JP6685223B2 - Method for producing cyclic olefin copolymer - Google Patents
Method for producing cyclic olefin copolymer Download PDFInfo
- Publication number
- JP6685223B2 JP6685223B2 JP2016521003A JP2016521003A JP6685223B2 JP 6685223 B2 JP6685223 B2 JP 6685223B2 JP 2016521003 A JP2016521003 A JP 2016521003A JP 2016521003 A JP2016521003 A JP 2016521003A JP 6685223 B2 JP6685223 B2 JP 6685223B2
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- Japan
- Prior art keywords
- group
- copolymer
- carbon atoms
- cyclic olefin
- catalyst
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title description 11
- 239000004713 Cyclic olefin copolymer Substances 0.000 title description 10
- 229920001577 copolymer Polymers 0.000 claims description 46
- -1 cyclic olefin Chemical class 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000004711 α-olefin Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 239000003426 co-catalyst Substances 0.000 description 10
- WLTSXAIICPDFKI-FNORWQNLSA-N (E)-3-dodecene Chemical compound CCCCCCCC\C=C\CC WLTSXAIICPDFKI-FNORWQNLSA-N 0.000 description 9
- 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 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 5
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 125000006267 biphenyl group Chemical group 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 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 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 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 3
- 230000003287 optical effect Effects 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
- 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 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
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- WLTSXAIICPDFKI-UHFFFAOYSA-N 3-dodecene Chemical compound CCCCCCCCC=CCC WLTSXAIICPDFKI-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BERUAZSDWPAHKG-UHFFFAOYSA-L [Cl-].[Cl-].[Ti++].C[SiH](C)C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].[Ti++].C[SiH](C)C1c2ccccc2-c2ccccc12 BERUAZSDWPAHKG-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 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
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- 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 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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-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
- 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
- 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
- MDLZXSCRAIESJZ-UHFFFAOYSA-N 5-octadecylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCCCCCCCCCCCC)CC1C=C2 MDLZXSCRAIESJZ-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JUCGLXJRZMNKAH-UHFFFAOYSA-N CCCCCCCC[Zn]CCCCCCCC Chemical compound CCCCCCCC[Zn]CCCCCCCC JUCGLXJRZMNKAH-UHFFFAOYSA-N 0.000 description 1
- XCYPJGWIZAMEGJ-UHFFFAOYSA-N CO[Zn]C Chemical compound CO[Zn]C XCYPJGWIZAMEGJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [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
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 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 1
- MNBIQZQDQOPSKO-UHFFFAOYSA-N pentadeca-1,3,5,10-tetraene Chemical compound CCCCC=CCCCC=CC=CC=C MNBIQZQDQOPSKO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 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
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
- NMLXKNNXODLJIN-UHFFFAOYSA-M zinc;carbanide;chloride Chemical compound [CH3-].[Zn+]Cl NMLXKNNXODLJIN-UHFFFAOYSA-M 0.000 description 1
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- 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
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
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- 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
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- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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Description
本発明は、環状オレフィン共重合体の製造方法に関する。 The present invention relates to a method for producing a cyclic olefin copolymer.
環状オレフィン重合体及び環状オレフィン共重合体（それぞれ「ＣＯＰ」及び「ＣＯＣ」等とも呼ばれる。）は、低吸湿性及び高透明性を有し、光ディスク基板、光学フィルム、光学ファイバー等の光学材料の分野をはじめ、様々な用途に使用されている。代表的なＣＯＣとして環状オレフィンとエチレンとの共重合体があるが、共重合体のガラス転移温度が環状オレフィンとエチレンとの共重合組成で変えることが可能なため、ＣＯＰよりガラス転移温度（Ｔｇ）の高い共重合体として製造することができ、ＣＯＰでは困難な２００℃超のＴｇを実現することも可能であるが、硬くて脆い性質を有しており、機械的強度が低く、ハンドリング性及び加工性が悪いという問題点があった。 The cyclic olefin polymer and the cyclic olefin copolymer (also referred to as “COP” and “COC”, respectively) have low hygroscopicity and high transparency, and are used for optical materials such as optical disk substrates, optical films and optical fibers. It is used for various purposes including fields. A typical COC is a copolymer of a cyclic olefin and ethylene, but since the glass transition temperature of the copolymer can be changed by the copolymerization composition of the cyclic olefin and ethylene, the glass transition temperature (Tg ), It is possible to achieve a Tg of more than 200 ° C., which is difficult for COP, but it is hard and brittle, and has low mechanical strength and handleability. Also, there is a problem that the workability is poor.
また、高Ｔｇ重合体は種々存在するが、これらは、極性基を持っているため、吸湿性及び誘電特性に限界がある。そのため、極性基を有さず、オレフィン系骨格からなり、光学特性、誘電特性、及び機械的強度に優れた高Ｔｇ重合体が求められている。 Further, there are various high Tg polymers, but these have polar groups, so that they have a limit in hygroscopicity and dielectric properties. Therefore, there is a demand for a high Tg polymer which does not have a polar group, is composed of an olefin skeleton, and is excellent in optical properties, dielectric properties, and mechanical strength.
高ＴｇＣＯＣの機械的強度を改善する方法の１つとして、環状オレフィンとエチレン以外のα−オレフィン（以下、「特定α−オレフィン」という）とを共重合させる方法がある。環状オレフィンと特定α−オレフィンとの共重合については、種々の研究がなされている。 As one of the methods for improving the mechanical strength of high TgCOC, there is a method of copolymerizing a cyclic olefin and an α-olefin other than ethylene (hereinafter, referred to as “specific α-olefin”). Various studies have been conducted on the copolymerization of cyclic olefins with specific α-olefins.
環状オレフィンと特定α−オレフィンとの共重合は、環状オレフィンとエチレンとの共重合とは大きく異なる。環状オレフィンとエチレンとの共重合で高分子量体が得られる条件では、環状オレフィンと特定α−オレフィンとの共重合において、特定α−オレフィンに起因する連鎖移動反応が生じるため、これまで高分子量体が得られにくかった。よって、環状オレフィンと特定α−オレフィンとの共重合体は、成形材料には適さないとされていた（例えば、非特許文献１を参照）。 The copolymerization of a cyclic olefin and a specific α-olefin is significantly different from the copolymerization of a cyclic olefin and ethylene. Under the condition that a high molecular weight polymer is obtained by copolymerization of a cyclic olefin and ethylene, a chain transfer reaction due to the specific α-olefin occurs in the copolymerization of the cyclic olefin and the specific α-olefin, and thus the high molecular weight polymer has been used so far. Was hard to get. Therefore, a copolymer of a cyclic olefin and a specific α-olefin is not suitable as a molding material (for example, see Non-Patent Document 1).
特許文献１には、特定のＴｉ系触媒により環状オレフィンと特定α−オレフィンからなる高分子量体が得られ、Ｔｇが２４５から２６２℃であり、低吸湿であり、線膨張係数が８０ｐｐｍ未満である優れた物性のフィルムが得られたことが記載されている。しかし、特許文献１で開示されている重合法では触媒及び助触媒を多量に使用するため、省資源化を図りにくく、共重合体を得るのにかかる費用が高価であるとともに、触媒及び助触媒が残存してフィルムの透明性を損なう問題があった。なお、特許文献１では、触媒１ｇ当たり９２−１６４ｇの共重合体が得られることが記載されている。 In Patent Document 1, a specific Ti-based catalyst is used to obtain a high molecular weight product composed of a cyclic olefin and a specific α-olefin, Tg is 245 to 262 ° C., low moisture absorption, and a linear expansion coefficient of less than 80 ppm. It is described that a film having excellent physical properties was obtained. However, since the polymerization method disclosed in Patent Document 1 uses a large amount of a catalyst and a co-catalyst, it is difficult to achieve resource saving, the cost required to obtain a copolymer is high, and the catalyst and co-catalyst are expensive. Remained and impaired the transparency of the film. Note that Patent Document 1 describes that 92-164 g of a copolymer can be obtained per 1 g of the catalyst.
特許文献２には、打抜き特性に優れたフィルムが開示されているが、Ｔｇは１７０℃未満である。また、特許文献２では、触媒及び助触媒を多量に使用するため、省資源化を図りにくく、共重合体を得るのにかかる費用が高価であるとともに、フィルムの透明性や熱安定性が損なわれる問題があった。なお、特許文献２では、触媒１ｇ当たり１２７−２７５ｇの共重合体が得られることが記載されている。 Patent Document 2 discloses a film having excellent punching characteristics, but Tg is less than 170 ° C. Further, in Patent Document 2, since a large amount of a catalyst and a co-catalyst is used, it is difficult to save resources, the cost required to obtain a copolymer is high, and the transparency and thermal stability of the film are impaired. There was a problem. Note that Patent Document 2 describes that 127-275 g of a copolymer can be obtained per 1 g of the catalyst.
本発明は、上記の状況に鑑みてなされたものであり、より少ない触媒量で、力学特性に優れ、かつ通常の成形加工に適した分子量の環状オレフィン共重合体をより多く得ることができる共重合体の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, with a smaller catalyst amount, excellent mechanical properties, and more can obtain a cyclic olefin copolymer having a molecular weight suitable for normal molding It is an object to provide a method for producing a polymer.
本発明者らは、より少ない量のチタノセン触媒を用いて、力学特性に優れ、かつ通常の成形加工に適した分子量の環状オレフィン共重合体をより多く得ることができることを見出し、本発明を完成するに至った。より具体的には、本発明は以下のものを提供する。 The present inventors have found that a smaller amount of a titanocene catalyst can be used to obtain a larger amount of a cyclic olefin copolymer having excellent mechanical properties and a molecular weight suitable for ordinary molding processing, thus completing the present invention. Came to do. More specifically, the present invention provides the following.
（１） チタノセン触媒の存在下で、少なくとも、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）とＣ４〜Ｃ１２のα−オレフィンから誘導されるα−オレフィンモノマー（Ｂ）とを重合させて共重合体を得る重合工程を含み、前記重合工程において得られる前記共重合体の量は、前記チタノセン触媒１ｇ当たり１０００ｇ以上であり、かつ、前記共重合体の数平均分子量は２０，０００以上２００，０００以下である、共重合体の製造方法。 (1) A copolymer obtained by polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin monomer (B) derived from a C4 to C12 α-olefin in the presence of a titanocene catalyst. The amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst, and the number average molecular weight of the copolymer is 20,000 or more and 200,000 or less. Which is a method for producing a copolymer.
（２） 前記重合工程は、前記チタノセン触媒とともに、アルキルアルミノキサンからなる助触媒と連鎖移動剤との存在下で行われる、（１）に記載の製造方法。 (2) The production method according to (1), wherein the polymerization step is performed in the presence of a cocatalyst made of alkylaluminoxane and a chain transfer agent together with the titanocene catalyst.
（３） 前記連鎖移動剤は、アルキルアルミニウムである（２）に記載の製造方法。 (3) The production method according to (2), wherein the chain transfer agent is alkylaluminum.
（４） 前記アルキルアルミニウムは、トリメチルアルミニウムである（３）に記載の製造方法。 (4) The production method according to (3), wherein the alkylaluminum is trimethylaluminum.
（５） 前記共重合体のガラス転移温度（Ｔｇ）は、１７０℃以上である（１）から（４）のいずれか１項に記載の製造方法。 (5) The production method according to any one of (1) to (4), wherein the glass transition temperature (Tg) of the copolymer is 170 ° C. or higher.
本発明によれば、より少ない触媒量で、力学特性に優れ、かつ通常の成形加工に適した分子量の環状オレフィン共重合体をより多く得ることができる共重合体の製造方法を提供することができる。特に、連鎖移動剤の量を制御することで、本発明の効果を更に向上させることができる。本発明では、使用する触媒の量が少ないため、それに応じて助触媒の量も低減することができる。よって、より少量の触媒及び助触媒で安価に、分子量の範囲を保ちながら、１バッチ当たりの環状オレフィン共重合体量を増やすことができ、省資源化を実現することもできる。また、得られる共重合体に残存する触媒及び助触媒が少ないため、この共重合体から得られるフィルム等の成形体は、透明性及び機械物性が向上しやすい。 According to the present invention, it is possible to provide a method for producing a copolymer capable of obtaining a larger amount of a cyclic olefin copolymer having a smaller catalyst amount, excellent mechanical properties, and a molecular weight suitable for ordinary molding processing. it can. In particular, by controlling the amount of the chain transfer agent, the effect of the present invention can be further improved. In the present invention, since the amount of the catalyst used is small, the amount of the cocatalyst can be reduced accordingly. Therefore, the amount of the cyclic olefin copolymer per batch can be increased at a low cost with a smaller amount of the catalyst and the co-catalyst, and the resource saving can be realized. Further, since the amount of catalyst and co-catalyst remaining in the obtained copolymer is small, the molded product such as a film obtained from this copolymer is likely to have improved transparency and mechanical properties.
以下、本発明の実施形態について詳細に説明する。なお、本発明は以下の実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments below.
本発明に係る共重合体の製造方法は、チタノセン触媒の存在下で、少なくとも、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）とＣ４〜Ｃ１２のα−オレフィンから誘導されるα−オレフィンモノマー（Ｂ）とを重合させて共重合体を得る重合工程を含み、上記重合工程において得られる上記共重合体の量は、上記チタノセン触媒１ｇ当たり１０００ｇ以上であり、かつ、上記共重合体の数平均分子量は２０，０００以上２００，０００以下である。本発明に係る共重合体の製造方法によれば、より少ない触媒量でも、分子量の範囲を保ちながら、１バッチで高分子量の環状オレフィン共重合体をより多く得ることができる。特に、用いる触媒量、並びに、得られる共重合体の量及び数平均分子量の観点から、本発明に係る共重合体の製造方法において、重合工程は、チタノセン触媒とともに、アルキルアルミノキサンからなる助触媒と連鎖移動剤との存在下で行われることが好ましい。 The method for producing a copolymer according to the present invention comprises a cyclic olefin monomer (A) derived from norbornene and an α-olefin monomer (B derived from α-olefin of C4 to C12) in the presence of a titanocene catalyst. ) And a polymerization step of polymerizing to obtain a copolymer, the amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst, and the number average molecular weight of the copolymer. Is 20,000 or more and 200,000 or less. According to the method for producing a copolymer of the present invention, it is possible to obtain a large amount of a high molecular weight cyclic olefin copolymer in one batch while maintaining the molecular weight range even with a smaller catalyst amount. In particular, in terms of the amount of catalyst used, and the amount and number average molecular weight of the resulting copolymer, in the method for producing a copolymer according to the present invention, the polymerization step includes a titanocene catalyst and a co-catalyst composed of an alkylaluminoxane. It is preferably carried out in the presence of a chain transfer agent.
［共重合体］
本発明に係る共重合体の製造方法により得られる共重合体は、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）由来の構造単位と、Ｃ４〜Ｃ１２のα−オレフィンから誘導されるα−オレフィンモノマー（Ｂ）由来の構造単位と、を含む。
上記製造方法に含まれる重合工程において得られる上記共重合体の量は、上記重合工程で用いられるチタノセン触媒１ｇ当たり１０００ｇ以上であり、好ましくは２０００ｇ以上である。[Copolymer]
The copolymer obtained by the method for producing a copolymer according to the present invention comprises a structural unit derived from a cyclic olefin monomer (A) derived from norbornene and an α-olefin monomer derived from a C4 to C12 α-olefin. And a structural unit derived from (B).
The amount of the copolymer obtained in the polymerization step included in the production method is 1000 g or more, preferably 2000 g or more, per 1 g of the titanocene catalyst used in the polymerization step.
本発明における共重合体の数平均分子量は、好ましくは２０，０００以上２００，０００以下であり、より好ましくは３０，０００以上、１５０，０００以下である。上記数平均分子量が２０，０００以上であると、得られる共重合体は、ガラス転移温度（Ｔｇ）が過度に低くなりにくい。上記数平均分子量が２００，０００以下であると、得られる共重合体の溶液は、粘度が過度に高くなりにくい。なお、本明細書において、数平均分子量は、ゲルパーミエーションクロマトグラフィにより測定されたポリスチレン換算の数平均分子量をいう。 The number average molecular weight of the copolymer in the present invention is preferably 20,000 or more and 200,000 or less, more preferably 30,000 or more and 150,000 or less. When the number average molecular weight is 20,000 or more, the copolymer obtained is unlikely to have an excessively low glass transition temperature (Tg). When the number average molecular weight is 200,000 or less, the viscosity of the resulting copolymer solution does not easily become excessively high. In the present specification, the number average molecular weight refers to the polystyrene equivalent number average molecular weight measured by gel permeation chromatography.
本発明における共重合体のガラス転移温度（Ｔｇ）は、１７０℃以上であり、好ましくは２００℃以上、より好ましくは２３０℃以上、特に好ましくは２６０℃以上である。上記ガラス転移温度が１７０℃以上であると、上記共重合体から得られる透明フィルムは、十分な耐熱性を有し、よって、例えば、ＩＴＯ蒸着用の基板として好適に用いることができる。特に、上記ガラス転移温度が２６０℃以上であると、上記共重合体から得られる透明フィルムは、更に十分な耐熱性を有するため、例えば、溶融した鉛フリー半田に接しても、変形、亀裂、融解等が生じにくいため、鉛フリー半田用部材として好適に用いることができる。また、上記共重合体のガラス転移温度の上限は特に限定されないが、ガラス転移温度が高くなると共重合体中のα−オレフィン由来の構造単位が少なくなるため、α−オレフィン共重合による機械的強度の改善効果が小さくなる傾向にあることから、上記ガラス転移温度は、３５０℃以下であることが好ましく、３３０℃以下であることがより好ましい。なお、本明細書において、ガラス転移温度は、ＤＳＣ法（ＪＩＳ Ｋ ７１２１記載の方法）によって昇温速度２０℃／分の条件で測定した値を採用する。 The glass transition temperature (Tg) of the copolymer in the present invention is 170 ° C or higher, preferably 200 ° C or higher, more preferably 230 ° C or higher, and particularly preferably 260 ° C or higher. When the glass transition temperature is 170 ° C. or higher, the transparent film obtained from the copolymer has sufficient heat resistance, and thus can be suitably used as, for example, a substrate for vapor deposition of ITO. In particular, when the glass transition temperature is 260 ° C. or higher, the transparent film obtained from the copolymer has more sufficient heat resistance, and therefore, for example, even when contacted with molten lead-free solder, deformation, cracks, Since melting or the like is unlikely to occur, it can be suitably used as a lead-free soldering member. Further, the upper limit of the glass transition temperature of the copolymer is not particularly limited, but since the structural unit derived from α-olefin in the copolymer decreases as the glass transition temperature increases, the mechanical strength by α-olefin copolymerization The glass transition temperature is preferably 350 ° C. or lower, and more preferably 330 ° C. or lower, since the effect of improving the above tendency tends to be small. In this specification, as the glass transition temperature, a value measured by a DSC method (method described in JIS K 7121) at a temperature rising rate of 20 ° C./min is adopted.
［チタノセン触媒］
チタノセン触媒としては、特に限定されず、公知のものを使用することができる。チタノセン触媒は、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。
チタノセン触媒としては、例えば、下記式（１）で表されるものが挙げられる。[Titanocene catalyst]
The titanocene catalyst is not particularly limited, and known ones can be used. The titanocene catalysts can be used alone or in combination of two or more.
Examples of the titanocene catalyst include those represented by the following formula (1).
Ｒ１〜Ｒ３は、それぞれ独立に、炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基である。その具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基等のアルキル基；フェニル基、ビフェニル基、上記アルキル基を置換基として有するフェニル基又はビフェニル基、ナフチル基、上記アルキル基を置換基として有するナフチル基等のアリール基を挙げることができる。R 1 to R 3 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group and cyclohexyl group; phenyl group, biphenyl group. Examples thereof include aryl groups such as a phenyl group or a biphenyl group having the above alkyl group as a substituent, a naphthyl group, and a naphthyl group having the above alkyl group as a substituent.
Ｒ４及びＲ５は、それぞれ独立に、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、又はハロゲン原子であり、具体的には、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、シクロペンチル基、シクロヘキシル基、上記ハロゲン原子を置換基として有するこれらのアルキル基；フェニル基、ビフェニル基、ナフチル基、上記ハロゲン原子又はアルキル基を置換基として有するこれらのアリール基を挙げることができる。R 4 and R 5 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and specifically, a fluorine atom, a chlorine atom, a bromine atom, or iodine. Halogen atom such as atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, the above halogen atom Examples thereof include those alkyl groups having a substituent; phenyl groups, biphenyl groups, naphthyl groups, and the above aryl groups having a halogen atom or an alkyl group as a substituent.
Ｒ６〜Ｒ１３は、それぞれ独立に、水素原子、炭素数１〜１２のアルキル基、炭素数６〜１２のアリール基、又は炭素数１〜１２の１価炭化水素基を置換基として有していてもよいシリル基である。炭素数１〜１２のアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、シクロペンチル基、シクロヘキシル基等を挙げることができる。また、炭素数６〜１２のアリール基の具体例としては、フェニル基、ビフェニル基、ナフチル基、上記アルキル基を置換基として有するこれらのアリール基等を挙げることができる。更に、炭素数１〜１２の１価炭化水素基を置換基として有するシリル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、シクロペンチル基、シクロヘキシル基等の炭素数１〜１２のアルキル基を置換基として有するシリル基を挙げることができる。R 6 to R 13 each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent. Optionally a silyl group. Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group. Group, cyclohexyl group and the like. In addition, specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and these aryl groups having the above alkyl group as a substituent. Further, specific examples of the silyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl. Examples thereof include a silyl group having an alkyl group having 1 to 12 carbon atoms such as a group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group as a substituent.
一般式（１）で示されるチタノセン触媒の具体例としては、（イソプロピルアミド）ジメチル−９−フルオレニルシランチタンジメチル、（イソブチルアミド）ジメチル−９−フルオレニルシランチタンジメチル、（ｔ−ブチルアミド）ジメチル−９−フルオレニルシランチタンジメチル、（イソプロピルアミド）ジメチル−９−フルオレニルシランチタンジクロリド、（イソブチルアミド）ジメチル−９−（３，６−ジメチルフルオレニル）シランチタンジクロリド、（ｔ−ブチルアミド）ジメチル−９−フルオレニルシランチタンジクロリド、（イソプロピルアミド）ジメチル−９−（３，６−ジメチルフルオレニル）シランチタンジクロリド、（イソブチルアミド）ジメチル−９−（３，６−ジメチルフルオレニル）シランチタンジクロリド、（ｔ−ブチルアミド）ジメチル−９−（３，６−ジメチルフルオレニル）シランチタンジメチル、（イソプロピルアミド）ジメチル−９−［３，６−ジ（ｉ−プロピル）フルオレニル］シランチタンジクロリド、（イソブチルアミド）ジメチル−９−［３，６−ジ（ｉ−プロピル）フルオレニル］シランチタンジクロリド、（ｔ−ブチルアミド）ジメチル−９−［３，６−ジ（ｉ−プロピル）フルオレニル］シランチタンジメチル、（イソプロピルアミド）ジメチル−９−［３，６−ジ（ｔ−ブチル）フルオレニル］シランチタンジクロリド、（イソブチルアミド）ジメチル−９−［３，６−ジ（ｔ−ブチル）フルオレニル］シランチタンジクロリド、（ｔ−ブチルアミド）ジメチル−９−［３，６−ジ（ｔ−ブチル）フルオレニル］シランチタンジメチル、（イソプロピルアミド）ジメチル−９−［２，７−ジ（ｔ−ブチル）フルオレニル］シランチタンジクロリド、（イソブチルアミド）ジメチル−９−［２，７−ジ（ｔ−ブチル）フルオレニル］シランチタンジクロリド、（ｔ−ブチルアミド）ジメチル−９−［２，７−ジ（ｔ−ブチル）フルオレニル］シランチタンジメチル、（イソプロピルアミド）ジメチル−９−（２，３，６，７−テトラメチルフルオレニル）シランチタンジクロリド、（イソブチルアミド）ジメチル−９−（２，３，６，７−テトラメチルフルオレニル）シランチタンジクロリド、（ｔ−ブチルアミド）ジメチル−９−（２，３，６，７−テトラメチルフルオレニル）シランチタンジメチル等を挙げることができる。好ましくは（ｔ−ブチルアミド）ジメチル−９−フルオレニルシランチタンジメチル（（ｔ−ＢｕＮＳｉＭｅ２Ｆｌｕ）ＴｉＭｅ２）である。（ｔ−ＢｕＮＳｉＭｅ２Ｆｌｕ）ＴｉＭｅ２は、下記式（２）で表されるチタニウム錯体であり、例えば、「Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ、第３１巻、３１８４頁、１９９８年」の記載に基づき、容易に合成することができる。Specific examples of the titanocene catalyst represented by the general formula (1) include (isopropylamide) dimethyl-9-fluorenylsilane titanium dimethyl, (isobutylamide) dimethyl-9-fluorenylsilane titanium dimethyl, and (t-butylamide). ) Dimethyl-9-fluorenylsilane titanium dimethyl, (isopropylamido) dimethyl-9-fluorenylsilane titanium dichloride, (isobutylamido) dimethyl-9- (3,6-dimethylfluorenyl) silane titanium dichloride, ( t-butylamido) dimethyl-9-fluorenylsilane titanium dichloride, (isopropylamido) dimethyl-9- (3,6-dimethylfluorenyl) silane titanium dichloride, (isobutylamido) dimethyl-9- (3,6- Dimethylfluorenyl) silane titanium dioxide Lido, (t-butylamido) dimethyl-9- (3,6-dimethylfluorenyl) silane titanium dimethyl, (isopropylamido) dimethyl-9- [3,6-di (i-propyl) fluorenyl] silane titanium dichloride, (Isobutylamido) dimethyl-9- [3,6-di (i-propyl) fluorenyl] silane titanium dichloride, (t-butylamido) dimethyl-9- [3,6-di (i-propyl) fluorenyl] silane titanium dimethyl , (Isopropylamido) dimethyl-9- [3,6-di (t-butyl) fluorenyl] silane titanium dichloride, (Isobutylamido) dimethyl-9- [3,6-di (t-butyl) fluorenyl] silane titanium dichloride , (T-butylamido) dimethyl-9- [3,6-di (t-butyl) fluorenyl Silane titanium dimethyl, (isopropylamido) dimethyl-9- [2,7-di (t-butyl) fluorenyl] silane titanium dichloride, (isobutylamido) dimethyl-9- [2,7-di (t-butyl) fluorenyl] Silane titanium dichloride, (t-butylamido) dimethyl-9- [2,7-di (t-butyl) fluorenyl] silane titanium dimethyl, (isopropylamido) dimethyl-9- (2,3,6,7-tetramethylful (Olenyl) silane titanium dichloride, (isobutylamido) dimethyl-9- (2,3,6,7-tetramethylfluorenyl) silane titanium dichloride, (t-butylamido) dimethyl-9- (2,3,6,6) 7-tetramethylfluorenyl) silane titanium dimethyl etc. can be mentioned. Preferred is (t-butylamido) dimethyl-9-fluorenylsilane titanium dimethyl ((t-BuNSiMe 2 Flu) TiMe 2 ). (T-BuNSiMe 2 Flu) TiMe 2 is a titanium complex represented by the following formula (2), and can be easily synthesized based on the description in “Macromolecules, Vol. 31, page 3184, 1998”, for example. You can
［アルキルアルミノキサンからなる助触媒］
本発明において用いられる助触媒は、アルキルアルミノキサンからなる。上記助触媒は、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。
アルキルアルミノキサンとしては、特に限定されず、例えば、下記式（３）又は（４）で表される化合物が挙げられる。下記式（３）又は（４）で表されるアルキルアルミノキサンは、トリアルキルアルミニウムと水との反応により得られる生成物である。[Promoter composed of alkylaluminoxane]
The cocatalyst used in the present invention consists of an alkylaluminoxane. The above promoters can be used alone or in combination of two or more.
The alkylaluminoxane is not particularly limited, and examples thereof include compounds represented by the following formula (3) or (4). The alkylaluminoxane represented by the following formula (3) or (4) is a product obtained by the reaction of trialkylaluminum and water.
アルキルアルミノキサンとしては、メチルアルミノキサン及びメチルアルミノキサンのメチル基の一部を他のアルキル基で置換した修飾メチルアルミノキサンが挙げられる。修飾メチルアルミノキサンとしては、例えば、置換後のアルキル基として、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等の炭素数２〜４のアルキル基を有する修飾メチルアルミノキサンが好ましく、特に、メチル基の一部をイソブチル基で置換した修飾メチルアルミノキサンがより好ましい。アルキルアルミノキサンの具体例としては、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、中でも、メチルアルミノキサン及びメチルイソブチルアルミノキサンが好ましい。 Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane obtained by substituting a part of the methyl group of methylaluminoxane with another alkyl group. As the modified methylaluminoxane, for example, as a 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, an isobutyl group is preferable, and a methyl group is particularly preferable. A modified methylaluminoxane in which a part of the group is substituted with an isobutyl group is more preferable. Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like, among which methylaluminoxane and methylisobutylaluminoxane are preferable.
アルキルアルミノキサンは、公知の方法で調製することができる。また、アルキルアルミノキサンとしては、市販品を用いてもよい。アルキルアルミノキサンの市販品としては、例えば、ＭＭＡＯ−３Ａ、ＴＭＡＯ−２００シリーズ、ＴＭＡＯ−３４０シリーズ（いずれも東ソー・ファインケム（株）製）やメチルアルミノキサン溶液（アルベマール社製）等が挙げられる。 The alkylaluminoxane can be prepared by a known method. Moreover, you may use a commercial item as alkyl aluminoxane. Examples of commercial products of alkylaluminoxane include MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Tosoh Finechem Co., Ltd.), methylaluminoxane solution (manufactured by Albemarle) and the like.
［連鎖移動剤］
本発明において用いられる連鎖移動剤は、連鎖移動能を有する化合物である。連鎖移動剤は、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。[Chain transfer agent]
The chain transfer agent used in the present invention is a compound having chain transfer ability. The chain transfer agents may be used alone or in combination of two or more.
連鎖移動剤としては、特に限定されず、連鎖移動能を有する公知の化合物を用いることができ、例えば、アルキルアルミニウムが挙げられる。アルキルアルミニウムとしては、例えば、下記一般式（５）で示される化合物が挙げられる。
（Ｒ１０）ｚＡｌＸ３−ｚ （５）
（式中、Ｒ１０は炭素数が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、ｚは１〜３の整数である。）The chain transfer agent is not particularly limited, and a known compound having a chain transfer ability can be used, and examples thereof include alkylaluminum. Examples of the alkylaluminum include compounds represented by the following general formula (5).
(R 10 ) z AlX 3-z (5)
(In the formula, R 10 is an alkyl group having 1 to 15, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3.)
炭素数が１〜１５のアルキル基としては、例えば、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、ｎ−オクチル基等が挙げられる。 Examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group and the like.
アルキルアルミニウムの具体例としては、トリメチルアルミニウム、トリエチルアルミニウム、トリイソプロピルアルミニウム、トリｎ−ブチルアルミニウム、トリイソブチルアルミニウム、トリｓｅｃ−ブチルアルミニウム、トリｎ−オクチルアルミニウム等のトリアルキルアルミニウム；ジメチルアルミニウムクロリド、ジイソブチルアルミニウムクロリド等のジアルキルアルミニウムハライド；ジイソブチルアルミニウムハイドライド等のジアルキルアルミニウムハイドライド；ジメチルアルミニウムメトキシド等のジアルキルアルミニウムアルコキシドが挙げられる。 Specific examples of the alkyl aluminum include trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, and tri n-octyl aluminum; dimethyl aluminum chloride, diisobutyl. Examples thereof include dialkyl aluminum halides such as aluminum chloride; dialkyl aluminum hydrides such as diisobutyl aluminum hydride; and dialkyl aluminum alkoxides such as dimethyl aluminum methoxide.
その他の連鎖移動剤として、メタロセン触媒での重合で知られているＣｈａｉｎ Ｓｈｕｔｔｌｉｎｇ剤も用いることができる。Ｃｈａｉｎ Ｓｈｕｔｔｌｉｎｇ剤の例として、上述したアルキルアルミニウムやアルキル亜鉛が挙げられる。アルキル亜鉛としては、例えば、下記一般式（６）で示される化合物が挙げられる。
（Ｒ１１）ｚＺｎＸ２−ｙ （６）
（式中、Ｒ１１は炭素数が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、ｙは０〜２の整数である。）As the other chain transfer agent, a Chain Shutting agent known for polymerization with a metallocene catalyst can also be used. Examples of the chain shuttling agent include the above-mentioned alkyl aluminum and alkyl zinc. Examples of the alkylzinc include compounds represented by the following general formula (6).
(R 11 ) z ZnX 2-y (6)
(In the formula, R 11 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 y is an integer of 0 to 2.)
炭素数が１〜１５のアルキル基としては、例えば、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、ｎ−オクチル基等が挙げられる。 Examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group and the like.
アルキル亜鉛の具体例としては、ジメチル亜鉛、ジエチル亜鉛、ジイソプロピル亜鉛、ジｎ−ブチル亜鉛、ジイソブチル亜鉛、ジｓｅｃ−ブチル亜鉛アルミニウム、ジｎ−オクチル亜鉛等のジアルキル亜鉛；メチル亜鉛クロリド、イソブチル亜鉛クロリド等のアルキル亜鉛ハライド；イソブチル亜鉛ハイドライド等のアルキル亜鉛ハイドライド；メチル亜鉛メトキシド等のアルキル亜鉛アルコキシド；塩化亜鉛等のハロゲン化亜鉛等が挙げられる。 Specific examples of the alkylzinc include dialkylzinc such as dimethylzinc, diethylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, disec-butylzinc aluminum, and di-n-octylzinc; methylzinc chloride, isobutylzinc chloride. And the like; alkylzinc halides such as isobutylzinc hydride; alkylzinc alkoxides such as methylzinc methoxide; zinc halides such as zinc chloride.
アルキルアルミニウム又はアルキル亜鉛は、重合系内に直接投入しても、またアルキルアルミノキサン中に含有させた状態で投入してもよい。また、アルキルアルミノキサンを製造する際に用いられ、製造後に残存する原料のアルキルアルミニウムでもよい。また、アルキルアルミニウムとアルキル亜鉛は組み合わせて使用してもよい。 The alkylaluminum or alkylzinc may be added directly into the polymerization system or may be added while being contained in the alkylaluminoxane. Further, it may be a raw material alkylaluminum used when producing an alkylaluminoxane and remaining after the production. Also, alkylaluminum and alkylzinc may be used in combination.
［環状オレフィンモノマー（Ａ）］
ノルボルネンから誘導される環状オレフィンモノマー（Ａ）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。上記環状オレフィンモノマー（Ａ）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。[Cyclic olefin monomer (A)]
Examples of the cyclic olefin monomer (A) derived from norbornene include norbornene and substituted norbornene, and norbornene is preferred. The said cyclic olefin monomer (A) can be used individually by 1 type or in combination of 2 or more types.
上記置換ノルボルネンは特に限定されず、この置換ノルボルネンが有する置換基としては、例えば、ハロゲン原子、１価又は２価の炭化水素基が挙げられる。置換ノルボルネンの具体例としては、下記一般式（Ｉ）で示されるものが挙げられる。 The substituted norbornene is not particularly limited, and examples of the substituent that the substituted norbornene has include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include those represented by the following general formula (I).
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。）
R 9 and R 10 , and R 11 and R 12 may combine to form a divalent hydrocarbon group,
R 9 or R 10 and R 11 or R 12 may form a ring with each other.
In addition, n represents 0 or a positive integer,
When n is 2 or more, R 5 to R 8 may be the same or different in each repeating unit.
However, when n = 0, at least one of R 1 to R 4 and R 9 to R 12 is not a hydrogen atom. )
一般式（Ｉ）で示される置換ノルボルネンについて説明する。一般式（Ｉ）におけるＲ１〜Ｒ１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものである。The substituted norbornene represented by the general formula (I) will be described. R 1 to R 12 in formula (I) may be the same or different and are selected from the group consisting of hydrogen atom, halogen atom and hydrocarbon group.
Ｒ１〜Ｒ８の具体例としては、例えば、水素原子；フッ素、塩素、臭素等のハロゲン原子；炭素数１以上２０以下のアルキル基等を挙げることができ、これらはそれぞれ異なっていてもよく、部分的に異なっていてもよく、また、全部が同一であってもよい。Specific examples of R 1 to R 8 include a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; and an alkyl group having 1 to 20 carbon atoms, which may be different from each other. , May be partially different, or all may be the same.
また、Ｒ９〜Ｒ１２の具体例としては、例えば、水素原子；フッ素、塩素、臭素等のハロゲン原子；炭素数１以上２０以下のアルキル基；シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、エチルフェニル基、イソプロピルフェニル基、ナフチル基、アントリル基等の置換又は無置換の芳香族炭化水素基；ベンジル基、フェネチル基、その他アルキル基にアリール基が置換したアラルキル基等を挙げることができ、これらはそれぞれ異なっていてもよく、部分的に異なっていてもよく、また、全部が同一であってもよい。Specific examples of R 9 to R 12 include, for example, hydrogen atom; halogen atom such as fluorine, chlorine and bromine; alkyl group having 1 to 20 carbon atoms; cycloalkyl group such as cyclohexyl group; phenyl group and tolyl group. Group, ethylphenyl group, isopropylphenyl group, naphthyl group, substituted or unsubstituted aromatic hydrocarbon group such as anthryl group; benzyl group, phenethyl group, aralkyl group in which an alkyl group is substituted with an aryl group, and the like. However, they may be different from each other, partially different from each other, or all of them may be the same.
Ｒ９とＲ１０、又はＲ１１とＲ１２とが一体化して２価の炭化水素基を形成する場合の具体例としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基等のアルキリデン基等を挙げることができる。Specific examples of the case where R 9 and R 10 or R 11 and R 12 are integrated to form a divalent hydrocarbon group include, for example, an alkylidene group such as an ethylidene group, a propylidene group and an isopropylidene group. Can be mentioned.
Ｒ９又はＲ１０と、Ｒ１１又はＲ１２とが、互いに環を形成する場合には、形成される環は単環でも多環であってもよく、架橋を有する多環であってもよく、二重結合を有する環であってもよく、またこれらの環の組み合わせからなる環であってもよい。また、これらの環はメチル基等の置換基を有していてもよい。When R 9 or R 10 and R 11 or R 12 form a ring with each other, the ring formed may be a monocycle or a polycycle, or may be a polycycle having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.
一般式（Ｉ）で示される置換ノルボルネンの具体例としては、５−メチル−ビシクロ［２．２．１］ヘプタ−２−エン、５，５−ジメチル−ビシクロ［２．２．１］ヘプタ−２−エン、５−エチル−ビシクロ［２．２．１］ヘプタ−２−エン、５−ブチル−ビシクロ［２．２．１］ヘプタ−２−エン、５−エチリデン−ビシクロ［２．２．１］ヘプタ−２−エン、５−ヘキシル−ビシクロ［２．２．１］ヘプタ−２−エン、５−オクチル−ビシクロ［２．２．１］ヘプタ−２−エン、５−オクタデシル−ビシクロ［２．２．１］ヘプタ−２−エン、５−メチリデン−ビシクロ［２．２．１］ヘプタ−２−エン、５−ビニル−ビシクロ［２．２．１］ヘプタ−２−エン、５−プロペニル−ビシクロ［２．２．１］ヘプタ−２−エン等の２環の環状オレフィン； Specific examples of the substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo [2.2.1] hept-2-ene and 5,5-dimethyl-bicyclo [2.2.1] hepta-. 2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2. 1] Hepta-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [ 2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5- Bicyclic ring such as propenyl-bicyclo [2.2.1] hept-2-ene Olefin;
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；Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (conventional name: dicyclopentadiene), tricyclo [4.3.0.1 2,5 ] deca-3-ene; tricyclo [ 4.4.0.1 2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 2,5 ] undeca-3,8-diene or partial hydrogenation products thereof (or cyclopentadiene) And cyclohexene adduct) tricyclo [4.4.0.1 2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo 3 such as [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene Ring cyclic olefins;
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；Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 1 7,10] dodeca-3-ene, 8-vinyl-tetracyclo [4,4.0.1 2,5. 1 7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 2,5 . 4-ring cyclic olefin such as 1 7,10 ] dodec-3-ene;
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−へ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。8-Cyclopentyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 2,5 . 1 7,10] dodeca-3-ene; tetracyclo [7.4.1 3,6. 0 1,9 . 0 2,7] tetradeca -4,9,11,13- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo [8.4.1 4,7. 0 1,10 . 0 3,8 ] 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 . 0 9,14 ] -4-Hexadecene, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] -4-pentadecene, pentacyclo [7.4.0.0 2,7. 1 3,6 . 1 10,13] -4-pentadecene; heptacyclo [8.7.0.1 2,9. 1 4,7 . 1 11, 17 . 0 3,8 . 0 12, 16] -5-eicosene, heptacyclo [8.7.0.1 2,9. 0 3,8 . 1 4,7 . 0 12,17 . 1 13,16 ] -14-eicosene ; polycyclic cyclic olefins such as a tetramer of cyclopentadiene.
中でも、アルキル置換ノルボルネン（例えば、１個以上のアルキル基で置換されたビシクロ［２．２．１］ヘプタ−２−エン）、アルキリデン置換ノルボルネン（例えば、１個以上のアルキリデン基で置換されたビシクロ［２．２．１］ヘプタ−２−エン）が好ましく、５−エチリデン−ビシクロ［２．２．１］ヘプタ−２−エン（慣用名：５−エチリデン−２−ノルボルネン、又は、単にエチリデンノルボルネン）が特に好ましい。 Among them, alkyl-substituted norbornene (for example, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornene (for example, bicyclo substituted with one or more alkylidene groups) [2.2.1] hept-2-ene) is preferred, and 5-ethylidene-bicyclo [2.2.1] hept-2-ene (conventional name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene). ) Is particularly preferable.
［α−オレフィンモノマー（Ｂ）］
Ｃ４〜Ｃ１２のα−オレフィンから誘導されるα−オレフィンモノマー（Ｂ）としては、例えば、Ｃ４〜Ｃ１２のα−オレフィンや、ハロゲン原子等の少なくとも１種の置換基を有するＣ４〜Ｃ１２のα−オレフィンが挙げられ、Ｃ４〜Ｃ１２のα−オレフィンが好ましく、Ｃ６〜Ｃ１０のα−オレフィンがより好ましい。[Α-Olefin Monomer (B)]
Examples of the α-olefin monomer (B) derived from a C4 to C12 α-olefin include, for example, a C4 to C12 α-olefin, and a C4 to C12 α-olefin having at least one substituent such as a halogen atom. Examples of the olefin include C4 to C12 α-olefins, and C6 to C10 α-olefins are more preferable.
Ｃ４〜Ｃ１２のα−オレフィンは特に限定されないが、例えば、１−ブテン、１−ペンテン、１−へキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−へキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−へキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン等が挙げられる。中でも、１−ヘキセン、１−オクテン、１−デセンが好ましい。 The C4-C12 α-olefin is not particularly limited, but for example, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1- Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3- Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Among them, 1-hexene, 1-octene and 1-decene are preferable.
［重合工程の条件］
重合工程の条件は、所望の共重合体が得られる限り、特に限定されず、公知の条件を用いることができ、重合温度、重合圧力、重合時間等は適宜調整される。また、各成分の使用量は、以下のとおりに例示される。
α−オレフィンモノマー（Ｂ）の添加量は、環状オレフィンモノマー（Ａ）１００質量部に対し、１質量部以上５００質量部以下であることが好ましく、１０質量部以上３００質量部以下であることがより好ましい。
チタノセン触媒の使用量は、環状オレフィンモノマー（Ａ）１００質量部に対し、０．００００１質量部以上０．１質量部以下であることが好ましく、０．０００１質量部以上０．０５質量部以下であることがより好ましい。
アルキルアルミノキサンの使用量は、環状オレフィンモノマー（Ａ）１００質量部に対し、Ａｌ基準で０．０００１質量部以上５質量部以下であることが好ましく、０．０１質量部以上３質量部以下であることがより好ましい。
連鎖移動剤の使用量は、環状オレフィンモノマー（Ａ）１００質量部に対し、０．０００１質量部以上１０質量部以下であることが好ましく、０．０１質量部以上５質量部以下であることがより好ましい。[Conditions of polymerization process]
The conditions of the polymerization step are not particularly limited as long as the desired copolymer can be obtained, and known conditions can be used, and the polymerization temperature, the polymerization pressure, the polymerization time, etc. are appropriately adjusted. The amount of each component used is exemplified as follows.
The addition amount of the α-olefin monomer (B) is preferably 1 part by mass or more and 500 parts by mass or less, and 10 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferable.
The amount of the titanocene catalyst used is preferably 0.00001 parts by mass or more and 0.1 parts by mass or less, and 0.0001 parts by mass or more and 0.05 parts by mass or less with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferably.
The amount of alkylaluminoxane used is preferably 0.0001 parts by mass or more and 5 parts by mass or less, and 0.01 parts by mass or more and 3 parts by mass or less, based on Al, relative to 100 parts by mass of the cyclic olefin monomer (A). Is more preferable.
The amount of the chain transfer agent used is preferably 0.0001 parts by mass or more and 10 parts by mass or less, and 0.01 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferable.
以下、実施例を示し、本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。特に断らない限り、量を表す「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” indicating amounts means “parts by mass”.
［共重合体の作製］
乾燥し、窒素雰囲気下に保ったガラス反応器に、表１に記載された各モノマー、及び表２に記載された助触媒を加え、重合温度に保ったのち、表２に記載された触媒を加えた。なお、触媒及び助触媒は、それぞれトルエンに溶解させた状態で反応器に加えた。表３に示す重合温度及び重合時間で、反応器内を撹拌して重合を継続した後、２−プロパノール１質量部を添加して反応を終了させた。次いで、得られた重合反応液を多量の塩酸酸性メタノールに注いで重合体を完全に析出させ、濾別及び洗浄を行った後、６０℃で１日間以上減圧乾燥して共重合体を得た。得られた共重合体の質量を測定した（表３中の「収量」）。使用した触媒量に対する得られた共重合体の割合を算出した（表３中の「ｇ（共重合体）／ｇ（触媒）」）。[Preparation of copolymer]
Each of the monomers listed in Table 1 and the cocatalysts listed in Table 2 were added to a glass reactor which was dried and kept under a nitrogen atmosphere, and the catalysts listed in Table 2 were added after the polymerization temperature was maintained. added. The catalyst and the co-catalyst were added to the reactor while being dissolved in toluene. At the polymerization temperature and polymerization time shown in Table 3, the inside of the reactor was stirred to continue the polymerization, and then 1 part by mass of 2-propanol was added to terminate the reaction. Next, the obtained polymerization reaction liquid was poured into a large amount of hydrochloric acid-acidified methanol to completely precipitate the polymer, which was filtered and washed, and then dried under reduced pressure at 60 ° C. for 1 day or longer to obtain a copolymer. . The mass of the obtained copolymer was measured (“Yield” in Table 3). The ratio of the obtained copolymer to the amount of catalyst used was calculated (“g (copolymer) / g (catalyst)” in Table 3).
なお、使用した触媒及び助触媒の種類は下記のとおりである。ここで、ｔ−Ｂｕはｔｅｒｔ−ブチル基を、Ｆｌｕはフルオレニル基を示す。
触媒Ａ：（ｔ−ＢｕＮＳｉＭｅ２Ｆｌｕ）ＴｉＭｅ２
助触媒Ａ：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）
助触媒Ｂ：９．０質量％（Ａｌ原子の含有量として）ＴＭＡＯ−２１１トルエン溶液（メ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２６ｍｏｌ％のトリメチルアルミニウムを含有する）
助触媒Ｃ：トリイソブチルアルミニウム
助触媒Ｄ：ジメチルアニリウムテトラキス（ペンタフルオロフェニル）ボレートThe types of catalyst and co-catalyst used are as follows. Here, t-Bu represents a tert-butyl group, and Flu represents a fluorenyl group.
Catalyst A: (t-BuNSiMe 2 Flu ) TiMe 2
Cocatalyst A: 6.5 wt% (the content of Al atoms) MMAO-3A in toluene (methyl represented by [(CH 3) 0.7 (iso -C 4 H 9) 0.3 AlO] n A solution of isobutylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., containing 6 mol% of trimethylaluminum based on total Al)
Cocatalyst B: 9.0% by mass (as content of Al atom) TMAO-211 toluene solution (methylaluminoxane solution, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% of trimethylaluminum based on total Al). )
Promoter C: Triisobutylaluminum Promoter D: Dimethylanilium tetrakis (pentafluorophenyl) borate
各共重合体の数平均分子量、Ｔｇを表３に示した。 Table 3 shows the number average molecular weight and Tg of each copolymer.
表１、表２、及び表３中の「部」の値は、２−ノルボルネン１００部に対する値である。また、表２中の助触媒Ａ及び助触媒Ｂについて、「部」の値はトルエン溶液としての値である。 The value of "part" in Table 1, Table 2, and Table 3 is a value for 100 parts of 2-norbornene. Further, for the co-catalyst A and the co-catalyst B in Table 2, the value of "part" is the value as a toluene solution.
表３に示されるとおり、本発明によれば、使用した触媒量に対して得られる共重合体の割合が高い。 As shown in Table 3, according to the present invention, the ratio of the obtained copolymer to the amount of the catalyst used is high.
Claims (5)
で表されるチタノセン触媒と、アルキルアルミニウムからなる連鎖移動剤と、アルキルアルミノキサンからなる助触媒との存在下で、少なくとも、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）とＣ４〜Ｃ１２のα−オレフィンから誘導されるα−オレフィンモノマー（Ｂ）とを重合させて共重合体を得る重合工程を含み、
前記重合工程において得られる前記共重合体の量は、前記チタノセン触媒１ｇ当たり１０００ｇ以上であり、
前記連鎖移動剤の使用量が、環状オレフィンモノマー（Ａ）１００質量部に対し、０．０００１質量部以上１０質量部以下であり、
前記共重合体の数平均分子量は２０，０００以上２００，０００以下である、共重合体の製造方法。 Formula (1) below:
In the presence of a titanocene catalyst represented by, a chain transfer agent composed of alkylaluminum, and a cocatalyst composed of alkylaluminoxane , at least a cyclic olefin monomer (A) derived from norbornene and a C4 to C12 α-olefin. A polymerization step of polymerizing the α-olefin monomer (B) derived from
The amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst,
The amount of the chain transfer agent used is 0.0001 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cyclic olefin monomer (A),
The number average molecular weight before Symbol copolymer is 20,000 to 200,000, the production method of the copolymer.
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