単量体としては、例えば、ノルボルネン及び置換ノルボルネンが挙げられ、ノルボルネンが好ましい。ノルボルネン単量体は、1種単独で又は2種以上組み合わせて使用することができる。
R9とR10、R11とR12は、一体化して2価の炭化水素基を形成してもよく、
R9又はR10と、R11又はR12とは、互いに環を形成していてもよい。
また、nは、0又は正の整数を示し、
nが2以上の場合には、R5~R8は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。
ただし、n=0の場合、R1~R4及びR9~R12の少なくとも1個は、水素原子ではない。)
トリシクロ[4.3.0.12,5]デカ-3,7-ジエン(慣用名:ジシクロペンタジエン)、トリシクロ[4.3.0.12,5]デカ-3-エン;トリシクロ[4.4.0.12,5]ウンデカ-3,7-ジエン若しくはトリシクロ[4.4.0.12,5]ウンデカ-3,8-ジエン又はこれらの部分水素添加物(又はシクロペンタジエンとシクロヘキセンの付加物)であるトリシクロ[4.4.0.12,5]ウンデカ-3-エン;5-シクロペンチル-ビシクロ[2.2.1]ヘプタ-2-エン、5-シクロヘキシル-ビシクロ[2.2.1]ヘプタ-2-エン、5-シクロヘキセニルビシクロ[2.2.1]ヘプタ-2-エン、5-フェニル-ビシクロ[2.2.1]ヘプタ-2-エンといった3環の環状オレフィン;
テトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン(単にテトラシクロドデセンともいう)、8-メチルテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-エチルテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-メチリデンテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-エチリデンテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-ビニルテトラシクロ[4,4.0.12,5.17,10]ドデカ-3-エン、8-プロペニル-テトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エンといった4環の環状オレフィン;
8-シクロペンチル-テトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-シクロヘキシル-テトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-シクロヘキセニル-テトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン、8-フェニル-シクロペンチル-テトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン;テトラシクロ[7.4.13,6.01,9.02,7]テトラデカ-4,9,11,13-テトラエン(1,4-メタノ-1,4,4a,9a-テトラヒドロフルオレンともいう)、テトラシクロ[8.4.14,7.01,10.03,8]ペンタデカ-5,10,12,14-テトラエン(1,4-メタノ-1,4,4a,5,10,10a-ヘキサヒドロアントラセンともいう);ペンタシクロ[6.6.1.13,6.02,7.09,14]-4-ヘキサデセン、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[7.4.0.02,7.13,6.110,13]-4-ペンタデセン;ヘプタシクロ[8.7.0.12,9.14,7.111,17.03,8.012,16]-5-エイコセン、ヘプタシクロ[8.7.0.12,9.03,8.14,7.012,17.113,l6]-14-エイコセン;シクロペンタジエンの4量体等の多環の環状オレフィンを挙げることができる。
重合工程では、重合容器内のモノマーをそれぞれ所定の要件を満たすメタロセン触媒の存在下に重合させる。
重合時の温度は特に限定されない。環状オレフィン共重合体の収率が良好であること等から、重合時の温度は、20℃以上が好ましく、30℃以上がより好ましく、50℃以上がさらに好ましく、60℃以上がさらにより好ましく、70℃以上が特に好ましい。重合時の温度は80℃以上であってもよい。
重合時の温度の上限は特に限定されない、重合時の温度の上限は、例えば200℃以下であってよく、140℃以下であってもよく、120℃以下であってもよい。
Ra1~Ra5のうちの1つのみがハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基である場合、ハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基の炭素原子数及びケイ素原子数の合計が1以上10以下である。
Ra1~Ra5のうちの2つ以上がハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基である場合、Ra1~Ra5それぞれについての炭素原子数及びケイ素原子数を合計した値が2以上5以下であって、且つ、Ra1~Ra5が炭素原子数2以上4以下のハロゲン原子で置換されていてもよいアルキル基、又はトリメチルシリル基を含む場合、Ra1~Ra5のうちの1つのみが炭素原子数2以上4以下のハロゲン原子で置換されていてもよいアルキル基、又はトリメチルシリル基である。
Ra1~Ra5のうちの5員環上で隣接する2つの基は相互に結合して炭化水素環を形成してもよい。
Ra1~Ra5としてのアルキル基は、ハロゲン原子で置換されていてもよい。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子等が挙げられる、ハロゲン原子としては、フッ素原子が好ましい。
Ra1~Ra5が無置換のアルキル基である場合の好ましい具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、n-へプチル基、n-オクチル基、n-ノニル基、及びn-デシル基が挙げられる。
Ra1~Ra5としてのハロゲン原子で置換されたアルキル基の好適な具体例としては、フルオロメチル基、トリフルオロメチル基、トリクロロメチル基、ペンタフルオロエチル基、2,2,2-トリフルオロエチル基が挙げられる。
H:水素原子
Me:メチル基
Et:エチル基
nPr:n-プロピル基
iPr:イソプロピル基
nBu:n-ブチル基
iBu:イソブチル基
sBu:sec-ブチル基
tBu:tert-ブチル基
nPen:n-ペンチル基
nHex:n-ヘキシル基
nHep:n-へプチル基
nOct:n-オクチル基
nNon:n-ノニル基
nDec:n-デシル基
TMS:トリメチルシリル基
さらに、置換シクロペンタジエンに由来する配位子において、Ra1~Ra5についての上記の炭素原子数とケイ素原子数との条件を満たすように、シクロペンタジエン環に結合する置換基の構造と数とが制限される。このことによっても、式(a1a)で表される基が回転することにより安定な配置となるともに、式(a1)で表されるメタロセン化合物の中心金属Mの近傍に十分に広い反応場が確保される。
また、十分に広い反応場においては、エチレンより分子サイズの大きなノルボルネン単量体も良好に反応可能である。このことによって、環状オレフィン共重合体にノルボルネン単量体由来の構成単位が取り込まれやすく、ポリエチレン様の不純物の生成が抑制されると考えられる。
ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基については、有機置換基がヘテロ原子を含む場合、ヘテロ原子の種類は本発明の目的を阻害しない範囲で特に限定されない。ヘテロ原子の具体例としては、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子、セレン原子、及びハロゲン原子等が挙げられる。
Ra6、及びRa7としての、ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基の具体例及び好ましい例は、Ra1~Ra5としての、ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基の具体例及び好ましい例と同様である。
また、炭素原子数1~20の炭化水素基で置換されたモノ置換アミノ基、及び炭素原子数1~20の炭化水素基で置換されたジ置換アミノ基も、有機置換基として好ましい。
式(a1a)中のRa6、及びRa7としてのモノ置換アミノ基、又はジ置換アミノ基について、窒素原子に結合する炭素原子数1~20の炭化水素基の好適な例は、Ra1~Ra5についての有機置換基の好適な例に含まれる炭化水素基が挙げられる。
式(a1a)中のRa6、及びRa7としての無機置換基としては、上記式(a1)で表されるメタロセン化合物の生成反応を阻害しない基であれば特に限定されない。
無機置換基の具体例としては、ハロゲン原子、ニトロ基、無置換のアミノ基、及びシアノ基等が挙げられる。
前述の通り、中心金属MとしてはTiが好ましい。
式(a1)中の置換シクロペンタジエンに由来する配位子は、表1に記載の配位子5、配位子8、配位子15、又は配位子24であることがより好ましく、配位子15、又は配位子24であることがさらに好ましい。(
ここで、イオン化合物は、メタロセン触媒との反応によりカチオン性遷移金属化合物を生成させる化合物である。
アルミノキサンとしては、従来より種々のオレフィンの重合において助触媒等として使用されている種々のアルミノキサンを特に制限なく用いることができる。典型的には、アルミノキサンは有機アルミノキサンである。
触媒組成物の製造に際して、アルミノキサンは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
イオン化合物は、メタロセン触媒との反応によりカチオン性遷移金属化合物を生成する化合物である。
かかるイオン化合物としては、テトラキス(ペンタフルオロフェニル)ボレートのアニオン、ジメチルフェニルアンモニウムカチオン((CH3)2N(C6H5)H+)のような活性プロトンを有するアミンカチオン、(C6H5)3C+のような三置換カルボニウムカチオン、カルボランカチオン、メタルカルボランカチオン、遷移金属を有するフェロセニウムカチオン等のイオンを含むイオン性化合物を用いることができる。
フェノール性水酸基とハロゲン原子とを有する上記の芳香族化合物において、フェノール性水酸基とハロゲン原子とは、単環であっても縮合環であってもよい同一の芳香環上に結合する。
ヒンダードフェノールとは、フェノール性水酸基の2つの隣接位の少なくとも一方に、かさ高い置換基を有するフェノール類である。かさ高い置換基としては、例えば、イソプロピル基、イソブチル基、sec-ブチル基、及びtert-ブチル木等のメチル基以外のアルキル基、アルケニル基、アルキニル基、アリール基、複素環式基、アルコキシ基、アリールオキシ基、置換アミノ基、アルキルチオ基、並びにアリールチオ基等が挙げられる。
これらの中では、分子量が小さく、少量の使用によりヒンダードフェノールの使用による所望する効果を得やすいことから、2,6-ジ-tert-ブチル-p-クレゾール(BHT)、及び2,6-ジ-tert-ブチルフェノールが好ましい。
ヒンダードフェノールは、重合系内でアルキルアルミニウム化合物と反応することにより、環状オレフィン共重合体の収量増に寄与する。このため、ヒンダードフェノールは、アルキルアルミニウムとともに使用されるのが好ましい。また、ヒンダードフェノールは、重合機内でアルキルアルミニウムと混合させて用いられてもよい。重合前にアルキルアルミニウムとヒンダードフェノールとを混合して得た混合物を、重合機内に導入してもよい。
上記のメタロセン触媒と、アルキル金属化合物とを組み合わせて用いることにより、ポリエチレン様の不純物の生成と、分子量の過度の上昇とを抑制しつつ、ノルボルネン単量体と、エチレンとを含むモノマーを共重合させて環状オレフィン共重合体を効率良く製造できる。
(R01)z1AlX3-z1 (II)
(式(II)中、R01は炭素原子数が1~15のアルキル基であり、Xはハロゲン原子又は水素原子であり、z1は1~3の整数である。)
(R02)z2ZnX2-z2 (III)
(式(II)中、R02は炭素原子数が1~15、好ましくは1~8のアルキル基であり、Xはハロゲン原子又は水素原子であり、z2は1~3の整数である。)
触媒組成物の使用量は、その調製に用いられるメタロセン化合物の使用量から導出される。触媒組成物の使用量は、その調製に用いられたメタロセン化合物の質量として、ノルボルネン単量体1モルに対し、0.000000001~0.005モルが好ましく、0.00000001~0.0005モルがより好ましい。
重合時間は、温度や、触媒の組成や、単量体組成によっても異なるが、典型的には0.01時間~120時間であり、0.1時間~80時間が好ましく、0.2時間~10時間がより好ましい。
触媒組成物を連続的に添加することにより、環状オレフィン共重合体の連続製造が可能になり、環状オレフィン共重合体の製造コストを低減させることが可能になる。
得られる環状オレフィン共重合体のガラス転移温度は特に限定されないが、加工性の観点から、例えば185℃以下が好ましく、160℃以下がより好ましく、130℃以下がさらに好ましく、120℃以下がさらにより好ましく、100℃以下が特に好ましい。
また、上記の方法により製造される環状オレフィン共重合体の試料を、JIS K7121に記載の方法に従って、窒素雰囲気下、昇温速度20℃/分の条件で示差走査熱量計(DSC)により測定した場合、得られたDSC曲線が、ポリエチレン様の不純物に由来する融点(融解エンタルピー)のピークを有さないことが好ましい。このことは、環状オレフィン共重合体中のポリエチレン様の不純物が存在しないか極めて少ないことを意味する。なお、環状オレフィン共重合体中にポリエチレン様の不純物が含まれている場合、DSC曲線上のポリエチレン様の不純物に由来する融点のピークは、一般的に100℃~140℃の範囲内に検出される。
環状オレフィン樹脂組成物を製造するに際し、実施例1~18において、メタロセン触媒として、前述の式(a1)で表される化合物であって、MがTiであり、Xが塩素原子であり、Ra6及びRa7がtert-ブチル基であり、表3に記載の番号の配位子を有する化合物を用いた。なお、表3に記載される配位子の番号は、表1に記載される配位子の番号である。
比較例1~5において、メタロセン触媒として、前述の式(a1)で表される化合物であって、MがTiであり、Xが塩素原子であり、Ra6及びRa7がtert-ブチル基であり、表2に記載の番号の配位子を有する化合物を用いた。なお、表3に記載される配位子の番号は、表2に記載される配位子の番号である。
CC1:6.5質量%(Al原子の含有量として)MMAO-3Aトルエン溶液([(CH3)0.7(iso-C4H9)0.3AlO]nで表されるメチルイソブチルアルミノキサンの溶液、東ソー・ファインケム(株)製、なお全Alに対して6mol%のトリメチルアルミニウムを含有する)
CC2:40.6質量%(Al原子の含有量として)固体MAOトルエン溶液(平均粒径 d(0.5)5.6μm(測定分散媒:トルエン)、スラリー濃度12.2wt%、東ソー・ファインケム(株)製)
CC3:N-メチルジアルキ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(アルキル:C14~C18(平均:C17.5))(東ソー・ファインケム(株)製)
CC4:トリイソブチルアルミニウム(東ソー・ファインケム(株)製)
CC5:トリオクチルアルミニウム(東ソー・ファインケム(株)製)
CC6:ジイソプロピル亜鉛(アルドリッチ社製)
CC7:ジエチルアルミニウムクロリド(東ソー・ファインケム(株)製)
上記のように助触媒を添加した後、90℃までオートクレーブを加熱した後、メタロセン触媒溶液を、メタロセン触媒量が表3に記載した量となるように添加した。次いでゲージ圧0.9MPaのエチレン圧をかけた後、30秒後を重合開始点として重合反応を開始した。ただし、CC3を用いた実施例9、11、及び13では、メタロセン触媒溶液をメタロセン触媒量が表3に記載した量となるように添加した後、表3に記載の溶媒を用いて調製したCC3の溶液を加えてから、ゲージ圧0.9MPaのエチレン圧をかけた。
なお、エチレン圧をかける直前のモノマー溶液の全量を、80mLとした。
重合開始から15分後、エチレン供給を停止し、注意深く圧力を常圧に戻した後、反応溶液中にイソプロピルアルコールを加えて反応を停止させた。その後、アセトン300mL、メタノールあるいはイソプロピルアルコール200mL、塩酸5mLの混合溶媒に重合溶液を投入して共重合体を沈殿化させた。共重合体を吸引濾過にて回収し、アセトン、メタノールで洗浄後、共重合体を110℃で12時間真空乾燥を行い、ノルボルネンとエチレンとの共重合体を得た。
触媒の使用量と、共重合体の取得量とから算出される、触媒1g当たりの共重合体収量(kg)を、表3に記す。
DSC法(JIS K7121記載の方法)によって、環状オレフィン共重合体のTgを測定した。
DSC装置:示差走査熱量計(TA Instrument社製 DSC-Q1000)
測定雰囲気:窒素
昇温条件:20℃/分
数平均分子量(Mn)、及び重量平均分子量(Mw)を以下の測定条件に従って、ゲルパーミエーションクロマトグラフィーにより測定した。
装置:Malvern社製 Viscotek TDA302検出器+Pump autosampler装置
検出器:RI
溶媒:トルエン
カラム:東ソー社製 TSKgel GMHHR-M(300mm×7.8mmφ)
流速:1mL/分
温度:75℃
試料濃度:2.5mg/mL
注入量:100μL
標準試料:単分散ポリスチレン
ガラス転移温度の測定により得られたDSC曲線において、100℃~140℃の範囲内に観察されるポリエチレン様の不純物に由来する融点のピーク面積から発熱量(mJ/mg)を算出した。算出された発熱量が大きいほど、ポリエチレン様の不純物の含有量が多い。
なお、表3中のNDは、DSC曲線上においてポリエチレン様の不純物に由来する融点のピークが検出されないことを示す。
得られた環状オレフィン共重合体0.1gを、トルエン10gに溶解させた後、溶液における濁りの有無を観察した。濁りが認められた場合、環状オレフィン共重合体にポリエチレン様の不純物が含まれる。濁りが認められなかった場合、環状オレフィン共重合体にポリエチレン様の不純物が含まれない。濁り試験の結果、比較例1及び比較例2において濁りが観察され、その他の実施例及び比較例では濁りは観察されなかった。比較例1及び比較例2で濁りが認められた結果は、不純物熱分析の結果と一致する。
また、実施例3と、実施例4~6との比較によれば、所定の構造のメタロセン触媒と、アルキルアルミニウム化合物やアルキル亜鉛化合物のようなアルキル金属化合物とを組み合わせて使用する場合、共重合体の収量を過度に低下させることなく、得られる共重合体の分子量の増大を抑制しやすいことが分かる。
比較例1及び2によれば、前述のメタロセン触媒におけるシクロペンタジエン配位子が、無置換のシクロペンタジエン配位子である場合、ポリエチレン様の不純物が生成しやすいことが分かる。
また、比較例3~5によれば、前述のメタロセン触媒において、シクロペンタジエン配位子上の置換基についての炭素原子数及びケイ素原子数の合計が過多である場合、環状オレフィン共重合体を効率良く製造しにくいことが分かる。
Claims (6)
- ノルボルネン単量体由来の構成単位とエチレン由来の構成単位とを含む環状オレフィン共重合体の製造方法であって、
少なくとも、前記ノルボルネン単量体と、前記エチレンとをモノマーとして重合容器内に仕込むことと、
前記重合容器内の前記モノマーをメタロセン触媒の存在下に重合させることと、を含み、
前記メタロセン触媒が、下記式(a1):
Ra1~Ra5は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基であり、
Ra1~Ra5のうちの少なくとも1つはハロゲン原子で置換されていてもよいアルキル基、又はトリアルキルシリル基であり、
Ra1~Ra5のうちの1つのみがハロゲン原子で置換されていてもよい前記アルキル基、又は前記トリアルキルシリル基である場合、ハロゲン原子で置換されていてもよい前記アルキル基、又は前記トリアルキルシリル基の炭素原子数及びケイ素原子数の合計が1以上10以下であり、
Ra1~Ra5のうちの2つ以上がハロゲン原子で置換されていてもよい前記アルキル基、又は前記トリアルキルシリル基である場合、Ra1~Ra5それぞれについての炭素原子数及びケイ素原子数を合計した値が2以上5以下であって、且つ、Ra1~Ra5が炭素原子数2以上4以下のハロゲン原子で置換されていてもよい前記アルキル基、又は前記トリメチルシリル基を含む場合、Ra1~Ra5のうちの1つのみが炭素原子数2以上4以下のハロゲン原子で置換されていてもよい前記アルキル基、又は前記トリメチルシリル基であり、
Ra1~Ra5のうちの5員環上で隣接する2つの基は相互に結合して炭化水素環を形成してもよく、
Xは、ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基、又はハロゲン原子であり、
Lは下記式(a1a):
式(a1a)中、Ra6、及びRa7は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数1~20の有機置換基、又は無機置換基であり、Ra6、及びRa7の2つの基は相互に結合して環を形成してもよい。)
で表される化合物である、製造方法。 - Ra1~Ra5のうちの4つが水素原子、又はメチル基であり、Ra1~Ra5のうちの1つがトリアルキルシリル基である、請求項1に記載の環状オレフィン共重合体の製造方法。
- 前記MがTiである、請求項1又は2に記載の環状オレフィン共重合体の製造方法。
- 前記モノマーを、前記メタロセン触媒と、アルミノキサン及びボレート化合物の少なくとも一方との存在下に重合させる、請求項1~3のいずれか1項に記載の環状オレフィン共重合体の製造方法。
- 前記モノマーを、脂肪族炭化水素溶媒の存在下に重合させる、請求項1~4のいずれか1項に記載の環状オレフィン共重合体の製造方法。
- 前記環状オレフィン共重合体の試料を、JIS K7121に記載の方法に従って、窒素雰囲気下、昇温速度20℃/分の条件で示差走査熱量計による測定を行って得られたDSC曲線が、100℃~140℃の範囲内にポリエチレン様の不純物に由来する融点のピークを有さない、請求項1~5のいずれか1項に記載の環状オレフィン共重合体の製造方法。
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