JP2006193554A - Cyclohexene copolymer - Google Patents
Cyclohexene copolymer Download PDFInfo
- Publication number
- JP2006193554A JP2006193554A JP2005004073A JP2005004073A JP2006193554A JP 2006193554 A JP2006193554 A JP 2006193554A JP 2005004073 A JP2005004073 A JP 2005004073A JP 2005004073 A JP2005004073 A JP 2005004073A JP 2006193554 A JP2006193554 A JP 2006193554A
- Authority
- JP
- Japan
- Prior art keywords
- group
- cyclohexene
- substituted
- copolymer
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229920001577 copolymer Polymers 0.000 title claims abstract description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000005977 Ethylene Substances 0.000 claims abstract description 35
- 150000001935 cyclohexenes Chemical class 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000004711 α-olefin Substances 0.000 claims description 23
- 150000002430 hydrocarbons Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229910052736 halogen Chemical group 0.000 claims description 10
- 150000002367 halogens Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000003623 transition metal compounds Chemical class 0.000 claims description 8
- 125000005336 allyloxy group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- -1 cyclic olefin compounds Chemical class 0.000 description 70
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000007334 copolymerization reaction Methods 0.000 description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- 125000005808 2,4,6-trimethoxyphenyl group Chemical group [H][#6]-1=[#6](-[#8]C([H])([H])[H])-[#6](-*)=[#6](-[#8]C([H])([H])[H])-[#6]([H])=[#6]-1-[#8]C([H])([H])[H] 0.000 description 2
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical group COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-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
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-UHFFFAOYSA-N 0.000 description 2
- KGCRXHYTNRMHCF-UHFFFAOYSA-N 6-methyl-2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(C)O1 KGCRXHYTNRMHCF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003282 rhenium compounds Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VIOBFIJCQJNINF-UHFFFAOYSA-N (1-methylcyclohex-3-en-1-yl)methanol Chemical compound OCC1(C)CCC=CC1 VIOBFIJCQJNINF-UHFFFAOYSA-N 0.000 description 1
- FNCRYRFSEYFWQZ-UHFFFAOYSA-N (6-methylcyclohex-3-en-1-yl)methanol Chemical compound CC1CC=CCC1CO FNCRYRFSEYFWQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- RFFLAFLAYFXFSW-RHQRLBAQSA-N 1,2-dichloro-3,4,5,6-tetradeuteriobenzene Chemical compound [2H]C1=C([2H])C([2H])=C(Cl)C(Cl)=C1[2H] RFFLAFLAYFXFSW-RHQRLBAQSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- WMAUMTLIDVHITM-UHFFFAOYSA-N 1-methylcyclohex-2-ene-1-carboxylic acid Chemical compound OC(=O)C1(C)CCCC=C1 WMAUMTLIDVHITM-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- BOPCAWBPVSVBMM-UHFFFAOYSA-N 6-methylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1CC=CCC1C=O BOPCAWBPVSVBMM-UHFFFAOYSA-N 0.000 description 1
- RUSMDMDNFUYZTM-UHFFFAOYSA-N 8-chloroquinoline Chemical compound C1=CN=C2C(Cl)=CC=CC2=C1 RUSMDMDNFUYZTM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-O methyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[NH+](C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-O 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- RAYYZJTYTUPECK-UHFFFAOYSA-N n,n-diethyl-2,4-dinitroaniline Chemical compound CCN(CC)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RAYYZJTYTUPECK-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 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 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-O phenylphosphanium Chemical compound [PH3+]C1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-O 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 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
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
Description
本発明は、エチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとからなる共重合体及びその製造方法、並びにシクロヘキセン共重合体からなる成形体に関するものである。
さらに詳しくは、合成が容易でかつ高い共重合性を有する遷移金属触媒を用いてエチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとを共重合することにより得られるシクロヘキセン共重合体と該共重合体を効率よく製造する方法、その成形体に関するものである。
The present invention relates to a copolymer comprising ethylene and / or an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene, a production method thereof, and a molded article comprising a cyclohexene copolymer. .
More specifically, by copolymerizing ethylene and / or an α-olefin having 3 to 20 carbon atoms with substituted and / or unsubstituted cyclohexene using a transition metal catalyst that is easy to synthesize and has high copolymerizability. The present invention relates to a cyclohexene copolymer to be obtained, a method for efficiently producing the copolymer, and a molded product thereof.
従来、シクロペンテン、シクロオクテン、シクロへプテン、ノルボルネン、ノルボルナジエン、ジシクロペンタジエンに代表されるエチレン性不飽和結合を有する環状オレフィン化合物は遷移金属化合物を触媒とする付加重合、開環メタセシス重合に有意の反応性を示すことは公知である。近年、環状オレフィンとエチレンとの共重合体、水素添加環状オレフィン開環重合体は、非晶性構造を呈し透明性が高く、低密度、低複屈折率、低吸水率などの特性、更に環状オレフィン含量に依存し高い耐熱特性をも有することから光学材料用途にその需要を拡げていることは、例えば、特許文献１〜４に開示されている。
また１，３−シクロヘキサジエンをアニオン重合法で重合した後、水素添加処理して得られるポリシクロヘキサン重合体が、高透明性、高耐熱性を有する新規材料であることも特許文献５に開示され公知である。
一方、シクロヘキセンの付加重合に関する報告はごく限られた数しか存在しない。
Ｂ．Ｃ．Ａｎｄｅｒｓｏｎ等は、６５ｋｂａｒ、５００℃においてシクロヘキセンを重合する方法を報告している。６５ｋｂａｒ、５００℃という厳しい重合条件が必要であり、工業的に適用しにくいうえ、得られるシクロヘキセン付加重合体の分子量が低いという問題があることは非特許文献１に開示されている。
Conventionally, cyclic olefin compounds having an ethylenically unsaturated bond typified by cyclopentene, cyclooctene, cycloheptene, norbornene, norbornadiene, and dicyclopentadiene are significant for addition polymerization and ring-opening metathesis polymerization using a transition metal compound as a catalyst. It is known to show reactivity. In recent years, copolymers of cyclic olefin and ethylene, and hydrogenated cyclic olefin ring-opened polymers have an amorphous structure and high transparency, and have characteristics such as low density, low birefringence, low water absorption, and cyclicity. For example,
Patent Document 5 also discloses that a polycyclohexane polymer obtained by polymerizing 1,3-cyclohexadiene by an anionic polymerization method and then hydrogenating is a novel material having high transparency and high heat resistance. It is known.
On the other hand, there are only a limited number of reports on cyclohexene addition polymerization.
B. C. Anderson et al. Reported a method for polymerizing cyclohexene at 65 kbar and 500 ° C.
Ｃ．Ｔｓｏｎｉｓ等は、レニウム化合物と有機アルミニウムからなる触媒を用いてシクロヘキセンを重合する方法を非特許文献２で報告している。また、レニウム化合物、タングステン化合物、モリブデン化合物又はランタン化合物の遷移金属化合物と有機アルミニウムからなる触媒系を用いて、ノルボルネン等の他の環状オレフィン類を予備重合した後に、シクロヘキセンを重合する方法が特許文献６に開示されている。しかしながら、これらの方法によって得られるシクロヘキセン付加重合体は、分子量が低いうえ、いずれも反応時に開環反応を含む副反応を頻発して起こす、２量体を高い割合で含有する、などの問題がある。
近年、珪素あるいは炭素原子等で架橋した２分子のインデニル骨格を有する遷移金属錯体とアルミノキサン化合物からなる、いわゆる架橋メタロセン触媒を用いると２量体含量が少なく、変色のないシクロヘキセン付加重合体が得られることが特許文献７に開示されている。しかしながら、得られるシクロヘキセン付加重合体を十分に高分子量化することができない。
さらに、シクロヘキセンとエチレン、炭素数３〜２０のα−オレフィン、芳香族ビニル化合物及びビニリデン化合物等との共重合を行う場合、エチレン、炭素数３〜２０のα−オレフィン等の単独重合が進行するだけで、シクロヘキセンをランダムに取り込んだシクロヘキセン共重合体を得ることは困難であった。
従って、置換及び／又は未置換シクロヘキセンを構成単位として有し、且つ高分子量化されたシクロヘキセンからなる（共）重合体及びその工業的製造方法、並びに該（共）重合体からなる成形体の開発が望まれている。
C.
In recent years, when a so-called bridged metallocene catalyst comprising a transition metal complex having a bimolecular indenyl skeleton crosslinked with silicon or carbon atoms and an aluminoxane compound is used, a cyclohexene addition polymer having a low dimer content and no discoloration can be obtained. This is disclosed in Patent Document 7. However, the resulting cyclohexene addition polymer cannot be sufficiently increased in molecular weight.
Furthermore, when copolymerization with cyclohexene and ethylene, a C3-C20 alpha-olefin, an aromatic vinyl compound, a vinylidene compound, etc., homopolymerization, such as ethylene and a C3-C20 alpha-olefin, advances. Thus, it was difficult to obtain a cyclohexene copolymer in which cyclohexene was randomly incorporated.
Therefore, development of a (co) polymer comprising a cyclohexene having a substituted and / or unsubstituted cyclohexene as a constituent unit and having a high molecular weight, an industrial production method thereof, and a molded body comprising the (co) polymer Is desired.
本発明はエチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとからなるシクロヘキセン共重合体及びその工業的製造方法、並びに該共重合体からなる成形体を見出すことを目的としてなされたものである。 The present invention finds a cyclohexene copolymer comprising ethylene and / or an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene, an industrial production method thereof, and a molded article comprising the copolymer. It was made for the purpose.
本発明は、合成の容易な、特定のシクロペンタジエニル骨格を含む配位子１分子と、少なくとも１個のアリロキシ基が金属に配位した遷移金属化合物と活性化剤からなる触媒が、エチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとの共重合に対して重合活性を有し、かつ優れた共重合性を示した結果、従来なし得なかったシクロヘキセン共重合体を与えるという驚くべき事実に基づいてなされたものである。
すなわち、本発明は、エチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとからなるシクロヘキセン共重合体、下記式（１）で表される遷移金属化合物（Ａ）および有機アルミニウムオキシ化合物または有機ホウ素化合物から選ばれる１種以上の活性化剤（Ｂ）からなる遷移金属触媒の存在下にエチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとの共重合を行うことを特徴とするシクロヘキセン共重合体の製造方法、並びにシクロヘキセン共重合体からなる成形体に関する。
The present invention relates to an easily synthesized catalyst comprising one molecule of a ligand containing a specific cyclopentadienyl skeleton, a transition metal compound in which at least one allyloxy group is coordinated to a metal, and an activator. And / or having a polymerization activity for the copolymerization of an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene and exhibiting excellent copolymerizability, as a result, could not be achieved conventionally. This is based on the surprising fact that it gives a cyclohexene copolymer.
That is, the present invention relates to a cyclohexene copolymer comprising ethylene and / or an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene, a transition metal compound represented by the following formula (1) (A ) And one or more activators (B) selected from organoaluminum oxy compounds or organoboron compounds in the presence of a transition metal catalyst, ethylene and / or an α-olefin having 3 to 20 carbon atoms, Alternatively, the present invention relates to a method for producing a cyclohexene copolymer, which comprises copolymerizing with unsubstituted cyclohexene, and a molded article made of the cyclohexene copolymer.
さらに本発明は、前記一般式（１）で表される遷移金属化合物において、Ｍで表される遷移金属がＴｉ、ＺｒまたはＨｆである、エチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとの共重合体の製造方法に関するものである。
Furthermore, the present invention provides ethylene and / or an α-olefin having 3 to 20 carbon atoms in which the transition metal represented by M is Ti, Zr or Hf in the transition metal compound represented by the general formula (1). , And a method for producing a copolymer with substituted and / or unsubstituted cyclohexene.
本発明によって、エチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとからなるシクロヘキセン共重合体、その工業的な製造方法並びに該共重合体からなる成形体を提供する。 According to the present invention, a cyclohexene copolymer comprising ethylene and / or an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene, an industrial production method thereof, and a molded body comprising the copolymer are obtained. provide.
以下、本発明に関わるエチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとからなるシクロヘキセン共重合体、シクロヘキセン共重合体の製造方法並びにその成形体について詳細に説明する。
本発明で使用できる置換及び未置換シクロヘキセンとは、下記一般式（２）で表される化合物である。
式中、Ｒ9〜Ｒ16は、好ましくは、水素、または炭化水素基であり、より好ましくは水素である。炭化水素基の炭素数としては通常１〜２０、好ましくは１〜１０、より好ましくは１〜６の範囲である。炭化水素基の具体例としては、アルキル基、アルケニル基、アリル基またはアラルキル基などが挙げられ、好ましくはアルキル基であり、その中でも炭素数１〜６のアルキル基が特に好ましい。官能基が置換した炭化水素基としては、例えば、炭素数１〜２０、好ましくは１〜１０、より好ましくは１〜６のエステル基含有アルキル基などを挙げることができる。
Hereinafter, a cyclohexene copolymer comprising ethylene and / or an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene according to the present invention, a method for producing the cyclohexene copolymer, and a molded product thereof will be described in detail. explain.
The substituted and unsubstituted cyclohexene that can be used in the present invention is a compound represented by the following general formula (2).
In the formula, R 9 to R 16 are preferably hydrogen or a hydrocarbon group, and more preferably hydrogen. As carbon number of a hydrocarbon group, it is 1-20 normally, Preferably it is 1-10, More preferably, it is the range of 1-6. Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an allyl group, and an aralkyl group, preferably an alkyl group, and particularly preferably an alkyl group having 1 to 6 carbon atoms. Examples of the hydrocarbon group substituted with a functional group include an ester group-containing alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.
置換及び未置換シクロヘキセンの具体例としては、例えば、シクロヘキセン、４−メチル−１−シクロヘキセン、４−ビニル−１−シクロヘキセン、２−シクロヘキセン−１−オール、３−シクロヘキセン−１−イルメタノール、１−メチル−３−シクロヘキセン−１−イルメタノール、６−メチル−３−シクロヘキセン−１−イルメタノール、３−シクロヘキセン−１,１−ジメタノール、１−（２−シクロヘキセン−１−イル）−１−プロパノール、３−シクロヘキセン−１−カルボアルデヒド、６−メチル−３−シクロヘキセン−１−カルボアルデヒド、３−シクロヘキセン−１−カルボキシレート、１−メチル−２−シクロヘキセン−１−カルボキシレート、３−シクロヘキセン−１−カルボニトリル等を挙げることができる。これらのうち最も好ましくはシクロヘキセンである。
本発明で使用できる炭素数３〜２０のα−オレフィンの具体例としては、例えば、プロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−ヘプテン、１−オクテン、１−デセン、１−ドデセン等をあげることができる。これらのうち好ましくは１−ヘキセン、１−オクテンである。
また、本発明の炭素数３〜２０のα−オレフィン類には、下記一般式（３）で表されるオレフィン類（以下「極性オレフィン類」という。）が含まれる。
ＣＨ2＝ＣＲ17−Ｙ ・・・（３）
（式中、Ｒ17は、水素、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン化炭化水素基又は炭素数１〜２０のアルキルシリル基から選ばれた基であり、Ｙは、エステル基、カルボキシル基、水酸基、アミノ基、シアノ基、アミド基、ニトロ基の群から選ばれる少なくとも１種の官能基である。）
Specific examples of the substituted and unsubstituted cyclohexene include, for example, cyclohexene, 4-methyl-1-cyclohexene, 4-vinyl-1-cyclohexene, 2-cyclohexen-1-ol, 3-cyclohexen-1-ylmethanol, 1- Methyl-3-cyclohexen-1-ylmethanol, 6-methyl-3-cyclohexen-1-ylmethanol, 3-cyclohexene-1,1-dimethanol, 1- (2-cyclohexen-1-yl) -1-propanol 3-cyclohexene-1-carbaldehyde, 6-methyl-3-cyclohexene-1-carbaldehyde, 3-cyclohexene-1-carboxylate, 1-methyl-2-cyclohexene-1-carboxylate, 3-cyclohexene-1 -A carbonitrile etc. can be mentioned. Of these, most preferred is cyclohexene.
Specific examples of the α-olefin having 3 to 20 carbon atoms that can be used in the present invention include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-octene, and the like. Decene, 1-dodecene and the like can be mentioned. Of these, 1-hexene and 1-octene are preferred.
The C3-C20 α-olefins of the present invention include olefins represented by the following general formula (3) (hereinafter referred to as “polar olefins”).
CH 2 = CR 17 −Y (3)
(In the formula, R 17 is a group selected from hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms. Y is at least one functional group selected from the group consisting of ester group, carboxyl group, hydroxyl group, amino group, cyano group, amide group and nitro group.
極性オレフィン類の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−アミル（メタ）アクリレート、ｉ−アミル（メタ）アクリレート、（メタ）アクリル酸、クロトン酸、けい皮酸、マレイン酸、フマル酸、イタコン酸、マレイン酸モノメチル、マレイン酸モノエチル、ヒドロキシメチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ジメチルアミノエチル（メタ）アクリレート、２−ジエチルアミノエチル（メタ）アクリレート、２−ジメチルアミノプロピル（メタ）アクリレート、（メタ）アクリロニトリル、α−クロロアクリロニトリル、エタクリロニトリル、２−シアノエチル（メタ）アクリレート、２−シアノプロピル（メタ）アクリレート、（メタ）アクリルアミド、α−クロロ（メタ）アクリルアミド、エタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−ビニル−ε−カプロラクタム、Ｎ−ビニルピロリドン、２−ニトロエチル（メタ）アクリレート、３−ニトロプロピル（メタ）アクリレート等をあげることができる。
本発明のシクロヘキセン共重合体中、エチレン及び／又は炭素数３〜２０のα−オレフィンが０．１〜９９．９モル％、及び置換及び／又は未置換シクロヘキセンが０．１〜９９．９モル％の範囲にある。
Specific examples of polar olefins include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid , Fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2 -Dimethylaminoethyl (Meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, (meth) acrylonitrile, α-chloroacrylonitrile, ethacrylonitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl ( (Meth) acrylate, (meth) acrylamide, α-chloro (meth) acrylamide, ethacrylamide, N-methyl (meth) acrylamide, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-nitroethyl (meth) acrylate, 3- Examples thereof include nitropropyl (meth) acrylate.
In the cyclohexene copolymer of the present invention, ethylene and / or α-olefin having 3 to 20 carbon atoms is 0.1 to 99.9 mol%, and substituted and / or unsubstituted cyclohexene is 0.1 to 99.9 mol. % Range.
本発明のエチレン及び／又は炭素数３〜２０のα−オレフィンと、置換及び／又は未置換シクロヘキセンとの共重合に用いる遷移金属触媒の遷移金属化合物（Ａ）については、前記式（１）で表されるが、式中、Ｍは周期律表３〜５族の遷移金属を表す。好ましくは周期律表４族の遷移金属を表す。より好ましくはＴｉ，Ｚｒ又はＨｆを表す。最も好ましくはＴｉである。Ｘは、Ｘが複数有る場合、複数のＸはそれぞれ同じでも異なっていても良く、水素、炭素数１〜２０のアルキル基、アルコキシ基、アリール基、アリロキシ基またはハロゲンから選ばれる基である。好ましくは炭素数１〜２０のアルキル基またはハロゲンからなる基である。ｎは１〜３の整数である。Ｒ1〜Ｒ8はそれぞれ同じでも異なっていても良く、水素、炭素数１〜２０のアルキル基、アルコキシ基、アリール基、アリロキシ基またはハロゲンから選ばれた基であり、任意の２つまたは３つが結合し環を形成していても良い。環には共役２重結合を含んだ芳香族性を有するものも含む。好ましくは水素または炭素数１〜２０のアルキル基からなる。ｍは０〜３の整数である。なかでも１〜３置換のシクロペンタジエン環を有する場合は、さらに好適である。 The transition metal compound (A) of the transition metal catalyst used for the copolymerization of ethylene and / or an α-olefin having 3 to 20 carbon atoms with a substituted and / or unsubstituted cyclohexene is represented by the formula (1). In the formula, M represents a transition metal of Groups 3 to 5 in the periodic table. Preferably, it represents a transition metal of Group 4 of the periodic table. More preferably, it represents Ti, Zr or Hf. Most preferred is Ti. X is a group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a halogen, when a plurality of Xs are present, the Xs may be the same or different. Preferably, it is a group consisting of an alkyl group having 1 to 20 carbon atoms or halogen. n is an integer of 1 to 3. R 1 to R 8 may be the same or different and each is a group selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a halogen, and any two or three May be bonded to form a ring. The ring includes those having aromaticity including a conjugated double bond. Preferably it consists of hydrogen or a C1-C20 alkyl group. m is an integer of 0-3. Of these, the case of having a 1-3 substituted cyclopentadiene ring is more preferred.
前記式（１）におけるＸ及びＲ1〜Ｒ8のアルキル基、アルコキシ基、アリール基、アリロキシ基のアルキル、アリール部分の具体例としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｓｅｃ−ブチル、ｎ−ペンチル、イソペンチル、１−メチルブチル、２−メチルブチル、１，２−ジメチルプロピル、ネオペンチル、シクロペンチル、ｎ−ヘキシル、イソヘキシル、１−メチルペンチル、２，２−ジメチルブチル、１，１−エチルメチルプロピル、２−エチルブチル、シクロヘキシル、ｎ−ヘプチル、イソヘプチル、４−メチルヘキシル、１，２−ジメチルペンチル、２−エチルペンチル、２，４−ジメチルペンチル、１−エチル−３−メチルブチル、３−メチルシクロヘキシル、シクロヘプチル、１，１，３−トリメチルブチル、１，１，２，２−テトラメチルプロピル、ｎ−オクチル、１−メチルヘプチル、イソオクチル、４−エチルヘキシル、４，４−ジメチルヘキシル、１，３−ジメチルヘキシル、２，３−ジメチルヘキシル、１−エチル−３−メチルペンチル、２，２−エチルメチルペンチル、１，１−ジエチルブチル、２−メチル−１−プロピルブチル、４−エチルシクロヘキシル、３，４−ジメチルシクロヘキシル、１，１，２−トリメチルペンチル、１，１，３，３−テトラメチルブチル、ｎ−ノニル、イソノニル、１−メチルオクチル、４−エチルヘプチル、１，４−ジメチルヘプチル、１，１，３−トリメチルヘキシル、２，２−エチルメチルヘキシル、１，１−ジエチルペンチル、２，２−メチルプロピルペンチル、ｎ−デシル、イソデシル、１−メチルノニル、２−エチルオクチル、２，２−ジメチルオクチル、１，２−ジメチルオクチル、ｎ−ウンデシル、ｎ−ドデシル、フェニル、ベンジル、ｐ−トリル、ｍ−トリル、キシリル、メシチリル、２，６−ジメチルフェニル、２，４，６−トリメチルフェニル、２，６−ジメトキシフェニル、２，４，６−トリメトキシフェニル、２，６−ジイソプロピルフェニル、２，４，６−トリイソプロピルフェニル、ナフチル、２−メトキシフェニル、２−イソプロポキシフェニル、２−ｔ−ブトキシフェニル、２，６−ジ−ｔ−ブチルフェニル、２−メチルフェニル、２−イソプロピルフェニル、２−ｔ−ブチルフェニル、２−メチル−６−イソプロピルフェニル、２−メチル−６−ｔ−ブチルフェニルなどが挙げられる。これらの炭化水素基は水素原子を任意にハロゲン原子で置換していてもよい。ハロゲン原子で置換した炭化水素基の例としては、トリクロロメチル、トリフルオロメチル、ジクロロメチル、クロロメチル、ｏ−クロロフェニル、ペンタフルオロフェニルなどが挙げられる。これらは単独で用いてもよいし、組み合わせて用いてもよい。 Specific examples of the alkyl group, alkoxy group, aryl group, alkyl of aryloxy group, and aryl moiety of X and R 1 to R 8 in the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2,2- Dimethylbutyl, 1,1-ethylmethylpropyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, 4-methylhexyl, 1,2-dimethylpentyl, 2-ethylpentyl, 2,4-dimethylpentyl, 1-ethyl -3-methylbutyl, 3-methylcyclohexyl, cyclohexyl Til, 1,1,3-trimethylbutyl, 1,1,2,2-tetramethylpropyl, n-octyl, 1-methylheptyl, isooctyl, 4-ethylhexyl, 4,4-dimethylhexyl, 1,3-dimethyl Hexyl, 2,3-dimethylhexyl, 1-ethyl-3-methylpentyl, 2,2-ethylmethylpentyl, 1,1-diethylbutyl, 2-methyl-1-propylbutyl, 4-ethylcyclohexyl, 3,4 -Dimethylcyclohexyl, 1,1,2-trimethylpentyl, 1,1,3,3-tetramethylbutyl, n-nonyl, isononyl, 1-methyloctyl, 4-ethylheptyl, 1,4-dimethylheptyl, 1, 1,3-trimethylhexyl, 2,2-ethylmethylhexyl, 1,1-diethylpentyl, 2,2-methylpropylpe N-til, n-decyl, isodecyl, 1-methylnonyl, 2-ethyloctyl, 2,2-dimethyloctyl, 1,2-dimethyloctyl, n-undecyl, n-dodecyl, phenyl, benzyl, p-tolyl, m-tolyl Xylyl, mesitylyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6 -Triisopropylphenyl, naphthyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 2-t-butoxyphenyl, 2,6-di-t-butylphenyl, 2-methylphenyl, 2-isopropylphenyl, 2-t- Butylphenyl, 2-methyl-6-isopropylphenyl, 2-methyl-6-tert-butylpheny And the like. In these hydrocarbon groups, a hydrogen atom may be optionally substituted with a halogen atom. Examples of the hydrocarbon group substituted with a halogen atom include trichloromethyl, trifluoromethyl, dichloromethyl, chloromethyl, o-chlorophenyl, pentafluorophenyl and the like. These may be used alone or in combination.
前記式（１）で表される具体的な金属錯体として、例えば、ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、Ｃｐ*Ｔｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ＭｅＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−Ｍｅ2ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，２，３−Ｍｅ3ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，２，４−Ｍｅ3ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ｎ−ＢｕＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2 、ｔ−ＢｕＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−ｎ−Ｂｕ2ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−ｔ−Ｂｕ2ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、Ｃｐ*Ｚｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ＭｅＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−Ｍｅ2ＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，２，３−Ｍｅ3ＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，２，４−Ｍｅ3ＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ｎ−ＢｕＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ｔ−ＢｕＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−ｎ−Ｂｕ2ＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−ｔ−Ｂｕ2ＣｐＺｒ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、Ｃｐ*Ｈｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ＭｅＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−Ｍｅ2ＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，２，３−Ｍｅ3ＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，２，４−Ｍｅ3ＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ｎ−ＢｕＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ｔ−ＢｕＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−ｎ−Ｂｕ2ＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、１，３−ｔ−Ｂｕ2ＣｐＨｆ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2、ＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、Ｃｐ*ＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、ＭｅＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、１，３−Ｍｅ2ＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、１，２，３−Ｍｅ3ＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、１，２，４−Ｍｅ3ＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、ｎ−ＢｕＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、ｔ−ＢｕＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、１，３−ｎ−Ｂｕ2ＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）、１，３−ｔ−Ｂｕ2ＣｐＴｉＭｅ2（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）（前記構造式中、Ｃｐはシクロペンタジエニル基を、Ｃｐ*はペンタメチルシクロペンタジエニル基を、iＰｒはイソプロピル基を表す。）等を例示することが出来る。これらは単独で用いても良いし、組み合わせて用いても良い。 Specific examples of the metal complex represented by the formula (1) include CpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , Cp * Ti (O-2,6- i Pr 2). C 6 H 3 ) Cl 2 , MeCpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1,3-Me 2 CpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2, 1,2,3-Me 3 CpTi ( O-2,6- i Pr 2 C 6 H 3) Cl 2, 1,2,4-Me 3 CpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , n-BuCpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , t-BuCpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1, 3-n-Bu 2 CpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1,3-t-Bu 2 CpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2, CpZr (O-2,6- i P r 2 C 6 H 3 ) Cl 2 , Cp * Zr (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , MeCpZr (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1,3-Me 2 CpZr (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1,2,3-Me 3 CpZr (O-2,6- i Pr 2 C 6 H 3 ) Cl 2, 1,2,4-Me 3 CpZr ( O-2,6- i Pr 2 C 6 H 3) Cl 2, n-BuCpZr (O-2,6- i Pr 2 C 6 H 3) Cl 2, t-BuCpZr (O-2,6- i Pr 2 C 6 H 3) Cl 2, 1,3-n-Bu 2 CpZr (O-2,6- i Pr 2 C 6 H 3) Cl 2, 1, 3-t-Bu 2 CpZr ( O-2,6- i Pr 2 C 6 H 3) Cl 2, CpHf (O-2,6- i Pr 2 C 6 H 3) Cl 2, Cp * Hf (O- 2,6- i Pr 2 C 6 H 3 ) Cl 2, MeCp f (O-2,6- i Pr 2 C 6 H 3) Cl 2, 1,3-Me 2 CpHf (O-2,6- i Pr 2 C 6 H 3) Cl 2, 1,2,3- Me 3 CpHf (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1,2,4-Me 3 CpHf (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , n- BuCpHf (O-2,6- i Pr 2 C 6 H 3) Cl 2, t-BuCpHf (O-2,6- i Pr 2 C 6 H 3) Cl 2, 1,3-n-Bu 2 CpHf ( O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , 1,3-t-Bu 2 CpHf (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 , CpTiMe 2 (O-2 , 6- i Pr 2 C 6 H 3), Cp * TiMe 2 (O-2,6- i Pr 2 C 6 H 3), MeCpTiMe 2 (O-2,6- i Pr 2 C 6 H 3), 1,3-Me 2 CpTiMe 2 (O -2 6- i Pr 2 C 6 H 3 ), 1,2,3-Me 3 CpTiMe 2 (O-2,6- i Pr 2 C 6 H 3), 1,2,4-Me 3 CpTiMe 2 (O- 2,6- i Pr 2 C 6 H 3 ), n-BuCpTiMe 2 (O-2,6- i Pr 2 C 6 H 3), t-BuCpTiMe 2 (O-2,6- i Pr 2 C 6 H 3 ), 1,3-n-Bu 2 CpTiMe 2 (O-2,6- i Pr 2 C 6 H 3 ), 1,3-t-Bu 2 CpTiMe 2 (O-2,6- i Pr 2 C 6 H 3 ) (wherein Cp represents a cyclopentadienyl group, Cp * represents a pentamethylcyclopentadienyl group, and i Pr represents an isopropyl group. ) And the like. These may be used alone or in combination.
本発明で用いることのできる有機アルミニウムオキシ化合物としては下記一般式（４）、（５）、（６）および（７）で示される有機アルミニウムオキシ化合物のうち少なくとも１つの化合物があげられる。
これら有機アルミニウムオキシ化合物の具体例としては、メチルアルミノキサン、エチルアルミノキサン、プロピルアルミノキサン、ブチルアルミノキサン、イソブチルアルミノキサン、メチルエチルアルミノキサン、メチルブチルアルミノキサン、メチルイソブチルアルミノキサン等が挙げられる。特に、メチルアルミノキサン、イソブチルアルミノキサン、メチルイソブチルアルミノキサンが好適に使用できる。これらは２種以上組み合わせて用いてもよい。
また、これら有機アルミニウムオキシ化合物には、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム等の有機アルミニウム化合物を含んでいてもよい。
また、本発明で用いることのできる有機ホウ素化合物としては下記一般式（８）または（９）で示される有機ホウ素化合物のうち少なくとも１つの化合物が挙げられる。
（ＢＲ29Ｒ30Ｒ31）n ・・・（８）
（式中、Ｒ29〜Ｒ31はそれぞれ同じでも異なっていてもよく、炭素数１〜１４のハロゲン化アリール基またはハロゲン化アリロキシ基を含む炭化水素基、ｎは１〜４までの整数を表す。）
Ｑ（ＢＲ32Ｒ33Ｒ34Ｒ35）n ・・・（９）
（式中、Ｑは４級アミンまたは４級アンモニウム塩またはカルボカチオンまたは価数＋１〜＋４の金属カチオンであり、Ｒ32〜Ｒ35はそれぞれ同じでも異なっていてもよく、炭素数１〜１４のハロゲン化アリール基またはハロゲン化アリロキシ基を含む炭化水素基、ｎは１〜４までの整数を表す。）
Specific examples of these organoaluminum oxy compounds include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. In particular, methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane can be preferably used. Two or more of these may be used in combination.
These organoaluminum oxy compounds may contain organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum.
Moreover, as an organic boron compound which can be used by this invention, at least 1 compound is mentioned among the organic boron compounds shown by the following general formula (8) or (9).
(BR 29 R 30 R 31 ) n (8)
(In the formula, R 29 to R 31 may be the same or different and each represents a hydrocarbon group containing a halogenated aryl group having 1 to 14 carbon atoms or a halogenated allyloxy group, and n represents an integer of 1 to 4. .)
Q (BR 32 R 33 R 34 R 35) n ··· (9)
(In the formula, Q is a quaternary amine, a quaternary ammonium salt, a carbocation, or a metal cation having a valence of +1 to +4, and R 32 to R 35 may be the same or different, and have 1 to 14 carbon atoms. A hydrocarbon group containing a halogenated aryl group or a halogenated allyloxy group, n represents an integer of 1 to 4.)
前記一般式（８）および（９）の炭化水素基の具体例としてはフェニル、ベンジル、ｐ−トリル、ｍ−トリル、キシリル、メシチリル、２，６−ジメチルフェニル，２，４，６−トリメチルフェニル，２，６−ジメトキシフェニル，２，４，６−トリメトキシフェニル，２，６−ジイソプロピルフェニル，２，４，６−トリイソプロピルフェニル、ナフチル、ｏ−イソプロポキシフェニル、ペンタフルオロフェニル、ペンタフルオロベンジル、テトラフルオロフェニル、テトラフルオロトリル等が挙げられる。
また、前記一般式（９）のＱの具体例としては、ピリジニウム、２，４−ジニトロ−Ｎ，Ｎ−ジエチルアニリニウム、ｐ−ニトロアニリニウム、２，５−ジクロロアニリン、ｐ−ニトロ−Ｎ，Ｎ−ジメチルアニリニウム，キノリニウム、Ｎ，Ｎ−ジメチルアニリニウム，メチルジフェニルアンモニウム、Ｎ，Ｎ−ジエチルアニリニウム、８−クロロキノリニウム、トリメチルアンモニウム、トリプロピルアンモニウム、トリエチルアンモニウム、トリブチルアンモニウム、トリフェニルホスホニウム、アンモニウム、トリフェニルメチル、ナトリウム、リチウム、カリウム、セシウム、カルシウム、マグネシウム等が挙げられる。
Specific examples of the hydrocarbon groups of the general formulas (8) and (9) include phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl. 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, o-isopropoxyphenyl, pentafluorophenyl, pentafluorobenzyl , Tetrafluorophenyl, tetrafluorotolyl and the like.
Specific examples of Q in the general formula (9) include pyridinium, 2,4-dinitro-N, N-diethylanilinium, p-nitroanilinium, 2,5-dichloroaniline, p-nitro-N. , N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, methyldiphenylammonium, N, N-diethylanilinium, 8-chloroquinolinium, trimethylammonium, tripropylammonium, triethylammonium, tributylammonium, tri Examples include phenylphosphonium, ammonium, triphenylmethyl, sodium, lithium, potassium, cesium, calcium, magnesium, and the like.
これら有機ホウ素化合物の具体例としては、トリメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリエチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。これらは２種以上組み合わせて用いてもよい。最も好ましくはトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレートが挙げられる。
本発明において使用するのに好適な触媒は（Ａ）遷移金属化合物および（Ｂ）アルキルアルミニウムオキシ化合物または有機ホウ素化合物から選ばれる１種以上の活性化剤を任意の順序でかつ任意の好適な方法で組み合わせることによって製造される。
前記（Ａ）成分と（Ｂ）成分の触媒組成比（モル比）は、好ましくは（Ａ）：（Ｂ）＝１：０．０１〜１：１００００であり、更に好ましくは１：１００〜１：３０００である。
触媒調製はあらかじめ、窒素、アルゴン等の不活性ガス雰囲気下、好適な溶媒中で混合することにより行ってもよいし、（Ａ）、（Ｂ）それぞれの成分を別々にモノマーが共存するリアクター内に導入して、リアクター内において調製してもよい。触媒調製に好適な溶媒としては、ヘキサン、シクロヘキサン等のアルカンをはじめとする炭化水素系溶媒とトルエン、ベンゼン、エチルベンゼン等の芳香族系の溶媒が挙げられる。またこれらの溶媒は前処理において水分等を除去しておくことが好ましい。触媒の調製温度としては−２０℃〜１５０℃が最適である。
Specific examples of these organic boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl). ) Borate and the like. Two or more of these may be used in combination. Most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.
Suitable catalysts for use in the present invention are (A) transition metal compounds and (B) one or more activators selected from alkylaluminumoxy compounds or organoboron compounds in any order and in any suitable process. Manufactured by combining with.
The catalyst composition ratio (molar ratio) between the component (A) and the component (B) is preferably (A) :( B) = 1: 0.01 to 1: 10000, more preferably 1: 100 to 1. : 3000.
The catalyst may be prepared in advance by mixing it in a suitable solvent under an inert gas atmosphere such as nitrogen or argon, or (A) and (B) in a reactor in which each component separately coexists with a monomer. And may be prepared in a reactor. Suitable solvents for catalyst preparation include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene, and ethylbenzene. Moreover, it is preferable to remove water and the like from these solvents in the pretreatment. The optimum catalyst preparation temperature is -20 ° C to 150 ° C.
本発明の共重合方法は、モノマー類と触媒の存在下、減圧、大気圧、加圧のいずれかの条件のもと、バルク、溶液、スラリーのいずれの方法でも行うことができる。
共重合を行うのに好適な温度範囲としては−３０℃〜２６０℃であり、好ましくは０℃〜２００℃である。また、共重合においては、窒素、アルゴン等の不活性ガス雰囲気下で行ってもよいし、エチレン雰囲気下で行ってもよい、またエチレン及び／又はα−オレフィン類と上記の不活性ガスの混合雰囲気下でもかまわない。さらに、分子量調節のために上記のガスに加えて、水素を共存させてもかまわない。また、触媒成分をアルミナ、塩化マグネシウム、シリカのような好適な担体に担持させて用いてもかまわない。また所望ならば、共重合に際して溶媒を用いることも出来る。共重合に用いるのに好適な溶媒としては、ヘキサン、シクロヘキサン等のアルカンをはじめとする炭化水素系溶媒とトルエン、ベンゼン、エチルベンゼン等の芳香族系の溶媒が挙げられる。
The copolymerization method of the present invention can be carried out in any of bulk, solution, and slurry under the conditions of reduced pressure, atmospheric pressure, and increased pressure in the presence of monomers and a catalyst.
The temperature range suitable for carrying out the copolymerization is -30 ° C to 260 ° C, preferably 0 ° C to 200 ° C. The copolymerization may be performed in an inert gas atmosphere such as nitrogen or argon, or may be performed in an ethylene atmosphere, or a mixture of ethylene and / or α-olefins and the above inert gas. It does not matter even in the atmosphere. Furthermore, hydrogen may be coexisted in addition to the above gas for molecular weight adjustment. Further, the catalyst component may be used by being supported on a suitable carrier such as alumina, magnesium chloride, or silica. If desired, a solvent can be used in the copolymerization. Suitable solvents for use in the copolymerization include hydrocarbon solvents such as alkanes such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene, and ethylbenzene.
共重合における好適な触媒量は、［（生成ポリマー重量）ｋｇ］／［触媒（Ａ）成分１ｍｏｌ］＝１０ｋｇ／１ｍｏｌ〜１００００００ｋｇ／１ｍｏｌ程度のポリマーを与える量である。本発明における共重合後のポリマーの分離方法としては、例えば、共重合液にアセトン又は酸もしくはアルカリを混合したアルコール等の貧溶媒となる極性溶媒を加えて共重合体を沈澱させて回収する方法、反応液を撹拌下、熱湯中に投入後、溶媒と共に蒸留回収する方法、または直接反応液を加熱して溶媒を留去する方法、等を挙げることができる。
本発明のシクロヘキセン共重合体の製造方法において、３種類以上の成分を使用してもよく三元あるいは四元以上の共重合体の製造も可能である。すなわち、シクロヘキセン共重合体の製造方法において、上記モノマー以外にも必要に応じてプロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテンのような炭素数３〜２０のα−オレフィン、シクロペンテン、ノルボルネンのような環状オレフィン、スチレンのような芳香族ビニル化合物を共重合モノマーとして共重合することも可能である。
本発明のシクロヘキセン共重合体の製造方法において、共重合体中の組成は、エチレン及び／又は炭素数３〜２０のα−オレフィン０．１〜９９．９ｍｏｌ％に対し、置換及び／又は未置換シクロヘキセン９９．９〜０．１ｍｏｌ％の範囲で共重合できる。
A suitable catalyst amount in the copolymerization is an amount that gives a polymer of [(product polymer weight) kg] / [catalyst (A)
In the method for producing a cyclohexene copolymer of the present invention, three or more kinds of components may be used, and a ternary or quaternary or more copolymer can be produced. That is, in the method for producing a cyclohexene copolymer, if necessary, in addition to the above-mentioned monomers, a carbon number of 3 to 20 such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene is used. It is also possible to copolymerize a cyclic olefin such as α-olefin, cyclopentene or norbornene, or an aromatic vinyl compound such as styrene as a copolymerization monomer.
In the method for producing a cyclohexene copolymer of the present invention, the composition in the copolymer is substituted and / or unsubstituted with respect to 0.1 to 99.9 mol% of ethylene and / or α-olefin having 3 to 20 carbon atoms. Cyclohexene can be copolymerized in the range of 99.9 to 0.1 mol%.
以下に実施例などにより本発明を更に具体的に説明するが、本発明はこれら実施例などにより何ら限定されるものではない。
重合活性は重合終了後に得られたポリマー量から求めた。ポリマー中のコモノマー含有量は、「Macromolecules, 31, 5145(1998)」に記載されている水素添加シクロヘキサジエン重合体の帰属結果を参考に、13Ｃ−ＮＭＲスペクトルを用いて行った。ＮＭＲ測定はベンゼン−ｄ6／１，２−ジクロロベンゼン−ｄ4（１／１ｖｏｌ比）溶液中で行った。ポリマーの分子量はＧＰＣ法により１４０℃において、ｏ−ジクロルベンゼンを測定溶媒として、ＲＩにより検出し、ポリスチレン換算により求めた。
重合触媒として用いた金属錯体は、ｔ−ＢｕＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2（以下、金属錯体−１）、１，３，４−Ｍｅ3ＣｐＴｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2（以下、金属錯体−２）、Ｃｐ*Ｔｉ（Ｏ−２，６−iＰｒ2Ｃ6Ｈ3）Ｃｌ2（以下、金属錯体−３）、Ｃｐ2ＺｒＣｌ2（以下、金属錯体−４）、及びＭｅ4ＣｐＳｉ（Ｍｅ）2Ｎ（ｔ−Ｂｕ）ＴｉＣｌ2（以下、金属錯体−５）である。金属錯体１〜３については、Macromolecules, 31, 7588(1998)、Inorg. Chim. Acta., 345, 37(2003) 等記載の方法で合成した。金属錯体−５についてはＥＰ−Ａ１−０５１４８２８号公報等記載の方法で調製した。また、金属錯体−４は、アヅマックス（株）から購入し精製することなく、そのまま使用した。
EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to these examples.
The polymerization activity was determined from the amount of polymer obtained after completion of the polymerization. The comonomer content in the polymer was determined using a 13 C-NMR spectrum with reference to the assignment result of the hydrogenated cyclohexadiene polymer described in “Macromolecules, 31, 5145 (1998)”. NMR measurement was performed in a benzene-d 6 / 1,2-dichlorobenzene-d 4 (1/1 vol ratio) solution. The molecular weight of the polymer was determined by the GPC method at 140 ° C., detected by RI using o-dichlorobenzene as a measurement solvent, and calculated in terms of polystyrene.
The metal complex used as the polymerization catalyst was t-BuCpTi (O-2,6- i Pr 2 C 6 H 3 ) Cl 2 (hereinafter referred to as metal complex-1), 1,3,4-Me 3 CpTi (O— 2,6- i Pr 2 C 6 H 3 ) Cl 2 ( hereinafter, metal complexes -2), Cp * Ti (O -2,6- i Pr 2 C 6 H 3) Cl 2 ( hereinafter, metal complexes -3 ), Cp 2 ZrCl 2 (hereinafter metal complex-4), and Me 4 CpSi (Me) 2 N (t-Bu) TiCl 2 (hereinafter metal complex-5).
［実施例１］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で６ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ3を真空下で除いて使用した。）を導入した。次いで、活性アルミナカラムを通し脱水、窒素置換により脱酸素処理を施したシクロヘキセンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を３０ｍｌ仕込んだ。オートクレーブの内温を２５℃に保ち、金属錯体−１を２．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝４２３ｋｇ／ｍｏｌ−Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝３．２×１０4（Ｍｗ／Ｍｎ＝１．７）であった。13Ｃ−ＮＭＲから共重合体中のシクロヘキセン含有量は１６．２ｍｏｌ％と見積もられた。
13Ｃ−ＮＭＲ：３９．８７０（Ｃ1/Ｃ2）、３０．４８７、３０．４１８（Ｃ3／Ｃ6）、３０．１２０（ＣPE/Ｃγ/Ｃδ）、２９．４２４（Ｃβ）、２８．２８５（Ｃα）、２４．４２３、２４．３５４（Ｃ4/Ｃ5）
このものの13Ｃ−ＮＭＲスペクトルを図１に示す。
[Example 1]
The inside was vacuum degassed and nitrogen-substituted 100 ml autoclave was used as a white solid MAO (methylaluminoxane) (6 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that the solvent toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution (concentration: 5.0 mol / l) of cyclohexene that had been dehydrated through an activated alumina column and deoxygenated by nitrogen substitution was charged. The internal temperature of the autoclave was kept at 25 ° C., and 2 ml of a toluene solution containing 2.0 μmol of metal complex-1 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 423 kg / mol-Ti · h. From the GPC measurement, it was Mn = 3.2 × 10 4 (Mw / Mn = 1.7). From 13 C-NMR, the cyclohexene content in the copolymer was estimated to be 16.2 mol%.
13 C-NMR: 39.870 (C 1 / C 2 ), 30.487, 30.418 (C 3 / C 6 ), 30.120 (C PE / Cγ / Cδ), 29.424 (Cβ), 28.285 (Cα), 24.423, 24.354 (C 4 / C 5 )
The 13 C-NMR spectrum of this product is shown in FIG.
［実施例２］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ3を真空下で除いて使用した。）を導入した。次いで、活性アルミナカラムを通し脱水、窒素置換により脱酸素処理を施したシクロヘキセンのトルエン溶液（濃度：２．５ｍｏｌ／ｌ）を３０ｍｌ仕込んだ。オートクレーブの内温を２５℃に保ち、金属錯体−２を０．５μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝１８３６ｋｇ／ｍｏｌ−Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝７．７×１０4（Ｍｗ／Ｍｎ＝１．６）であった。13Ｃ−ＮＭＲから共重合体中のシクロヘキセン含有量は９．３ｍｏｌ％と見積もられた。
[Example 2]
The inside was vacuum degassed, and nitrogen-substituted 100 ml autoclave was used with white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution (concentration: 2.5 mol / l) of cyclohexene that had been dehydrated through an activated alumina column and deoxygenated by nitrogen substitution was charged. The internal temperature of the autoclave was kept at 25 ° C., and 2 ml of a toluene solution containing 0.5 μmol of metal complex-2 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 1836 kg / mol-Ti · h. From the GPC measurement, it was Mn = 7.7 × 10 4 (Mw / Mn = 1.6). From 13 C-NMR, the cyclohexene content in the copolymer was estimated to be 9.3 mol%.
［実施例３］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ3を真空下で除いて使用した。）を導入した。次いで、活性アルミナカラムを通し脱水、窒素置換により脱酸素処理を施したシクロヘキセンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を３０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−３を１．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝１９９８ｋｇ／ｍｏｌ−Ｔi・ｈであった。ＧＰＣ測定より、Ｍｎ＝２４．７×１０4（Ｍｗ／Ｍｎ＝１．８）であった。13Ｃ−ＮＭＲから共重合体中のシクロヘキセン含有量は０．１モル％と見積もられた。
[Example 3]
The inside was vacuum degassed, and nitrogen-substituted 100 ml autoclave was used with white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution (concentration: 5.0 mol / l) of cyclohexene that had been dehydrated through an activated alumina column and deoxygenated by nitrogen substitution was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 1.0 μmol of metal complex-3 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 1998 kg / mol-Ti · h. From the GPC measurement, it was Mn = 24.7 × 10 4 (Mw / Mn = 1.8). From 13 C-NMR, the cyclohexene content in the copolymer was estimated to be 0.1 mol%.
［比較例１］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ3を真空下で除いて使用した。）を導入した。次いで、活性アルミナカラムを通し脱水、窒素置換により脱酸素処理を施したシクロヘキセンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を３０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−４を１．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝２５６２ｋｇ／ｍｏｌ−Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝１０．４×１０4（Ｍｗ／Ｍｎ＝２．７）であった。13Ｃ−ＮＭＲから共重合体中にシクロヘキセンは含有されていなかった。
[Comparative Example 1]
The inside was vacuum degassed, and nitrogen-substituted 100 ml autoclave was used with white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution (concentration: 5.0 mol / l) of cyclohexene that had been dehydrated through an activated alumina column and deoxygenated by nitrogen substitution was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 1.0 μmol of metal complex-4 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 2562 kg / mol-Ti · h. From the GPC measurement, it was Mn = 10.4 × 10 4 (Mw / Mn = 2.7). From 13 C-NMR, cyclohexene was not contained in the copolymer.
［比較例２］
内部を真空脱気し、窒素置換した１００ｍｌのオートクレーブに白色固体ＭＡＯ（メチルアルミノキサン）（Ａｌ換算で３ｍｍｏｌ、東ソーアクゾ社製：ＰＭＡＯ−Ｓから溶媒のトルエンとＡｌＭｅ3を真空下で除いて使用した。）を導入した。次いで、活性アルミナカラムを通し脱水、窒素置換により脱酸素処理を施したシクロヘキセンのトルエン溶液（濃度：５．０ｍｏｌ／ｌ）を３０ｍｌ仕込んだ。オートクレーブの内温を室温に保ち、金属錯体−５を１．０μｍｏｌ含むトルエン溶液２ｍｌをオートクレーブに加えた。直ちに０．２ＭＰａのエチレンガスを導入し、重合反応を開始させた。オートクレーブの内温およびエチレン圧を保ちつつ、１０分間重合した。重合終了後、オートクレーブの内容物を大量の塩酸酸性メタノール中に移しポリマーを析出させた。共重合活性＝５３２ｋｇ／ｍｏｌ−Ｔｉ・ｈであった。ＧＰＣ測定より、Ｍｎ＝６．１×１０4（Ｍｗ／Ｍｎ＝１．８）であった。13Ｃ−ＮＭＲから共重合体中のシクロヘキセン含有量は痕跡量であった。
結果を表１にまとめる。
The inside was vacuum degassed, and nitrogen-substituted 100 ml autoclave was used with white solid MAO (methylaluminoxane) (3 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S under the condition that toluene and AlMe 3 were removed under vacuum. .) Was introduced. Next, 30 ml of a toluene solution (concentration: 5.0 mol / l) of cyclohexene that had been dehydrated through an activated alumina column and deoxygenated by nitrogen substitution was charged. The internal temperature of the autoclave was kept at room temperature, and 2 ml of a toluene solution containing 1.0 μmol of metal complex-5 was added to the autoclave. Immediately 0.2 MPa of ethylene gas was introduced to initiate the polymerization reaction. Polymerization was carried out for 10 minutes while maintaining the internal temperature and ethylene pressure of the autoclave. After completion of the polymerization, the content of the autoclave was transferred into a large amount of hydrochloric acid-methanol to precipitate a polymer. Copolymerization activity = 532 kg / mol-Ti · h. From GPC measurement, it was Mn = 6.1 × 10 4 (Mw / Mn = 1.8). From 13 C-NMR, the cyclohexene content in the copolymer was a trace amount.
The results are summarized in Table 1.
本発明によって、従来にないエチレン及び／又は炭素数３〜２０のα−オレフィンと置換及び／又は未置換シクロヘキセンからなるシクロヘキセン共重合体、その製造方法及びシクロヘキセン共重合体からなる成形体を提供することが可能となった。 According to the present invention, there are provided a cyclohexene copolymer composed of ethylene and / or an α-olefin having 3 to 20 carbon atoms and a substituted and / or unsubstituted cyclohexene, a production method thereof, and a molded body composed of the cyclohexene copolymer. It became possible.
Claims (5)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239960A (en) * | 2007-02-26 | 2008-10-09 | Mitsui Chemicals Inc | Olefinic polymer including cyclic olefin-derived skeletal structure |
| DE102011015401A1 (en) | 2010-03-30 | 2011-12-15 | Sumitomo Chemical Co., Ltd. | New copolymer and process for its preparation |
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2005
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239960A (en) * | 2007-02-26 | 2008-10-09 | Mitsui Chemicals Inc | Olefinic polymer including cyclic olefin-derived skeletal structure |
| DE102011015401A1 (en) | 2010-03-30 | 2011-12-15 | Sumitomo Chemical Co., Ltd. | New copolymer and process for its preparation |
| US8389656B2 (en) | 2010-03-30 | 2013-03-05 | Tokyo Institute Of Technology | Copolymer and method for producing same |
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