WO1999036427A1 - Process for the preparation of metallocene compounds - Google Patents
Process for the preparation of metallocene compounds Download PDFInfo
- Publication number
- WO1999036427A1 WO1999036427A1 PCT/EP1999/000188 EP9900188W WO9936427A1 WO 1999036427 A1 WO1999036427 A1 WO 1999036427A1 EP 9900188 W EP9900188 W EP 9900188W WO 9936427 A1 WO9936427 A1 WO 9936427A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- group
- methyl
- cyclopentadienyl
- indenyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000001255 actinides Chemical group 0.000 claims abstract description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 3
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 3
- -1 4-adamantyl-cyclopentadienyl Chemical group 0.000 claims description 40
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 15
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 13
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 13
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 239000000010 aprotic solvent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 229910003865 HfCl4 Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 2
- 229910018057 ScCl3 Inorganic materials 0.000 claims description 2
- 229910011005 Ti(OPr)4 Inorganic materials 0.000 claims description 2
- 229910008110 Zr(OPr)4 Inorganic materials 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 229960004132 diethyl ether Drugs 0.000 claims description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- XTTBFCWRLDKOQU-UHFFFAOYSA-N propan-1-ol;titanium Chemical compound [Ti].CCCO.CCCO.CCCO.CCCO XTTBFCWRLDKOQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 24
- 238000003786 synthesis reaction Methods 0.000 abstract description 18
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002431 hydrogen Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 239000007787 solid Substances 0.000 description 17
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 13
- 239000000725 suspension Substances 0.000 description 11
- 241000349731 Afzelia bipindensis Species 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002168 alkylating agent Substances 0.000 description 6
- 229940100198 alkylating agent Drugs 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 229910007928 ZrCl2 Inorganic materials 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IPBTZXODRJJQBJ-UHFFFAOYSA-N 3-tert-butyl-1-[(3-tert-butyl-1h-inden-1-yl)methyl]-1h-indene Chemical compound C12=CC=CC=C2C(C(C)(C)C)=CC1CC1C2=CC=CC=C2C(C(C)(C)C)=C1 IPBTZXODRJJQBJ-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WAADRLKGQPOVGL-UHFFFAOYSA-N 1-[1-(1h-inden-1-yl)ethyl]-1h-indene Chemical compound C1=CC2=CC=CC=C2C1C(C)C1C2=CC=CC=C2C=C1 WAADRLKGQPOVGL-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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 2
- LUKADOYBIWUGAR-UHFFFAOYSA-N ClC.C1=CC2=CC=CC=C2C1[Zr](=C(C)C)C1C2=CC=CC=C2C=C1 Chemical compound ClC.C1=CC2=CC=CC=C2C1[Zr](=C(C)C)C1C2=CC=CC=C2C=C1 LUKADOYBIWUGAR-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- PALFTCLHKGGKDW-UHFFFAOYSA-N 1-[2-(1h-inden-1-yl)propan-2-yl]-1h-indene Chemical compound C1=CC2=CC=CC=C2C1C(C)(C)C1C2=CC=CC=C2C=C1 PALFTCLHKGGKDW-UHFFFAOYSA-N 0.000 description 1
- GCZYAOLYVIHWLC-UHFFFAOYSA-N 1-[2-(4,7-dimethyl-1h-inden-1-yl)ethyl]-4,7-dimethyl-1h-indene Chemical compound C1=CC(C(=CC=C2C)C)=C2C1CCC1C(C(C)=CC=C2C)=C2C=C1 GCZYAOLYVIHWLC-UHFFFAOYSA-N 0.000 description 1
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 1
- HANWWAAUFXCNBS-UHFFFAOYSA-N 2,6,6-tris(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(CC(C)C)(CC(C)C)O1 HANWWAAUFXCNBS-UHFFFAOYSA-N 0.000 description 1
- USVQDQRLYYGLPV-UHFFFAOYSA-N 2-(2,4,4-trimethylpentyl)oxaluminane Chemical compound CC(C)(C)CC(C)C[Al]1CCCCO1 USVQDQRLYYGLPV-UHFFFAOYSA-N 0.000 description 1
- FSWNZCWHTXTQBY-UHFFFAOYSA-N 4,6-dimethylhept-1-ene Chemical compound CC(C)CC(C)CC=C FSWNZCWHTXTQBY-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- MWROANXKQLDDCZ-UHFFFAOYSA-L [Cl-].[Cl-].C1=C(C(C)(C)C)C2=CC=CC=C2C1[Zr+2](=C)C1C=C(C(C)(C)C)C2=CC=CC=C21 Chemical compound [Cl-].[Cl-].C1=C(C(C)(C)C)C2=CC=CC=C2C1[Zr+2](=C)C1C=C(C(C)(C)C)C2=CC=CC=C21 MWROANXKQLDDCZ-UHFFFAOYSA-L 0.000 description 1
- OYSUUFLNFATWBX-UHFFFAOYSA-L [Cl-].[Cl-].C1C2=CC=CC=C2C2=C1C([Zr+2]C=1C=CC=C3C4=CC=CC=C4CC=13)=CC=C2 Chemical compound [Cl-].[Cl-].C1C2=CC=CC=C2C2=C1C([Zr+2]C=1C=CC=C3C4=CC=CC=C4CC=13)=CC=C2 OYSUUFLNFATWBX-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-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
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- HKVFGFGPRISDFM-UHFFFAOYSA-N tris(2,3,3-trimethylbutyl)alumane Chemical compound CC(C)(C)C(C)C[Al](CC(C)C(C)(C)C)CC(C)C(C)(C)C HKVFGFGPRISDFM-UHFFFAOYSA-N 0.000 description 1
- WRZKUDJYHWOMSC-UHFFFAOYSA-N tris(2,3-diethylpentyl)alumane Chemical compound CCC(CC)C(CC)C[Al](CC(CC)C(CC)CC)CC(CC)C(CC)CC WRZKUDJYHWOMSC-UHFFFAOYSA-N 0.000 description 1
- SSEXLBWMXFFGTD-UHFFFAOYSA-N tris(2,3-dimethylbutyl)alumane Chemical compound CC(C)C(C)C[Al](CC(C)C(C)C)CC(C)C(C)C SSEXLBWMXFFGTD-UHFFFAOYSA-N 0.000 description 1
- XZIKSWMNFLIAQP-UHFFFAOYSA-N tris(2,4,4-trimethylpentyl)alumane Chemical compound CC(C)(C)CC(C)C[Al](CC(C)CC(C)(C)C)CC(C)CC(C)(C)C XZIKSWMNFLIAQP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the present invention relates to a new process, particularly simple, convenient and practical, for the preparation of metallocene compounds; more specifically, it relates to a process for the direct synthesis of metallocenes wherein the transition metal atom has at least one sigma ligand selected from the group consisting of linear or branched, saturated or unsaturated C r C 2o alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl and C 7 -C 20 arylalkyl radicals, optionally containing Si or Ge atoms.
- These metallocenes are useful as catalyst components, e.g. in the polymerization, oligomerization and hydrogenation of olefins, in association with alumoxanes and/or compounds able to form alk lmetallocene cations.
- Homogeneous catalytic systems based on metallocenes in association with an aluminum alkyl compound or an alumoxane are well known in the state of the art and are widely used in the polymerization reaction of olefins.
- the European Patent Application EP 0 129 368 discloses catalysts comprising mono, di and tricyclopentadienyl coordination complexes with a transition metal and an alumoxane; more specifically, said coordination complexes are metallocene compounds of general formula:
- (C 5 R' is an optionally substituted cyclopentadienyl group, in which R' can be hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl radical, having from 1 to 20 carbon atoms, or two or four substituents R' on the same cyclopentadienyl group can form one or two rings, having 4 to 6 carbon atoms;
- R" is a divalent radical bridging the two cyclopentadienyl groups;
- M is a transition metal belonging to groups 4, 5 or 6 of the Periodic Table of the Elements; p is 0, 1 or 2; s is 0 or 1; m is 0 to 5; and the sigma ligands Q, same or different from each other, can be halogen atoms, alkyl, cycloalkyl, alkenyl, aryl, al
- the sigma ligands of the central metal atom are usually halogen, preferably chlorine; also metallocene dialkyls, particularly dimethyls, have been developed and are widely used as catalyst components for olefin polymerization reactions, in association with suitable cocatalysts, such as alumoxanes and borate salts, e.g.
- metallocene dihalide usually the metallocene dichloride, by reacting suitable ligand/s with MX 4 , wherein X is halogen (usually TiCl 4 or ZrCl 4 );
- step (2) 2) converting the metallocene dihalide obtained in step (1) into the corresponding dialkyl or diaryl complex, by substitution of the halogens linked to the metal atom with the desired alkyl or aryl groups, by means of an alkylating agent such as alkyllithium, dialkylmagnesium or the corresponding Grignard reagent.
- an alkylating agent such as alkyllithium, dialkylmagnesium or the corresponding Grignard reagent.
- the International Patent Application WO 96/19488 describes a method for preparing metallocene alky Is comprising, among the others, the steps of reacting a cyclopentadienyl ligand metal salt with a perhalogenated group 4-6 transition metal compound and subsequently reacting the thus obtained metallocene dihalide with at least two molar equivalents of an alkylating agent; after separation and purification procedures, metallocene alky Is are isolated.
- Cp is a substituted or unsubstituted cyclopentadienyl group, optionally condensed to one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings, containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms;
- A is -O-, -S-, -N(R 2 )-, wherein R 2 is hydrogen, a linear or branched, saturated or unsaturated C r C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl, or A has the same meaning of Cp;
- M is a transition metal belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups of the Periodic Table of the Elements (IUPAC version);
- the substituents L same or different from each other, are monoanionic sigma ligands selected from the group consisting of linear or branched, saturated or unsaturated C J -C JO alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl and C 7 -C 20 arylalkyl groups, optionally containing one or more Si or Ge atoms; preferably, the substituents L are the same; the substituents L', same or different from each other, are halogens or -OR 5 , wherein R 5 has the same meaning of R 1 ; m is 1 or 2, and more specifically it is 1 when Z is N or P, and it is 2 when Z is C, Si or
- step (2) reacting the product obtained from step (1) with at least 1 molar equivalent of a compound of formula ML' S , wherein M and L' have the meaning reported above; s is an integer corresponding to the oxidation state of the metal and ranges from 3 to 6.
- the process of the invention allows to obtain metallocene compounds wherein the metal bears one or more sigma-bonded hydrocarbon substituents, in a simple, rapid and economic way, leading to the desired products with a one-step process starting from the suitable ligands; furthermore, said process leads to final yields much higher than the ones obtainable with the procedures known in the state of the art, therefore allowing a convenient industrial exploitation of the above metallocene compounds as catalyst components in the polymerization of olefins.
- the divalent bridge (ZR 1 n is preferably selected from the group consisting of CR' 2 , (CR 1 2 ) 2 , (CR 1 ⁇ , SiR' 2 , GeR ⁇ , NR 1 and PR 1 , R 1 having the meaning reported above; more preferably, said divalent bridge is Si(CH 3 ) 2 , SiPh 2 , CH 2 ,
- variable m is 1 or 2; the variable n ranges from 0 to 4 and, when n > 1, the atoms Z can be the same or different from each other, such as in divalent bridges -CH 2 -O-, -CH 2 -S- and -CH 2 -Si(CH 3 ) 2 -.
- the ligand Cp which is ⁇ -bonded to said metal M, is preferably selected from the group consisting of cyclopentadienyl, mono-, di-, tri- and tetra-methyl cyclopentadienyl; 4-'butyl- cyclopentadienyl; 4-adamantyl-cyclopentadienyl; indenyl; mono-, di-, tri- and tetra-methyl indenyl; 4,5,6,7-tetrahydroindenyl; fluorenyl; 5,10-dihydroindeno[l,2-b]indol-10-yl; N- methyl- or N-phenyl-5,10-dihydroindeno [l,2-b]indol-10-yl; 5,6-dihydroindeno[2J-b]indol-
- 6-yl N-methyl-or N-phenyl-5,6-dihydroindeno[2J-b]indol-6-yl; azapentalene-4-yl; thiapentalene-4-yl; azapentalene-6-yl; thiapentalene-6-yl; mono-, di- and tri-methyl- azapentalene-4-yl .
- the group A has preferably the same meaning of Cp, and more preferably is cyclopentadienyl, indenyl or tetrahydroindenyl.
- the metal M is preferably Ti, Zr or Hf, and more preferably Zr.
- the substituents L are preferably the same and are selected from the group consisting of C ,-
- the substituents L are selected from the group consisting of methyl, ethyl, n-butyl, sec-butyl, phenyl, benzyl and -CH 2 Si(CH 3 ) 3 .
- L is methyl.
- the substituents L' are preferably Cl, Br or OR 5 , wherein R 5 has the meaning reported above, and more preferably it is a C r C 6 alkyl or a C 6 -C ⁇ 0 aryl; even more preferably, L' is selected from the group consisting of Cl, -OEt, -OPr, -OBu and -OBz.
- n ranges from 0 to 4, and it is preferably 1 or 2.
- A can have only the meaning of Cp;
- Cp and A are preferably pentamethyl cyclopentadienyl, indenyl or 4,5,6,7- tetrahydroindenyl groups.
- Cp and A are preferably cyclopentadienyl, tetramethyl-cyclopentadienyl, indenyl, 4,5,6,7-tetrahydroindenyl, 2- methyl-4 ,5,6, 7-tetrahydroindenyl , 4 ,7-dimethyl-4 ,5,6, 7-tetrahydroindenyl , 2,4, 7-trimethy 1-
- (ZR' n is preferably (CH 3 ) 2 Si, CH 2 or C 2 H 4 .
- step (2) reacting the product obtained from step (1) with at least 1 molar equivalent of a compound of formula ML' S , wherein M and L' have the meaning reported above, and s is an integer corresponding to the oxidation state of the metal and ranges from 3 to 6.
- the metallocene compounds of formula (I) can be finally isolated from the reaction mixture obtained in step (2) and optionally purified according to standard procedures.
- said leaving group Y is preferably selected from the group consisting of -H, -SiR 3 and -SnR 3 , wherein the groups R are C r C 20 -alkyl,
- the metal M is preferably Ti, Zr or Hf, and the substituents L' are preferably the same and are selected from the group consisting of -Cl, -Br, -OMe, -OEt, - OPr, -OBu and -OBz; the variable s ranges from 3 to 6 and corresponds to the oxidation state of the metal M.
- Said reactant is preferably selected from the group consisting of TiCl 4 ,
- L j B and LMgL' are alkylating agents, wherein L is preferably a C r C 7 alkyl group, a C 6 -C 14 aryl group, or a C 7 -C 14 arylalkyl group, optionally substituted with Si or Ge, and more preferably L is selected from the group consisting of methyl, ethyl, n-butyl, sec-butyl, phenyl, benzyl and -CH 2 Si(CH 3 ) 3 ; even more preferably, L is methyl.
- B is an alkaline or alkaline-earth metal, and preferably Li or Mg; j can be 1 or 2, as already reported.
- the compound LMgL' is a Grignard reagent, wherein Mg is magnesium and L and L' have the meanings reported above; L' is preferably Cl or Br.
- said alkylating agent is methyllithium
- the process of the invention is carried out in an aprotic solvent, either polar or apolar; said aprotic solvent is preferably an aromatic or aliphatic hydrocarbon or an ether, and more preferably it is selected from the group consisting of benzene, toluene, pentane, hexane, heptane, cyclohexane, diethylether, tetrahydrofurane or mixtures thereof.
- aprotic solvent is preferably an aromatic or aliphatic hydrocarbon or an ether, and more preferably it is selected from the group consisting of benzene, toluene, pentane, hexane, heptane, cyclohexane, diethylether, tetrahydrofurane or mixtures thereof.
- step (1) said ligand (Y-1)
- Cp)(ZR 1 n (A-Y) r is previously dissolved in an aprotic solvent and to the resulting solution is added the alkylating agent L j B or LMgL'; this addition is preferably carried out at a temperature ranging from -100°C and +80°C, and more preferably from -80°C and -20°C, over a period of 5-45 minutes, and more preferably of 10-20 minutes.
- the alkylating agent is preferably added in the form of a solution in one of the above mentioned aprotic solvents, and preferably by slowly dropping.
- reaction mixture is preferably allowed to react, under stirring, for a period ranging from 1 hour to 6 hours, and more preferably from 2 hours to 3 hours, at a temperature comprised between -10°C and +80°C, and more preferably at room temperature.
- step (2) the mixture obtained from step (1) is preferably cooled to a temperature ranging from -100°C and +80°C, and more preferably from -80°C and -70°C; then, ML' S is quickly added to the cooled mixture, in the form of a solution in one of the above mentioned aprotic solvents, preferably pentane.
- aprotic solvents preferably pentane.
- reaction mixture is then allowed to react for a period ranging from 6 hours to 36 hours, and more preferably from 12 hours and 18 hours, at a temperature comprised between -
- metallocene compounds of formula (I) can be isolated according to common procedures known in the state of the art. Mixtures of racemic and meso isomers can be obtained and pure isomers can be separated in high yields by using standard procedures.
- the process according to the present invention allows even to obtain pure isomeric forms (racemic or meso) of said metallocene compounds, in very high yield and using a convenient one-pot reaction.
- metallocene compounds obtained with the process according to the present invention are useful in homo or co-polymerization of olefins, in particular of ⁇ -olefins of formula
- CH 2 CHR wherein R is hydrogen or a C r C 20 alkyl, such as propylene, 1-butene,
- 1-pentene, 4-methyl-l-pentene, 1-hexene and 1-octene when contacted with alumoxanes and/or organometallic aluminum compounds. They can be advantageously used for the production of isotactic, syndiotactic or atactic polypropylene.
- cycloolefins such as cyclopentene, cyclohexene, norbornene and 4,6-dimethyl-l-heptene
- polyenes such as 1,4-hexadiene, isoprene, 1,3 -butadiene
- the above metallocenes form suitable polymerization catalytic systems in association with alumoxanes of formula: wherein the substituents R 3 can be a linear or branched, saturated or unsaturated, C.-C 20 alkyl, alkenyl or alkylaryl radical; or in association with an organometaUic aluminum compound of formula A1R 4 3.Z H Z , wherein
- R 4 can be C r C 10 alkyl, alkenyl or alkylaryl radicals, optionally containing one or more Si or
- alumoxanes acting as cocatalysts with the above metallocenes, are methylalumoxane (MAO), tris(2-methyl-propyl)alumoxane (TIBAO) and 2,4,4-trimethyl- pentylalumoxane (TIOAO).
- MAO methylalumoxane
- TIBAO tris(2-methyl-propyl)alumoxane
- TIOAO 2,4,4-trimethyl- pentylalumoxane
- organometaUic aluminum are trimethylaluminum (TMA), tris(2,4,4-trimethyl-pentyl)aluminum (TIOA), tris(2-methyl-propyl)aluminum (TIBA), tris(2,3,3-trimethyl-butyl)aluminum, tris(2J-dimethyl-hexyl)aluminum, tris(2,3-dimethyl- butyl)aluminum, tris(2,3-di ethyl-pentyl)aluminum, ttis(2,3-dimemyl-heptyl)aluminum, tris(2-memyl-3-ethyl-pentyl)aluminum and tris(2-ethyl-3,3-dimethyl-butyl).
- TMA trimethylaluminum
- TIOA tris(2,4,4-trimethyl-pentyl)aluminum
- TIBA tris(2-methyl-prop
- Suitable cocatalysts are compounds capable of forming a metallocene cation, having formula Y + Z " , wherein Y + is a Br ⁇ nsted acid (such as Ph 3 C + or HN + (n-Bu) 3 ) and Z " is a Br ⁇ nsted acid (such as Ph 3 C + or HN + (n-Bu) 3 ) and Z " is a Br ⁇ nsted acid (such as Ph 3 C + or HN + (n-Bu) 3 ) and Z " is a
- the above catalysts can be used on inert supports, such as silica, alumina, styrene/divinylbenzene copolymers, polyethylene or polypropylene, particularly suitable in gas phase polymerizations.
- inert supports such as silica, alumina, styrene/divinylbenzene copolymers, polyethylene or polypropylene, particularly suitable in gas phase polymerizations.
- the polymerization processes can be carried out in liquid phase, optionally in the presence of an inert hydrocarbon solvent either aromatic (e.g. toluene) or aliphatic (e.g. propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane).
- an inert hydrocarbon solvent either aromatic (e.g. toluene) or aliphatic (e.g. propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane).
- the polymerization temperature generally ranges from about 0°C to about 250°C, and preferably from 20 to 150°C.
- the ligand bis-(3-tetra-butyl-l-indenyl)methane was prepared by the base-catalyzed condensation of indene with formaldehyde, as described in Example 3 (a) and (b) of the European Patent Application No.97200933.6.
- the cooling bath was removed.
- the reaction mixture was stirred overnight (about 16 hours) at room temperature.
- the black mixture thus obtained was brought to dryness under reduced pressure.
- the resulting black powder was suspended in 100 mL of pentane and transferred into a filtration apparatus equipped with side arm (to allow solvent refluxing), connecting the system above and below the frit, a receiving flask on the bottom and bubble condenser on the top.
- the filtered 100 mL pentane solution (A) were separated and the remaining solid was extracted with refluxing pentane for about 6 hours.
- Ethylenebis(4,7-dimethyl-l-indenyl) zirconium dichloride was prepared by reacting 1,2- bis(4,7-dimethyl-indenyl)ethane with ZrCl 4 , as reported by L. Resconi et al.
- the reaction mixture was allowed to warm slowly to room temperature overnight (about
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP53674499A JP4208265B2 (en) | 1998-01-14 | 1999-01-14 | Method for producing metallocene compound |
CA002283880A CA2283880A1 (en) | 1998-01-14 | 1999-01-14 | Process for the preparation of metallocene compounds |
DE69903388T DE69903388T2 (en) | 1998-01-14 | 1999-01-14 | METHOD FOR PRODUCING METALLOCENES |
EP99902538A EP0979232B1 (en) | 1998-01-14 | 1999-01-14 | Process for the preparation of metallocene compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP98200077.0 | 1998-01-14 | ||
EP98200077 | 1998-01-14 |
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WO1999036427A1 true WO1999036427A1 (en) | 1999-07-22 |
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ID=8233295
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PCT/EP1999/000188 WO1999036427A1 (en) | 1998-01-14 | 1999-01-14 | Process for the preparation of metallocene compounds |
Country Status (8)
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US (1) | US6191294B1 (en) |
EP (1) | EP0979232B1 (en) |
JP (1) | JP4208265B2 (en) |
KR (1) | KR20000076111A (en) |
CN (1) | CN1243763C (en) |
CA (1) | CA2283880A1 (en) |
DE (1) | DE69903388T2 (en) |
WO (1) | WO1999036427A1 (en) |
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WO1999054369A1 (en) * | 1998-04-21 | 1999-10-28 | Montell Technology Company B.V. | Process for the preparation of copolymers of ethylene with alpha-olefins |
WO2000075151A1 (en) * | 1999-06-04 | 2000-12-14 | Basell Technology Company B.V. | Process for the preparation of titanium complexes |
WO2001053360A1 (en) * | 2000-01-18 | 2001-07-26 | Basell Technology Company B.V. | Process for producing substantially amorphous propylene-based polymers |
WO2003057705A1 (en) * | 2002-01-08 | 2003-07-17 | Basell Polyolefine Gmbh | Preparation of silicon-bridged metallocene compounds |
US6693156B1 (en) | 1998-11-18 | 2004-02-17 | Basell Polyolefine Gmbh | Methylene bridged metallocenes as olefin-polymerization-catalyst components |
JP2004535505A (en) * | 2001-07-17 | 2004-11-25 | バセル ポリオレフィン ジーエムビーエイチ | Multi-step method for olefin (co) polymerization |
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- 1999-01-14 CN CNB99800037XA patent/CN1243763C/en not_active Expired - Fee Related
- 1999-01-14 EP EP99902538A patent/EP0979232B1/en not_active Expired - Lifetime
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Cited By (25)
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US6448350B1 (en) | 1998-04-21 | 2002-09-10 | Basell Technology Company Bv | Process for the preparation of copolymers of ethylene with alpha-olefins |
WO1999054369A1 (en) * | 1998-04-21 | 1999-10-28 | Montell Technology Company B.V. | Process for the preparation of copolymers of ethylene with alpha-olefins |
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Publication number | Publication date |
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US6191294B1 (en) | 2001-02-20 |
KR20000076111A (en) | 2000-12-26 |
EP0979232A1 (en) | 2000-02-16 |
CN1243763C (en) | 2006-03-01 |
EP0979232B1 (en) | 2002-10-09 |
DE69903388T2 (en) | 2003-06-18 |
DE69903388D1 (en) | 2002-11-14 |
JP4208265B2 (en) | 2009-01-14 |
CN1255925A (en) | 2000-06-07 |
JP2001516367A (en) | 2001-09-25 |
CA2283880A1 (en) | 1999-07-22 |
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