JPH04168105A - Catalyst for olefin polymerization, production thereof and production of olefin polymer using the same catalyst - Google Patents
Catalyst for olefin polymerization, production thereof and production of olefin polymer using the same catalystInfo
- Publication number
- JPH04168105A JPH04168105A JP29357290A JP29357290A JPH04168105A JP H04168105 A JPH04168105 A JP H04168105A JP 29357290 A JP29357290 A JP 29357290A JP 29357290 A JP29357290 A JP 29357290A JP H04168105 A JPH04168105 A JP H04168105A
- Authority
- JP
- Japan
- Prior art keywords
- component
- catalyst
- dilithium
- group
- yttrium
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920000098 polyolefin Polymers 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 title abstract description 21
- -1 yttrium compound Chemical class 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 13
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 229910052710 silicon Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002685 polymerization catalyst Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 abstract description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- RQLKAKQYERUOJD-UHFFFAOYSA-N lithium;1,3,5-trimethylbenzene-6-ide Chemical compound [Li+].CC1=CC(C)=[C-]C(C)=C1 RQLKAKQYERUOJD-UHFFFAOYSA-N 0.000 description 2
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- DHKSRXPZBCVHEZ-UHFFFAOYSA-N (2,3-dimethyl-1H-inden-1-yl)-(1H-inden-1-yl)silane Chemical compound CC1=C(C(C2=CC=CC=C12)[SiH2]C1C=CC2=CC=CC=C12)C DHKSRXPZBCVHEZ-UHFFFAOYSA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- CTWJQOQFTNPBCX-UHFFFAOYSA-N 1-[2-(1h-inden-1-yl)ethyl]-1h-indene Chemical compound C1=CC2=CC=CC=C2C1CCC1C2=CC=CC=C2C=C1 CTWJQOQFTNPBCX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- GRMXFZGBPICEAU-UHFFFAOYSA-N 2-methylocta-1,7-diene Chemical compound CC(=C)CCCCC=C GRMXFZGBPICEAU-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021601 Yttrium(III) bromide Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- KVWLUDFGXDFFON-UHFFFAOYSA-N lithium;methanidyl(trimethyl)silane Chemical compound [Li+].C[Si](C)(C)[CH2-] KVWLUDFGXDFFON-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BHGADZKHWXCHKX-UHFFFAOYSA-N methane;potassium Chemical compound C.[K] BHGADZKHWXCHKX-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- UWLFCNHEPBTLHT-UHFFFAOYSA-N neopentyllithium Chemical compound [Li]CC(C)(C)C UWLFCNHEPBTLHT-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LFWQXIMAKJCMJL-UHFFFAOYSA-K yttrium(3+);triiodide Chemical compound I[Y](I)I LFWQXIMAKJCMJL-UHFFFAOYSA-K 0.000 description 1
- FSDCGXUNLWDJNL-UHFFFAOYSA-K yttrium(iii) bromide Chemical compound Br[Y](Br)Br FSDCGXUNLWDJNL-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は新規なオレフィン重合用触媒、その製法および
それを用いたオレフィン重合体の製造法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel catalyst for olefin polymerization, a method for producing the same, and a method for producing an olefin polymer using the same.
(従来の技術)
従来、オレフィン重合用触媒として、チーグラー・ナツ
タ型触媒が一般に広く知られている。−方、中心金属を
イツトリウムとした錯体触媒に間してはあまり知られて
いない。(Prior Art) Ziegler-Natsuta type catalysts have been widely known as catalysts for olefin polymerization. On the other hand, not much is known about complex catalysts with yttrium as the central metal.
近年、シクロペンタジェンを配位子とするイツトリウム
錯体触媒に関していくつか報告されている [J、
Chew、 Soe、 Chew、 Commu
n、、(1978)、<22>。In recent years, several reports have been made regarding yttrium complex catalysts with cyclopentadiene as a ligand [J,
Chew, Soe, Chew, Commu
n, (1978), <22>.
994およびJ、 Orgioomet、 Chem、
、(1987)、323゜181など]、シかしながら
、これら公知文献に記載の触媒は、活性や分子量制御性
に関して工業的使用にはいずれもまだ不十分である。994 and J, Orgioomet, Chem.
(1987), 323° 181, etc.] However, the catalysts described in these known documents are still insufficient for industrial use in terms of activity and molecular weight controllability.
(発明が解決しようとする課題)
本発明は、立体的に固定された配位子を有するイツトリ
ウム化合物を用いた高活性で活性持続性の良いオレフィ
ン重合用触媒、その製法およびそれを用いたオレフィン
重合体の製造法を提供するものである。(Problems to be Solved by the Invention) The present invention provides a highly active and long-lasting olefin polymerization catalyst using a yttrium compound having a sterically fixed ligand, a method for producing the same, and an olefin polymerization catalyst using the same. A method for producing a polymer is provided.
(課題を解決するための手段)
本発明は、
1、下記構成要素AおよびBを有するイツトリウム化合
物からなるオレフィン重合用触媒:A:2つのシクロペ
ンタジェニル基が相互に炭化水素残基またはケイ素原子
を介して結合した置換基を有すること、
B:水素原子、アルキル基およびアリール基から選ばれ
る置換基を有すること、
2、下記成分a、bおよびCを接触させことを特徴とす
る、第1項記載のオレフィン重合用触媒の製法:
成分a:2つのシクロペンタジェニル基が相互に炭化水
素残基またはケイ素原子
を介して結合した2僅の置換基を有
する化合物のアルカリ金属塩または
アルカリ土類金属塩、
成分b:周期律表I〜■族の有機金属化合物、成分C:
イツトリウムハロゲン化物、および3、第1項記載の触
媒の存在下に、一般式CH2=CHR(式中、Rは水素
原子または炭素数1〜8の炭化水素残基を示す、)で表
されるオレフィンを重合することを特徴とするオレフィ
ン重合体の製造法、
である。(Means for Solving the Problems) The present invention provides: 1. A catalyst for olefin polymerization consisting of a yttrium compound having the following constituent elements A and B: A: two cyclopentadienyl groups mutually containing hydrocarbon residues or silicon B: has a substituent selected from a hydrogen atom, an alkyl group, and an aryl group; 2. The following components a, b, and C are brought into contact with each other. Method for producing an olefin polymerization catalyst according to item 1: Component a: an alkali metal salt or alkali of a compound having two substituents in which two cyclopentadienyl groups are bonded to each other via a hydrocarbon residue or a silicon atom. Earth metal salt, component B: organometallic compound of groups I to ■ of the periodic table, component C:
In the presence of yttrium halide and 3. the catalyst described in item 1, the reaction mixture is expressed by the general formula CH2=CHR (wherein R represents a hydrogen atom or a hydrocarbon residue having 1 to 8 carbon atoms). A method for producing an olefin polymer, characterized by polymerizing an olefin.
(発明の詳細な説明)
[触!!]
本発明触媒は、AおよびBの構成要素を有するイツトリ
ウム化合物からなるオレフィン重合用触媒である。(Detailed description of the invention) [Touch! ! ] The catalyst of the present invention is an olefin polymerization catalyst comprising a yttrium compound having the constituent elements A and B.
構成要素Aは、2つのシクロペンタジェニル基が相互に
炭化水素残基またはケイ素原子を介して結合した置換基
(配位子)を有することである。Component A is that two cyclopentagenyl groups have a substituent (ligand) bonded to each other via a hydrocarbon residue or a silicon atom.
ここでシクロペンタジェニル基は、シクロペンタジェン
環を有する置換および無置換の化合物を示し、具体的に
はシクロペンタジェニル基、インデニル基、フェナンス
レニル基、フルオレニル基、ビシクロ[3,3,0)オ
クタ−1,3−ジェニル基、4,5,6.7−チトラヒ
ドロインデニル基、ビシクロ〔5,3,0〕デカ−8,
11−ジェニル基、トリシクロ〔5,2,1,0”、a
デカ−2,5−ジェニル基およびこれらのアルキル、ア
ルキルシリルもしくはアルキルゲルミル置換体などを例
示することができる。なかでも、シクロペンタジェニル
基、インデニル基、フルオレニル基、4,5.6.7−
チトラヒドロインデニル基の置換もしくは無置換体が好
ましい。Here, the cyclopentadienyl group refers to substituted and unsubstituted compounds having a cyclopentadiene ring, specifically cyclopentadienyl group, indenyl group, phenanthrenyl group, fluorenyl group, bicyclo[3,3,0 ) octa-1,3-genyl group, 4,5,6,7-titrahydroindenyl group, bicyclo[5,3,0]deca-8,
11-genyl group, tricyclo[5,2,1,0'', a
Examples include deca-2,5-genyl group and alkyl, alkylsilyl or alkylgermyl substituted products thereof. Among them, cyclopentadienyl group, indenyl group, fluorenyl group, 4,5.6.7-
Substituted or unsubstituted titrahydroindenyl groups are preferred.
また、2つのシクロペンタジェニル基を結合するには、
炭化水素残基またはケイ素原子が用いられる。ここで、
炭化水素残基は、好ましくは主鎖の炭素数が1〜4のア
ルキレン基またはそのアルキル基もしくはアリール置換
体である。また、ケイ素原子で結合したものは、好まし
くはジアルキルもしくはアリール置換シリル基である。In addition, to combine two cyclopentadienyl groups,
Hydrocarbon residues or silicon atoms are used. here,
The hydrocarbon residue is preferably an alkylene group having 1 to 4 carbon atoms in the main chain, or an alkyl group or aryl substituted product thereof. Moreover, those bonded with silicon atoms are preferably dialkyl or aryl substituted silyl groups.
なかでも、メチレン基、ジメチルメチレン基、エチレン
基、テトラメチルエチレン基、プロピレン基、ジメチル
シリル基、ジフェニルシリル基が好ましい。Among these, methylene group, dimethylmethylene group, ethylene group, tetramethylethylene group, propylene group, dimethylsilyl group, and diphenylsilyl group are preferable.
構成要素Bは、水素原子、アルキル基およびアリール基
から選ばれる置換基を有することである。Component B has a substituent selected from a hydrogen atom, an alkyl group and an aryl group.
アルキル基としては、炭素数1〜12、好ましくは炭素
数1〜8のアルキル基もしくはアルキル(炭素数1〜8
)置換ケイ素基を有するアルキル基が、アリール基とし
ては、炭素数6〜18、好ましくは炭素数6〜12のア
リール基もしくはアルキル(炭素数1〜8)置換ケイ素
を有するアリール基が例示される。The alkyl group includes an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms (1 to 8 carbon atoms).
) An alkyl group having a substituted silicon group is exemplified by an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, or an aryl group having an alkyl (1 to 8 carbon atoms) substituted silicon. .
これらの中でも立体的に嵩高い置換基、例えばα位に炭
素数1〜8のアルキル基もしくはアルキル(炭素数1〜
8)置換シリル基を、好ましくは複数個有するアルキル
基またはオルソ置換アリール基などであり、更にβ水素
またはアルキル脱離の起こりにくい構造のもの、例えば
トリアルキルシリル置換メチル基、オルソ置換アリール
基などが好ましく、具体的にはビストリメチルシリルメ
チル基、メシチル基を挙げることができる。Among these, sterically bulky substituents, such as alkyl groups with 1 to 8 carbon atoms or alkyl groups (with 1 to 8 carbon atoms) at the α-position,
8) An alkyl group or an ortho-substituted aryl group having a plurality of substituted silyl groups, preferably one having a structure in which β-hydrogen or alkyl elimination is difficult to occur, such as a trialkylsilyl-substituted methyl group, an ortho-substituted aryl group, etc. is preferable, and specific examples include bistrimethylsilylmethyl group and mesityl group.
上記の構成要素AおよびBを有する触媒は、具体的には
それぞれの構成要素をもつ下記成分a。The catalyst having the above components A and B specifically includes the following component a having each component.
bおよびCを用いて調製することができる。It can be prepared using b and c.
構成要素Aをもつ成分aは、2つのシクロペンタジェニ
ル基が相互に炭化水素残基またはケイ素原子を介して結
合した2価の置換基を有する化合物のアルカリ金属塩も
しくはアルカリ土類金属塩である。Component a having component A is an alkali metal salt or alkaline earth metal salt of a compound having a divalent substituent in which two cyclopentadienyl groups are bonded to each other via a hydrocarbon residue or a silicon atom. be.
好ましい成分aを具体的に示すと、一般式%式%
で表される化合物である。ここで、Qは炭化水素残基ま
たはケイ素原子を示す、CpおよびC′pは同一でも異
なってもよいシクロペンタジェニル基を示す1Mlおよ
びM2は同一でも異なってもよいアルカリ金属もしくは
アルカリ土類金属をそれぞれ示す、なお、MlおよびM
2がアルカリ土類金属の場合は、ハロゲンまたはアルキ
ル基がそれぞれ1個結合していることが必要である。こ
こでM。Preferred component a is specifically a compound represented by the general formula %. Here, Q represents a hydrocarbon residue or a silicon atom, Cp and C'p represent a cyclopentadienyl group which may be the same or different, and 1Ml and M2 represent an alkali metal or alkaline earth group which may be the same or different. Ml and M represent metals, respectively.
When 2 is an alkaline earth metal, it is necessary that one halogen or alkyl group is bonded thereto. M here.
およびM2は、好ましくはリチウム、ナトリウム、カリ
ウム、マグネシウムなどである。and M2 are preferably lithium, sodium, potassium, magnesium, etc.
成分aの具体例としては、メチレンビス(シクロペンタ
ジェニル)ジリチウム1、エチレンビス(シクロペンタ
ジェニル)ジリチウム、エチレンビス(2−メチルシク
ロペンタジェニル)ジリチウム、エチレンビス(3−メ
チルシクロペンタジェニル)ジリチウム、エチレンビス
(2,3−ジメチルシクロペンタジェニル)ジリチウム
1、エチレンビス(2,4−ジメチルシクロペンタジェ
ニル)ジリチウム、エチレンビス(2,3,4−トリメ
チルシクロペンタジェニル)ジリチウム、エチレンビス
(2,3,5−トリメチルシクロペンタジェニル)ジリ
チウム、エチレンビス(2゜3.4.5−テトラメチル
シクロペンタジェニル)ジリチウム、エチレンビス(3
−エチルシクロペンタジェニル)ジリチウム、エチレン
ビス(3−t−ブチルシクロペンタジェニル)ジリチウ
ム、エチレンビス(3−フェニルシクロペンタジェニル
)ジリチウム、エチレンビス(3−ベンジルシクロペン
タジェニル)ジリチウム、エチレンビス(3−メンチル
シクロペンタジェニル)ジリチウム、イソプロピリデン
ビス(シクロペンタジェニル)ジリチウム、1,3−プ
ロピレンビス(シクロペンタジェニル)ジリチウム、ジ
メチルシリレンビス(シクロペンタジェニル)ジリチウ
ム、ジメチルシリレンビス(2,3,4,5−テトラメ
チルシクロペンタジェニル)ジリチウム、ジフェニルシ
リレンビス(2,3,4,5−テトラメチルシクロペン
タジェニル)ジリチウム、ジメチルシリレン(シクロペ
ンタジェニル−2,3,4゜5−テトラメチルシクロペ
ンタジェニル)ジリチウム、ジメチルシリレンビス(3
−トリメチルシクロペンタジェニル)ジリチウム、シク
ロへキシリデンビス(3−メチルシクロペンタジェニル
)ジリチウム、エチレンビス〈インデニル)ジリチウム
、エチレンビス(インデニル)ジナトリウム、エチレン
ビス(インデニル)ジカリウム、エチレンビス(インデ
ニル)ジマグネシウムクロリド、エチレンビス(インデ
ニル)ジマグネシウムブロミド、エチレンビス(2−メ
チルインデニル)ジリチウム、エチレンビス(3−メチ
ルインデニル)ジリチウム、エチレンビス(4−メチル
インデニル)ジリチウム、エチレンビス(7−メチルイ
ンデニル)ジリチウム、メチレンビス(インデニル)ジ
リチウム、1.3−プロピレンビス(インデニル)ジリ
チウム、イソプロピリデンビス(インデニル)ジリチウ
ム、ジフェニルメチレンビス(インデニル)ジリチウム
、シクロへキシリデンビス(インデニル)ジリチウム、
エチレンビス(4゜5.6.7−チトラヒドロインデニ
ル)ジリチウム、エチレンビス(フルオレニル)ジリチ
ウム、2.2−プロピレン(シクロへキシリデンビス。Specific examples of component a include methylenebis(cyclopentagenyl)dilithium 1, ethylenebis(cyclopentagenyl)dilithium, ethylenebis(2-methylcyclopentagenyl)dilithium, ethylenebis(3-methylcyclopentagenyl)dilithium, ) dilithium, ethylenebis(2,3-dimethylcyclopentadienyl)dilithium 1, ethylenebis(2,4-dimethylcyclopentadienyl)dilithium, ethylenebis(2,3,4-trimethylcyclopentadienyl) Dilithium, ethylenebis(2,3,5-trimethylcyclopentadienyl)dilithium, ethylenebis(2゜3.4.5-tetramethylcyclopentadienyl)dilithium, ethylenebis(3
-ethylcyclopentagenyl) dilithium, ethylenebis(3-t-butylcyclopentagenyl)dilithium, ethylenebis(3-phenylcyclopentagenyl)dilithium, ethylenebis(3-benzylcyclopentagenyl)dilithium, Ethylenebis(3-menthylcyclopentagenyl)dilithium, isopropylidenebis(cyclopentagenyl)dilithium, 1,3-propylenebis(cyclopentagenyl)dilithium, dimethylsilylenebis(cyclopentagenyl)dilithium, dimethyl silylenebis(2,3,4,5-tetramethylcyclopentadienyl)dilithium, diphenylsilylenebis(2,3,4,5-tetramethylcyclopentadienyl)dilithium, dimethylsilylene(cyclopentadienyl-2) ,3,4゜5-tetramethylcyclopentadienyl)dilithium, dimethylsilylenebis(3
-trimethylcyclopentadienyl) dilithium, cyclohexylidenebis(3-methylcyclopentagenyl)dilithium, ethylenebis(indenyl)dilithium, ethylenebis(indenyl)disodium, ethylenebis(indenyl)dipotassium, ethylenebis(indenyl) Dimagnesium chloride, ethylenebis(indenyl)dimagnesium bromide, ethylenebis(2-methylindenyl)dilithium, ethylenebis(3-methylindenyl)dilithium, ethylenebis(4-methylindenyl)dilithium, ethylenebis(7-methylindenyl)dilithium -methylindenyl) dilithium, methylenebis(indenyl)dilithium, 1,3-propylenebis(indenyl)dilithium, isopropylidenebis(indenyl)dilithium, diphenylmethylenebis(indenyl)dilithium, cyclohexylidenebis(indenyl)dilithium,
Ethylenebis(4°5.6.7-titrahydroindenyl)dilithium, ethylenebis(fluorenyl)dilithium, 2,2-propylene(cyclohexylidenebis).
フルオレニル)ジリチウム、ジメチルシリル(ビスイン
デニル)ジリチウム、ジメチルシリル(4゜5.6.7
−チトラヒドロインデニル)ジリチウム、ジメチルシリ
ル(シクロペンタジェニル、)ルオレニル)ジリチウム
などを例示できる。fluorenyl) dilithium, dimethylsilyl (bisindenyl) dilithium, dimethylsilyl (4°5.6.7
-titrahydroindenyl)dilithium, dimethylsilyl(cyclopentagenyl,)luorenyl)dilithium, and the like.
構成要素Bをもつ成分すは、アルキル基およびアリール
基から選ばれる置換基を有する、好ましくは周期律表I
〜■族の有機金属化合物である。The components with component B have substituents selected from alkyl groups and aryl groups, preferably from Periodic Table I
It is an organometallic compound of group ~■.
成分すの具体例としては、メチルリチウム、メチルカリ
ウム、メチルナトリウム、メチルマグネシウムクロリド
、メチルマグネシウムプロミド、メチルマグネシウムク
ロリド、エチルリチウム、ジエチルマグネシウム、n−
ブチルリチウム、5ee−ブチルリチウム、tert−
ブチルリチウム、イソプレニルリチウム、ネオペンチル
リチウム、ジーtert−ブチルメチルリチウム、フェ
ニルリチウム、0−トリルリチウム、2.6−シメチル
フエニルリチウム、メシチルリチウム、0−エチルフェ
ニルリチウム、o −tert−ブチルフェニルリチウ
ム、0−トリメチルシリルフェニルリチウム、ベンジル
リチウム、ネオフィルリチウム、トリメチルシリルメチ
ルリチウム、ビストリメチルシリルメチルリチウム、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、ジメチルアルミニウムクロリ
ド、エチルアルミニウムセスキクロリド、ジエチルアル
ミニウムヒドリド、ジイソブチルアルミニウムヒドリド
、メチルアルミノキサン、トリエチルホウ素などを例示
するこができる。なかでも、ビストリメチルシリルメチ
ルリチウムのようなトリアルキルシリル置換メチル基や
、メシチルリチウムのようなオルソ置換アリール基のア
ルカリ金属もしくはアルカリ土類金属塩が好ましい。Specific examples of the components include methyllithium, methylpotassium, methylsodium, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium chloride, ethyllithium, diethylmagnesium, n-
Butyllithium, 5ee-butyllithium, tert-
Butyllithium, isoprenyllithium, neopentyllithium, di-tert-butylmethyllithium, phenyllithium, 0-tolyllithium, 2,6-dimethylphenyllithium, mesityllithium, 0-ethylphenyllithium, o -tert- Butylphenyllithium, 0-trimethylsilylphenyllithium, benzyllithium, neophylllithium, trimethylsilylmethyllithium, bistrimethylsilylmethyllithium, trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutyl Examples include aluminum hydride, methylaluminoxane, and triethylboron. Among these, alkali metal or alkaline earth metal salts of trialkylsilyl-substituted methyl groups such as bistrimethylsilylmethyllithium and ortho-substituted aryl groups such as mesityllithium are preferred.
成分Cは、イツトリウムハロゲン化物である。Component C is yttrium halide.
具体例としては、三塩化イツトリウム、三臭化イツトリ
ウム、三ヨウ化イツトリウムなどを例示できる。なかで
も好ましくは、三塩化イツトリウムである。Specific examples include yttrium trichloride, yttrium tribromide, and yttrium triiodide. Among them, yttrium trichloride is preferred.
本発明に使用する触媒は公知の手法を応用して合成でき
る0例えば、好ましくは上記成分aの化合物をテトラヒ
ドロフラン、ジエチルエーテル、ジメトキシエタンなど
のエーテル系有機溶!(成分Cに対して重量比で5〜1
000倍の有機溶媒)の存在下、成分Cの化合物を一2
00〜200℃の温度範囲で、成分a:酸成分 =0.
5 : 1〜1.25 :1の割合(モル比)で接触さ
せ、得られた生成物に成分すを反応させて得られる。こ
の反応に使用する溶媒は、例えばペンタン、ヘキサン、
ヘプタンなどの脂肪族炭化水素、シクロヘキサンなどの
脂環族炭化水素、ベンゼン、トルエンなどの芳香族炭化
水素溶媒もしくは前記エーテル系有機溶媒(成分すに対
して重量比で5〜1000倍の有機溶媒)を用い、使用
する成分すの量は初めに使用した成分Cに対して0.5
〜5の割合であり、反応温度は一200〜200℃であ
る。The catalyst used in the present invention can be synthesized by applying a known method. For example, preferably, the compound of component a above is mixed in an ether-based organic solution such as tetrahydrofuran, diethyl ether, or dimethoxyethane. (5 to 1 weight ratio to component C)
000 times the amount of organic solvent), the compound of component C was mixed with
In the temperature range of 00 to 200°C, component a: acid component = 0.
5:1 to 1.25:1 (molar ratio), and the resulting product is reacted with the components. Solvents used in this reaction include, for example, pentane, hexane,
Aliphatic hydrocarbons such as heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, etc., or the above-mentioned ether-based organic solvents (5 to 1000 times the weight ratio of the organic solvents to the components) The amount of component C used is 0.5 for the component C used at the beginning.
5, and the reaction temperature is -200 to 200°C.
上記触媒の製造においては、成分すとしてアルキル基ま
たはアリール基を有するアルカリ金属またはアルカリ土
類金属化合物を使用する場合には、成分すの反応時に、
同時にまたは後で水素ガスを使用することができる。In the production of the above catalyst, when an alkali metal or alkaline earth metal compound having an alkyl group or an aryl group is used as a component, during the reaction of the component,
Hydrogen gas can be used at the same time or later.
上記の本発明触媒は、反応生成物のまま単味で重合に用
いることができるが、適当な支持体に担持してもよい、
この際用いられる支持体としては、シリカゲル、アルミ
ナ、ゼオライト、塩化マグネシウム、酸化マグネシウム
などの無機担体およびポリエチレン粒子、ポリプロピレ
ン粒子などのポリマー担体を用いることができる。The catalyst of the present invention described above can be used alone as a reaction product for polymerization, but it may also be supported on a suitable support.
As the support used in this case, inorganic supports such as silica gel, alumina, zeolite, magnesium chloride, and magnesium oxide, and polymer supports such as polyethylene particles and polypropylene particles can be used.
本発明のイツトリウム触媒を使用して重合するモノマー
は、一般式 CI(2=CH−Rで表される末端二重結
合を有するオレフィン化合物である。The monomer polymerized using the yttrium catalyst of the present invention is an olefin compound having a terminal double bond represented by the general formula CI (2=CH-R).
ここで、Rは水素原子もしくは炭素数1〜8の炭化水素
残基を示す、具体的には、エチレン、プロピレン、1−
ブテン、3−メチルブテン−1,1−ヘキセン、4−メ
チルペンテン−1,1−オクテン、1−デセン、スチレ
ン、ブタジェン、イソプレン、1.5−へキサジエン、
7−メチル−1,7−オクタジエンなどを例示すること
ができる。これらモノマーは1種だけでなく、2種以上
使用することもできる。Here, R represents a hydrogen atom or a hydrocarbon residue having 1 to 8 carbon atoms, specifically, ethylene, propylene, 1-
Butene, 3-methylbutene-1,1-hexene, 4-methylpentene-1,1-octene, 1-decene, styrene, butadiene, isoprene, 1,5-hexadiene,
Examples include 7-methyl-1,7-octadiene. These monomers can be used alone or in combination of two or more.
重合は気相、液相、他の公知のいずれの方法も採用しう
る。溶媒を用いる場合は、不活性の有機溶媒の使用が好
ましく、例えばベンゼン、トルエン、キシレンのどの芳
香族炭化水素溶媒、n−ぺンタン、n−ヘキサン、n−
へブタン、n−パラフィンなどの脂肪族炭化水素溶媒、
シクロヘキサン、メチルシクロペンタンのどの脂環式炭
化水素溶媒を用いうる0本発明では、脂肪族炭化水素溶
媒でも有効であることが特徴の一つである。Polymerization can be carried out in a gas phase, in a liquid phase, or by any other known method. When using a solvent, it is preferable to use an inert organic solvent, such as aromatic hydrocarbon solvents such as benzene, toluene, xylene, n-pentane, n-hexane, n-
aliphatic hydrocarbon solvents such as hebutane, n-paraffin,
Any alicyclic hydrocarbon solvent such as cyclohexane or methylcyclopentane can be used. One of the features of the present invention is that aliphatic hydrocarbon solvents are also effective.
重合温度は一20〜260℃、好ましくは40〜200
℃である。Polymerization temperature is -20~260℃, preferably 40~200℃
It is ℃.
重合に際し、分子量調節剤を用いることができる0分子
量調節剤としては水素ガスが有効である。A molecular weight regulator can be used during polymerization. Hydrogen gas is effective as the molecular weight regulator.
また、水素は触媒活性向上効果をもたらすので、重合系
に存在させることが好ましい。Moreover, since hydrogen brings about the effect of improving catalyst activity, it is preferable to make it exist in the polymerization system.
重合圧力は、常圧〜3000 kg/em2Gの範囲で
適宜選択される。The polymerization pressure is appropriately selected within the range of normal pressure to 3000 kg/em2G.
(発明の効果)
本発明によれば、特定の配位子を有する新規なイツトリ
ウム化合物を用いることにより、高活性且つ活性持続性
に優れるオレフィン重合触媒が得られ、分子量分布の狭
い、低分子量から高分子量までの幅広い分子量を有する
オレフィン重合体を製造することができる。(Effects of the Invention) According to the present invention, by using a novel yttrium compound having a specific ligand, an olefin polymerization catalyst with high activity and excellent activity persistence can be obtained, and it is possible to obtain an olefin polymerization catalyst with a narrow molecular weight distribution and a low molecular weight Olefin polymers having a wide range of molecular weights up to high molecular weights can be produced.
(実施例)
実施例−1
1監立11
充分に窒素置換した撹拌買付の300m1のフラスコに
、1.2−ジインデニルエタン10.0mmolと精製
T HF 120m1を入れ、−78℃に冷却して、n
−ブチルリチウム1.6Nヘキサン溶液12.5mlを
滴下した。(Example) Example-1 1 Supervision 11 Put 10.0 mmol of 1,2-diindenyl ethane and 120 ml of purified THF into a stirred 300 ml flask that has been sufficiently purged with nitrogen, and cool to -78°C. Then, n
-12.5 ml of a 1.6N hexane solution of butyllithium was added dropwise.
室温まで温度を上昇させ、8時間反応させた。The temperature was raised to room temperature and the reaction was continued for 8 hours.
これに、1.95gの無水塩化イツトリウムを一78℃
にて100m1のTHFでスラリー化したものを、0℃
にて加え8時間還流した。Add 1.95 g of anhydrous yttrium chloride to this at -78°C.
Slurry the slurry with 100ml of THF at 0°C.
and refluxed for 8 hours.
反応終了後、10℃に冷却して溶媒を減圧下に留去した
。これに精製ジエチルエーテル100m1を加え撹拌し
た後、10℃に冷却して溶媒を減圧下に留去した。この
操作を2度繰り返した。After the reaction was completed, the mixture was cooled to 10° C. and the solvent was distilled off under reduced pressure. After adding 100 ml of purified diethyl ether and stirring, the mixture was cooled to 10°C and the solvent was distilled off under reduced pressure. This operation was repeated twice.
得られた生成物に精製トルエン100m1を加え、0℃
にてビストリメチルシリルメチルリチウム0.67M−
ジエチルエーテル溶液15.0+*lを加え、8時間反
応させた0反応生成物の溶媒を減圧下に留去した後、精
製トルエン100m1にて抽出し、枦遇して枦液を濃縮
し、再結晶して生成物を得た。Add 100 ml of purified toluene to the obtained product and heat at 0°C.
Bistrimethylsilylmethyllithium 0.67M-
15.0+*l of diethyl ether solution was added and reacted for 8 hours. After distilling off the solvent of the reaction product under reduced pressure, it was extracted with 100ml of purified toluene, and the solution was concentrated and reconstituted. The product was crystallized.
得られた生成物を、精製トルエンに希釈し、0.063
m5oiY /+mL−)ルエンの触媒溶液として重合
に供した。The resulting product was diluted in purified toluene to 0.063
m5oiY /+mL-) It was subjected to polymerization as a catalyst solution of toluene.
七
充分に乾燥、窒素置換した撹拌翼付11オートクレーブ
に精製トルエン300m1を導入し、次いで窒素雰囲気
下に上記で製造した触媒溶液2.5m1(0,157m
5ol)を添加し、これに水素を重合槽圧2 kg/c
*”Gまで導入し、15℃にて1時間撹拌した。300 ml of purified toluene was introduced into a 11 autoclave equipped with a stirring blade that had been thoroughly dried and purged with nitrogen, and then 2.5 ml (0.157 ml) of the catalyst solution prepared above was introduced under a nitrogen atmosphere.
5 ol) was added, and hydrogen was added to this at a polymerization tank pressure of 2 kg/c.
*”G was introduced and stirred at 15° C. for 1 hour.
次いで、水素をパージし、系内を窒素置換した後にエチ
レンを導入し、重合槽圧を6 kg/cm2Gに保ち、
80℃にて3時間重合させた。Next, after purging hydrogen and replacing the inside of the system with nitrogen, ethylene was introduced, and the polymerization tank pressure was maintained at 6 kg/cm2G.
Polymerization was carried out at 80°C for 3 hours.
その結果、66.6gのポリエチレンが得られ、その分
子量は、Mnが2.40x 10’、M wが5.90
X 10’、Q値(Mw/Mn)は2.46であった。As a result, 66.6 g of polyethylene was obtained, the molecular weight of which was 2.40 x 10' for Mn and 5.90 for M w.
X10' and Q value (Mw/Mn) were 2.46.
実施例−2
七
実施例−1と同様のオートクレーブを充分に乾燥、窒素
置換して、精製トルエン3QQw+lおよび実施例−1
で用いた触媒溶液2.5請1(0,157s+mol)
を導入し、さらに水素1200m1およびエチレンを導
入し、重合槽圧を8 kg/em’Gに保ち、60℃に
て3時間重合させた。Example-2 7 An autoclave similar to Example-1 was sufficiently dried and replaced with nitrogen to produce purified toluene 3QQw+l and Example-1.
Catalyst solution used in 2.5 ml (0,157 s + mol)
was introduced, and further 1200 ml of hydrogen and ethylene were introduced, and the polymerization tank pressure was maintained at 8 kg/em'G, and polymerization was carried out at 60° C. for 3 hours.
その結果、37.2gのポリエチレンが得られ、その分
子量は、Mnが1.31 X 10’ 、M wが2.
96X10’。As a result, 37.2 g of polyethylene was obtained, the molecular weight of which was 1.31 x 10' for Mn and 2.
96X10'.
Q値は2.26であった。The Q value was 2.26.
実施例−3
実施例−1と同様にして、触媒溶液を5−1(0,31
mmol)とし、プロピレンにて60℃で重合させた。Example-3 In the same manner as in Example-1, the catalyst solution was mixed with 5-1 (0,31
mmol) and polymerized at 60°C in propylene.
重合終了後、溶媒を留去して0.47gのポリマーを得
た。生成物は、13C−N M Rにより、アタクチッ
クポリプロピレンであることが確認された。After the polymerization was completed, the solvent was distilled off to obtain 0.47 g of polymer. The product was confirmed to be atactic polypropylene by 13C-NMR.
実施例−4
隨l久11
実施例−1と同様にして、充分に窒素置換した撹拌買付
の300m1のフラスコに、ジメチルシリレンビスイン
デン10.0−−01と精製T HF 150m1を入
れ、−78℃に冷却して、n−ブチルリチウム1,6N
ヘキサン溶液14.0mlを滴下した0反応混合物を室
温まで温度を上昇させ、8時間反応させた。Example 4 11 In the same manner as in Example 1, dimethylsilylene bisindene 10.0--01 and purified THF 150 ml were placed in a stirred 300 ml flask that had been sufficiently purged with nitrogen. Cool to 78°C, add n-butyllithium 1,6N
The temperature of the reaction mixture to which 14.0 ml of hexane solution was added dropwise was raised to room temperature and reacted for 8 hours.
これに、1.95gの無水塩化イツトリウムを一78℃
にて75−1のTHFでスラリー化したものを、0℃に
て加え8時間還流した。Add 1.95 g of anhydrous yttrium chloride to this at -78°C.
A slurry of 75-1 THF was added at 0°C and refluxed for 8 hours.
反応終了後、10℃に冷却して溶媒を減圧下に留去した
。これに精製ジエチルエーテル120s+1を加え、抽
出し、溶媒を留去して褐色の反応生成物3.34gを得
た。After the reaction was completed, the mixture was cooled to 10° C. and the solvent was distilled off under reduced pressure. 120s+1 purified diethyl ether was added to this, extracted, and the solvent was distilled off to obtain 3.34 g of a brown reaction product.
得られた生成物に精製トルエンloomlを加え、0℃
にてビストリメチルシリルメチルリチウム0゜53トジ
エチルエーテル溶液10.3mlを加え、8時間反応さ
せた0反応生成物の溶媒を減圧下に留去した後に精製ト
ルエン100m1にて抽出し、濾過して重合に供した。Add purified toluene looml to the obtained product and heat at 0°C.
10.3 ml of bistrimethylsilylmethyllithium 0.53 diethyl ether solution was added and reacted for 8 hours. After distilling off the solvent of the reaction product under reduced pressure, it was extracted with 100 ml of purified toluene, filtered, and polymerized. Served.
このものの触媒濃度は0.067m5+oiY /鋤1
)ルエンであった。The catalyst concentration of this product is 0.067 m5 + oiY / plow 1
) was Luen.
実施例−1と同様にして、触媒溶液5.0+sl(0,
337smol )とし、エチレンにて60℃で重合さ
せた。In the same manner as in Example-1, a catalyst solution of 5.0+sl (0,
337 smol) and polymerized with ethylene at 60°C.
その結果、31.8gのポリエチレンが得られ、その分
子量は、Mnが1.48x 10’、M wが4.57
X 10’、Q値は3.08であった。As a result, 31.8 g of polyethylene was obtained, the molecular weight of which was 1.48 x 10' for Mn and 4.57 for M w.
X10', Q value was 3.08.
実施例−5
実施例−4と同様にして、エチレン重合時プロピレンを
151(液体換算)共存させて重合を行った。Example 5 In the same manner as in Example 4, ethylene polymerization was carried out in the presence of propylene 151 (liquid equivalent).
その結果、11.8gのポリマーが得られ、その分子量
は、Mnが6.82x 10’、M wが2.04X
105、Q値は2.99であった。As a result, 11.8 g of polymer was obtained, the molecular weight of which was 6.82x 10' for Mn and 2.04x for Mw.
105, and the Q value was 2.99.
実施例−6
11五11
実施例−4と同様にして、充分に窒素置換した撹拌買付
の300m1のフラスコに、ジメチルシリレン(シクロ
ペンタジェン、フルオレン) 8.5mmolと精製T
HF 150m1を入れ、−78℃に冷却して、n−
ブチルリチウム1.6Nヘキサン溶液11.1mlを滴
下した0反応混合物の温度を室温まで上昇させ、8時間
反応させた。Example-6 11511 In the same manner as in Example-4, 8.5 mmol of dimethylsilylene (cyclopentadiene, fluorene) and purified T were placed in a stirred 300 ml flask that had been sufficiently purged with nitrogen.
Pour 150ml of HF, cool to -78°C, and
11.1 ml of a 1.6N hexane solution was added dropwise to the reaction mixture, and the temperature of the reaction mixture was raised to room temperature, followed by a reaction for 8 hours.
これに、1.65gの無水塩化イツトリウムを一78℃
にて50a+lのTHFでスラリー化したものを、0℃
にて加え8時間還流させた。Add 1.65 g of anhydrous yttrium chloride to this at -78°C.
Slurry the slurry with 50a+l of THF at 0°C.
and refluxed for 8 hours.
反応終了後、生成物を10℃に冷却して溶媒を減圧下に
留去した。これに精製ジエチルエーテル1001を加え
、撹拌した後に再度溶媒を減圧下に留去した。この操作
を2度繰り返した。After the reaction was completed, the product was cooled to 10° C. and the solvent was distilled off under reduced pressure. Purified diethyl ether 1001 was added to this, and after stirring, the solvent was distilled off again under reduced pressure. This operation was repeated twice.
得られた生成物に精製トルエン100m1を加え、0℃
にてビストリメチルシリルメチルリチウム0.67M−
ジエチルエーテル溶液12.6e+Iを加え、8時間反
応させた0反応生成物の溶媒を減圧下に留去した後、精
製n−ペンタン75s!にて洗浄し、さらに精製トルエ
ン100m1にて抽出し、P遇して重合に供した。Add 100 ml of purified toluene to the obtained product and heat at 0°C.
Bistrimethylsilylmethyllithium 0.67M-
After adding diethyl ether solution 12.6e+I and reacting for 8 hours, the solvent of the reaction product was distilled off under reduced pressure, and purified n-pentane 75s! The mixture was washed with water, extracted with 100 ml of purified toluene, treated with P, and subjected to polymerization.
このものの触媒濃度は0.045mmol−Y /ml
)ルエンであった。The catalyst concentration of this product is 0.045 mmol-Y/ml
) was Luen.
実施例−1と同様にして、触媒溶液5.0簡1(0,2
25−mol)とし、エチレンにて25℃で重合させた
。In the same manner as in Example-1, a catalyst solution of 5.0 kg (0,2
25-mol) and polymerized with ethylene at 25°C.
その結果、5.0gのポリエチレンが得られ、その分子
量は、Mnがz、tzx 105、M wが5.80x
105、Q値は2.74であった。As a result, 5.0 g of polyethylene was obtained, and its molecular weight was as follows: Mn: z, tzx: 105, Mw: 5.80x
105, and the Q value was 2.74.
Claims (1)
物からなるオレフィン重合用触媒。 A:2つのシクロペンタジエニル基が相互に炭化水素残
基またはケイ素原子を介して結合した置換基を有するこ
と、 B:水素原子、アルキル基およびアリール基から選ばれ
る置換基を有すること。 2、下記成分a、bおよびcを接触させことを特徴とす
る、第1項記載のオレフィン重合用触媒の製法。 成分a:2つのシクロペンタジエニル基が相互に炭化水
素残基またはケイ素原子を介して結合した2価の置換基
を有する化合物のアルカリ金属塩またはアルカリ土類金
属塩、 成分b:周期律表 I 〜III族の有機金属化合物、 成分c:イットリウムハロゲン化物。 3、第1項記載の触媒の存在下に、一般式 CH_2=CHR(式中、Rは水素原子または炭素数1
〜8の炭化水素残基を示す。)で表されるオレフィンを
重合することを特徴とするオレフィン重合体の製造法。[Scope of Claims] 1. An olefin polymerization catalyst comprising an yttrium compound having the following constituent elements A and B. A: Two cyclopentadienyl groups have a substituent bonded to each other via a hydrocarbon residue or a silicon atom, B: A substituent selected from a hydrogen atom, an alkyl group, and an aryl group. 2. The method for producing an olefin polymerization catalyst according to item 1, which comprises bringing the following components a, b, and c into contact with each other. Component a: Alkali metal salt or alkaline earth metal salt of a compound having a divalent substituent in which two cyclopentadienyl groups are bonded to each other via a hydrocarbon residue or a silicon atom, Component b: Periodic table Organometallic compound of groups I to III, component c: yttrium halide. 3. In the presence of the catalyst described in item 1, the general formula CH_2=CHR (wherein R is a hydrogen atom or
~8 hydrocarbon residues are shown. ) A method for producing an olefin polymer, which comprises polymerizing an olefin represented by:
Priority Applications (1)
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JP29357290A JP2956042B2 (en) | 1990-11-01 | 1990-11-01 | Method for producing olefin polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29357290A JP2956042B2 (en) | 1990-11-01 | 1990-11-01 | Method for producing olefin polymer |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05148166A (en) * | 1991-05-09 | 1993-06-15 | Phillips Petroleum Co | New fluorenyl compound and preparation thereof |
JP2006516997A (en) * | 2003-01-07 | 2006-07-13 | トータル・ペトロケミカルズ・リサーチ・フエリユイ | Group III bridged metallocenes based on cyclopentadienyl-fluorenyl ligands |
-
1990
- 1990-11-01 JP JP29357290A patent/JP2956042B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05148166A (en) * | 1991-05-09 | 1993-06-15 | Phillips Petroleum Co | New fluorenyl compound and preparation thereof |
JP2006516997A (en) * | 2003-01-07 | 2006-07-13 | トータル・ペトロケミカルズ・リサーチ・フエリユイ | Group III bridged metallocenes based on cyclopentadienyl-fluorenyl ligands |
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