WO1997049712A2 - Production of bridged metallocene complexes and intermediates therefor - Google Patents
Production of bridged metallocene complexes and intermediates therefor Download PDFInfo
- Publication number
- WO1997049712A2 WO1997049712A2 PCT/US1997/010684 US9710684W WO9749712A2 WO 1997049712 A2 WO1997049712 A2 WO 1997049712A2 US 9710684 W US9710684 W US 9710684W WO 9749712 A2 WO9749712 A2 WO 9749712A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- group
- metal
- bridged
- silicon
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000543 intermediate Substances 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 57
- 230000008569 process Effects 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 116
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 13
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- -1 alkaline earth metal aluminum hydride Chemical class 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052801 chlorine Chemical group 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- VGRFVJMYCCLWPQ-UHFFFAOYSA-N germanium Chemical compound [Ge].[Ge] VGRFVJMYCCLWPQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011369 resultant mixture Substances 0.000 claims 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 150000004292 cyclic ethers Chemical class 0.000 claims 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 claims 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 abstract description 18
- 229910007932 ZrCl4 Inorganic materials 0.000 abstract description 13
- KXYGKDBONOVZOM-UHFFFAOYSA-N 1h-cyclopenta[a]naphthalene Chemical class C1=CC=CC2=C3CC=CC3=CC=C21 KXYGKDBONOVZOM-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- HMDUFJHTFREFSA-UHFFFAOYSA-N 2,3-dihydro-1h-cyclopenta[a]naphthalen-1-ol Chemical class C1=CC=CC2=C3C(O)CCC3=CC=C21 HMDUFJHTFREFSA-UHFFFAOYSA-N 0.000 abstract description 5
- KQBXYYMELBQTFL-UHFFFAOYSA-N 2,3-dihydrocyclopenta[a]naphthalen-1-one Chemical class C1=CC=CC2=C3C(=O)CCC3=CC=C21 KQBXYYMELBQTFL-UHFFFAOYSA-N 0.000 abstract description 5
- 150000004696 coordination complex Chemical class 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract description 3
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical class [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 150000001983 dialkylethers Chemical class 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KARBAWHAZAEEEE-UHFFFAOYSA-N 2,3-dihydro-1H-cyclopenta[a]naphthalen-5-ol Chemical compound C1CCC2=CC(=C3C(=C12)C=CC=C3)O KARBAWHAZAEEEE-UHFFFAOYSA-N 0.000 description 1
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- BWTBHGDNJBIYAQ-UHFFFAOYSA-N n,n'-diethyl-n,n'-dimethylethane-1,2-diamine Chemical compound CCN(C)CCN(C)CC BWTBHGDNJBIYAQ-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- UNEXJVCWJSHFNN-UHFFFAOYSA-N n,n,n',n'-tetraethylmethanediamine Chemical compound CCN(CC)CN(CC)CC UNEXJVCWJSHFNN-UHFFFAOYSA-N 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
Definitions
- This invention relates to a new, efficacious process for producing bridged metallocene complexes, such as for example dihydrocarbylsilyl-bridged zirconocene complexes, and for producing key intermediates used in the overall synthesis process.
- This invention provides, inter alia, a new process for producing bridged metallocene compounds — such as are described in the foregoing Rohrmann et al. patent - which is both efficacious and of promising commercial utility in plant-sized operations.
- One of the key steps of the process involves converting a deprotonated silicon- , germanium- or tin-containing ligand into the metallocene.
- this is accomplished to great advantage by adding a diamine adduct of a Group IV, V, or VI metal tetrahalide to a solution or slurry formed from a deprotonated silicon-, germanium- or tin- containing ligand and an organic liquid medium so as to form a metallocene.
- a diamine adduct of a Group IV, V, or VI metal tetrahalide to a solution or slurry formed from a deprotonated silicon-, germanium- or tin- containing ligand and an organic liquid medium so as to form a metallocene.
- the overall process of the invention involves the direct conversion of benzoindanones to benzoindanols which, without isolation, are converted to benzoindenes. Thereupon the benzoindenes are bridged by deprotonating the benzoindenes with a strong base such as butyllithium and reacting the resultant deprotonated product with a suitable silicon-, germanium- or tin-containing bridging reactant such as dichlorodimethylsilane.
- the resultant bridged product is deprotonated with a strong base such as butyllithium and reacted with a suitable Group IV, V, or VI metal-containing reactant such as ZrCl 4 to provide a silicon-, germanium- or tin-bridged Group IV, V, or VI metal complex, such as a dihydrocarbylsilyl-bridged zirconocene complex.
- a strong base such as butyllithium
- a suitable Group IV, V, or VI metal-containing reactant such as ZrCl 4 to provide a silicon-, germanium- or tin-bridged Group IV, V, or VI metal complex, such as a dihydrocarbylsilyl-bridged zirconocene complex.
- this last step can be conducted in various ways but preferably is conducted by adding a diamine adduct of a Group IV, V, or VI metal tetrahalide to a solution or slurry formed from a deprotonated silicon-, germanium- or tin-containing ligand and an organic liquid medium so as to form a metallocene.
- the overall processes of this invention involve the direct conversion of benzoindanones to benzoindanols which, without isolation, in turn are converted to benzoindenes. Thereupon the benzoindenes are bridged by deprotonating the benzoindenes with a strong base such as butyllithium and reacting the resultant deprotonated product with a suitable silicon-, germanium- or tin-containing bridging reactant.
- a strong base such as butyllithium
- the resultant bridged product so formed is then deprotonated with a strong base such as butyllithium and reacted with a suitable Group IV, V, or VI (formerly known as Groups IVb, Vb and VIb) metal -containing reactant to provide a silicon-, germanium- or tin-bridged Group IV, V, or VI metal complex, such as a dihydrocarbylsilyl-bridged zirconocene complex.
- a strong base such as butyllithium
- a suitable Group IV, V, or VI previously known as Groups IVb, Vb and VIb
- metal -containing reactant to provide a silicon-, germanium- or tin-bridged Group IV, V, or VI metal complex, such as a dihydrocarbylsilyl-bridged zirconocene complex.
- the initial benzoindanones used in the practice of such sequence can be formed readily and in high yield by reaction of a 2-haloacyl halide with naphthalenes unsubstituted in at least the 1- and 2-positions.
- This reaction normally produces a mixture of two isomers, namely a 4,5-benzoindan-l-one as the major isomer and a 4,5-benzoindan-3-one as the minor isomer.
- These isomers can, if desired, be separated from each other by known procedures.
- 4,5-benzoindanone refers to at least one 4,5- benzoindan-1-one or at least one 4,5-benzoindan-3-one, or a mixture of at least one 4,5-benzoindan-l-one and at least one 4,5-benzoindan-3-one.
- the conversion of a 4,5- benzoindanone to a 4,5-benzoindanol can form one or more 4,5-benzoindan-l-ols or one or more 4,5-benzoindan-3-ols, or a mixture of one or more 4,5-benzoindan-l-ols and one or more 4,5-benzoindan-3-ols.
- 4,5-benzoindanol refers to at least one 4,5-benzoindan-l-ol or at least one 4,5-benzoindan-3-ol, or a mixture of at least one 4,5-benzoindan-l-ol and at least one 4,5-benzoindan-3-ol.
- this invention provides a process of forming a 4,5- benzoindanol which comprises mixing together at least one of each of the following:
- a 4,5-benzoindanone (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, and (c) a hydroxyl -containing compound capable of interacting with (b) to serve as a hydrogen source, such that a 4,5-benzoin- danol is formed.
- borohydride or aluminum hydride reductions of the carbonyl group can be conducted with high selectivity and in good yields.
- the operation is preferably conducted in a liquid ether reaction medium such as tetrahydrofuran and alky ltetrahydrofurans .
- the preferred 4,5-benzoindanones for use in the process are 4,5-benzoindan-l- ones or mixtures of a major molar proportion of one or more 4,5-benzoindan-l-ones and a minor molar proportion of one or more 4,5-benzoindan-3-ones, such as for example a mixture of about 90 mol % of a 4,5-benzoindan-l-one and about 10 mol
- Sodium borohydride is the preferred reducing agent, but use can be made of other compounds such as sodium aluminum tetrahydride, sodium aluminum hexahydride, and their lithium or potassium analogs.
- the alkali metal derivatives are preferred over the alkaline earth compounds, and as compared to the hexahydrides, the tetrahydrides are the more preferred reagents, especially the borohydrides.
- Such more preferred reagents may thus be depicted by the formula AMH x (OR) v wherein A is an alkali metal, M is boron or aluminum, R is hydrocarbyl, x is an integer in the range of 2 to 4, and y is an integer in the range of 0 to 2, the sum of x and y being 4. Most preferably y is zero and M is boron.
- the hydroxyl-containing component used in the reaction as a source of hydrogen is either water or a suitable hydroxyorganic compound such as an alcohol, a polyol, or a phenol. Water or lower alkanols or mixtures thereof are preferred.
- the 4,5-benzoindanones used in this reaction are illustrated by formula (A) below which for convenience depicts the 4,5-benzoindan-l-ones.
- the 4,5-benzoin- dan-3-ones have the same formula except that the keto functionality is in the 3- position of the 5-membered ring instead of the 1-position as shown.
- R 3 and R 5 through R 10 are the same or different and are a hydrogen atom; a halogen atom (preferably a fluorine, chlorine or bromine atom); a hydrocarbyl group containing up to about 10 carbon atoms each (e.g., a C, to C 10 , and preferably a C, to C 4 alkyl group, a C 6 to C, 0 aryl group, a C 3 to C, 0 cycloalkyl group, a C 2 to C, 0 , and preferably a C 2 to C 4 alkenyl group, a C, to C 10 aralkyl group, etc.); a halohydrocarbyl group containing up to about 10 carbon atoms and up to about 3 halogen atoms each; an -NR 2 , -SR, -OSiR 3 , -SiR 3 , or -PR 2 group in which R is a hydrocarbyl group containing up to about 10 carbon atoms
- the 4,5-benzoindanols formed in this reaction likewise can exist in either of two isomeric forms derived from the isomeric forms of the 4,5-benzoindanone(s) used as the starting material.
- Such 4,5-benzoindanols are thus illustrated by formula (B) below which depicts the 4,5-benzoindan-l-ols.
- the 4,5-benzoindan-3-ols have the same formula except that the hydroxyl group is in the 3-position of the 5-membered ring instead of the 1-position as shown.
- R 3 and R 5 through R 10 are as described above.
- Another embodiment of this invention is the process of forming 4,5-benzoin- dene which comprises reducing a 4,5-benzoindanone to a 4,5-benzoindanol as described above, and catalytically dehydrating the 4,5-benzoindanol (Formula (B) above) so formed.
- the 4,5-benzoindenes formed in this reaction can be depicted by the formula:
- Formula (C) depicts an isomer having a double bond of the 5-membered ring in the 1-position. In another isomer that double bond can instead be in the 2-position, and mixtures of these respective isomers can be formed.
- the preferred method of effecting the dehydration step involves use of an arylsulfonic acid catalyst such as p-toluenesulfonic acid.
- an arylsulfonic acid catalyst such as p-toluenesulfonic acid.
- the reduction of the benzoindanone (Formula (A) above) to the benzoindanol (Formula (B) above) is preferably terminated by quenching the reaction mixture with water or a suitable aqueous solution or mixture, and separating off the aqueous phase before proceeding with the catalytic dehydration reaction.
- the separations after the aqueous quench can be readily accomplished by extracting the quenched reaction mixture with a liquid hydrocarbon, preferably a mononuclear aromatic hydrocarbon such as toluene or xylene, having a higher boiling point or higher initial boiling point than the ether, and distilling at least the ether from the resultant extract.
- a liquid hydrocarbon preferably a mononuclear aromatic hydrocarbon such as toluene or xylene
- the water formed during the dehydration plus residual water, if any, from the quenching step can be readily removed by azeotropic distillation.
- the catalytic dehydration is best carried out using an arylsulfonic acid catalyst, other ways of performing the dehydration can be used especially for laboratory scale operations. Such methods include use of oxalic acid as dehydration catalyst or reaction of the benzoindanol with dehydrating substances such as magnesium sulfate or molecular sieves.
- dehydrating substances such as magnesium sulfate or molecular sieves.
- a preferred process sequence per this invention for con ⁇ verting a 4,5-benzoindanone to a 4,5-benzoindene comprises: (a) a 4,5-benzoindanone is reduced to a 4, 5 -benzoindanol in an ether-containing reaction medium by use of an alkali metal borohydride and water or an alcohol or a mixture thereof; (b) the reduction is terminated by quenching the reaction mixture with a suitably large amount of water (or appropriate aqueous mixture); (c) a separation is made between the water and organic constituents of the reaction mixture, by extracting the quenched reaction mixture with a liquid hydrocarbon having a higher boiling point or higher initial boiling point than the ether, and, if present, the alcohol; (d) distilling off said ether and, if present, the alcohol to leave a liquid hydrocarbon solution of the 4,5- benzoindanol; (e) catalytically dehydrating 4,5-benzoindanol so formed to the corresponding
- R 3 be an alkyl group, most preferably a methyl group, and that at least four and most preferably all six of R 5 through R 10 be hydrogen atoms.
- Another embodiment of this invention comprises converting the 4,5-benzoin- denes (Formula C above) to a silicon-, germanium- or tin-bridged complex of the formula:
- M 1 is a silicon, germanium or tin atom (preferably a silicon atom)
- R n and R 12 are the same or different and are a hydrocarbyl group containing up to about 18 carbon atoms each (e.g., a C, to C.
- a and preferably a C, to C 4 alkyl group, a C 6 to C 18 aryl group, a C 3 to C lg cycloalkyl group, a C 2 to C lg , and preferably a C 2 to C 4 alkenyl group, a C 7 to C, g aralkyl group, etc.); or a hydrocarbyl(oxyalkylene) or hydrocarbylpoly(oxyalkylene) group containing up to about 100 carbon atoms (preferably where the oxyalkylene moiety or moieties are oxyethylene and or oxymethylethylene, and in the case of long chain polyoxyalkylenes, the oxyalkylene moieties are in random or block arrangements.
- M 1 is a silicon atom
- R" and R 12 are the same and are C, to C 4 alkyl groups, most preferably methyl or ethyl groups
- R 3 is an alkyl group, most preferably a methyl group, and at least four and most preferably all six of R 5 through R 10 are hydrogen atoms.
- the benzoindenes (Formula (C) above) are deprotonated with a strong base such as butyllithium and reacted with a suitable silicon, germanium or tin reactant, which can be depicted by the formula R u R l2 M 1 X 2 where X is a halogen atom (preferably a chlorine or bromine atom) and M 1 , R 11 and R 12 are as described above.
- these operations are conveniently conducted in a dialkyl ether medium, typically a lower alkyl ether such as diethyl ether, dipropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl tert-amyl ether, or dibutyl ether, most preferably diethyl ether.
- a dialkyl ether medium typically a lower alkyl ether such as diethyl ether, dipropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl tert-amyl ether, or dibutyl ether, most preferably diethyl ether.
- a liquid dialkyl ether enables the bridged product to form a slurry which is easily separated from the liquid phase by such procedures as filtration, centrifugation or decantation.
- the bridged compound of Formula (D) above is transformed into a metallocene complex of the formula:
- M 2 is a group IV, V, or VI metal atom (i.e. , Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W);
- X 1 and X 2 are the same or different and each is a halogen atom (preferably a chlorine atom); and
- M ⁇ R 3 and R 5 through R 12 are as described above.
- M 2 is Ti, Zr or Hf, most preferably Zr;
- X 1 and X 2 are chlorine atoms;
- M 1 is a silicon atom;
- R 11 and R 12 are the same and are C, to C 4 alkyl groups, most preferably methyl or ethyl groups,
- R 3 is an alkyl group, most preferably a methyl group, and at least four and most preferably all six of R 5 through R 10 are hydrogen atoms.
- Compounds of Formula (E) above are formed by deprotonating a bridged com ⁇ pound of Formula (D) above with a strong base such as butyllithium and reacting the deprotonated intermediate so formed with a suitable Group IV, V, or VI metal-con ⁇ taining reactant, such as a Group IV, V, or VI metal tetrahalide.
- the deprotonation is typically performed in an ether medium such as tetrahydrofuran or lower dialkyl ether.
- the metallation reaction can be conducted by adding the ether solution of the deprotonated intermediate portionwise to a preformed complex or mixture of the Group IV, V, or VI metal-containing reactant and an ether such as tetrahydrofuran in a hydrocarbon solvent such as toluene or xylenes or the like.
- a hydrocarbon solvent such as toluene or xylenes or the like.
- the bridged metallocene of Formula (E) is produced by adding a chelate diamine adduct of the Group IV, V or VI metal tetrahalide to a solution or slurry of a deprotonated bridged compound of Formula (D) above, such as a dilithium or disodium derivative thereof.
- the advantages of this embodiment may be realized not only with dilithium or disodium derivatives of silicon-, germanium- or tin-bridged complexes depicted in Formula (D) but in addition, with dilithium or disodium derivatives of silicon-, germanium- or tin-bridged complexes analogous to those depicted in Formula (D) having other cyclopentadienyl moieties regardless of whether the moieties are composed of bridged single rings (e.g., cyclopentadienyl and hydrocarbyl-substituted cyclopentadienyl moieties) or bridged fused rings (e.g.
- dilithium or disodium deriva ⁇ tives of silicon-, germanium- or tin-bridged cyclopentadienyl-moiety-containing com- pounds having 5 to about 75 carbon atoms in the molecule can be used as the ligand.
- the chelate diamine adduct of a Group IV, V, or VI metal tetrahalide can be formed from such amines as N,N,N',N'-tetramethyldiaminomethane, N,N,N',N'- tetraethyldiaminomethane,N,N'-diethyl-N,N'-dimethyldiaminomethane, N,N,N',N'- tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N'-diethyl- N,N'-dimethylethylenediamine, and like diamines capable of forming an adduct with such metal tetrahalides.
- the preferred diamine is N,N,N',N'-tetramethylethylene- diamine.
- Various compounds of Formula (E) are useful as components for catalyst systems for producing polyolefins such as polyethylene
- Examples 1-4 illustrate preferred procedures for conducting the overall sequence of steps that can be employed in the practice of this invention.
- Examples 5-7 illustrate preferred procedures for transforming the dilithium or disodium derivatives of silicon-, germanium- or tin-bridged cyclopentadienyl-moiety-containing compounds into the bridged metallocenes by addition thereto of the chelate diamine adduct of the Group IV, V, or VI metal tetrahalide pursuant to this invention.
- Examples 8-10 which show procedures that can be used in the overall sequence of reactions for effecting the same transformation, highlight the dramatic superiority and advantages of the preferred procedures illustrated in Examples 5-7. Unless otherwise specified, all percentages in the Example are by weight. It is to be clearly understood that Examples 1-7 are for the purposes of illustrating current best modes for carrying out the operations. None of the Examples is intended to limit, and should not be construed as limiting, the invention to the specific procedures set forth therein.
- reaction slurry was then transferred to 2 to 3 liters of ice/water in a separate flask with agitation. HCl/HBr gas formed during the hydrolysis was scrubbed by a caustic solution.
- the organic phase (lower layer) of the hydrolyzed mixture was separated and saved.
- the upper aqueous layer was extracted once with 500 mL of methylene chloride.
- the combined organic phase and extract were washed with water (2x, 500 mL each) and the solvent was removed in vacuo to obtain crude product as a brown oil.
- the brown oil was flashed under 5 mm Hg vacuum and 158-160°C head temperature (or 170-210°C pot temperature) to collect 276 g (87% yield) of product as an orange oil.
- NMR analysis of the oil confirmed it was 2-methyl-4,5-benzoindanone; GC analysis of the oil indicated it was 96% pure.
- ZrCl 4 (56.8 g; 0.244 mol) was slurred in 500 mL of anhydrous toluene. THF (70 g; 0.97 mol) was added to this slurry to form the complex, ZrCl 4 (THF) 2 . The reaction was stirred overnight and then the solution of the dilithium derivative was added dropwise to the ZrCl 4 (THF) 2 slurry over 75 minutes. An orange-yellow slurry formed. After 2 hours, the reaction mixture was heated in an oil bath and 350 mL of solvent were flash distilled. A vacuum was applied and an additional 450 mL of volatiles were removed.
- the crude product was slurried in 900 mL of anhydrous THF and heated to reflux overnight. The slurry was cooled to room temperature and filtered on a coarse frit. The yellow solids were washed with 35 mL of THF and dried in vacuo. The dried weight of dimethylsilylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride was 41.4 grams (30% yield based on the initial silyl-bridged reactant). 'H NMR determined the rac/meso ratio to be greater than 99: 1.
- THF and ZrCl 4 (2.33 g; 10 mmol) were quickly mixed in a 50 mL flask (while the temperature increased from 22°C to 38°C due to the heat of ether adduct formation).
- the resultant white slurry was stirred at about 30°C for 2.5 hours.
- N,N,N',N'-tetramethylethylene diamine (TMEDA, 0.85 g; 7.3 mmol) was added (in an approximately 5-minute period) and a white solid adduct dissolved to form a solution. After stirring at about 27°C for approximately 10 minutes, the diamine adduct solution was used for reaction with the dilithium derivative of the silyl-bridged reactant as now to be described.
- This solution was added in about a 7-minute period to a solution (31.88 g) containing about 4.28 g Li 2 LIG (about 10 mmol), 7.3 g Et/), 20.1 g THF, 0.15 g (about 0.36 mmoles) LiLIG, and 0.04 g hexane (the last two of which were undesired impurities) at temperatures ranging from 25 to 30°C. Additional THF (0.5 g) was used for rinsing the contents of the first flask into the second flask. The reaction mass was stirred at ca. 30°C for ca. 19.5 hours. Then the mixture was heated to 60°C to strip off 7.81 g of Et ⁇ O and THF.
- the ZrCl 4 was added to the dilithium ligand as the ZrCl 4 »(THF) 2 adduct; no chelating diamine was used.
- ZrCl 4 (2.80 g; 12 mmol) and 15 g of THF were quickly mixed and stirred for 1 hour resulting in a white slurry.
- the slurry was added to a 22.8 g solution composed of 20.9% (ca. 11.1 mmol), 78% THF, 0.1 % LiLIG and 1. 1 % pentane at about 25-30°C over a 20- minute period using an additional 3 g of THF for wash.
- the slurry was heated up to 60°C for 4 hours (to improve the filtration).
- the filtration was slow (about 1.5 hours or about 5 to 10 times slower than when operating as in Examples 5-7 above).
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US08/853,698 US5861522A (en) | 1996-06-27 | 1997-05-08 | Production of bridged metallocene complexes and intermediates therefor |
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WO1998057975A1 (en) * | 1997-06-17 | 1998-12-23 | Albemarle Corporation | Enhanced production of bridged hafnocenes |
US6743932B2 (en) | 2000-04-07 | 2004-06-01 | Basell Polyolefine Gmbh | Polymerization catalyst |
KR100676302B1 (en) | 2005-01-06 | 2007-01-30 | 주식회사 엘지화학 | Preparation method of ansa-metallocene compounds |
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EP0545304A1 (en) * | 1991-11-30 | 1993-06-09 | Hoechst Aktiengesellschaft | Process for the preparation of substituted indenes and their use as ligands for metallocene catalysts |
EP0549900A1 (en) * | 1991-11-30 | 1993-07-07 | Hoechst Aktiengesellschaft | Metallocenes containing benzocondensed indenyl derivatives as ligands, process for their preparation and their use as catalysts |
EP0654476A1 (en) * | 1993-11-24 | 1995-05-24 | Hoechst Aktiengesellschaft | Metallocenes, their preparation and use as catalysts |
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JPH06345809A (en) * | 1993-06-07 | 1994-12-20 | Mitsui Petrochem Ind Ltd | New transition metallic compound, catalyst component for polymerizing olefin composed of the same transition metallic compound, catalyst for polymerizing olefin containing the same catalyst component for polymerizing olefin and method for polymerizing olefin |
JPH08208733A (en) * | 1995-01-31 | 1996-08-13 | Mitsubishi Chem Corp | Olefin polymerization catalyst |
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EP0545304A1 (en) * | 1991-11-30 | 1993-06-09 | Hoechst Aktiengesellschaft | Process for the preparation of substituted indenes and their use as ligands for metallocene catalysts |
EP0549900A1 (en) * | 1991-11-30 | 1993-07-07 | Hoechst Aktiengesellschaft | Metallocenes containing benzocondensed indenyl derivatives as ligands, process for their preparation and their use as catalysts |
EP0654476A1 (en) * | 1993-11-24 | 1995-05-24 | Hoechst Aktiengesellschaft | Metallocenes, their preparation and use as catalysts |
Non-Patent Citations (2)
Title |
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CHEMICAL ABSTRACTS, vol. 124, no. 23, 3 June 1996 Columbus, Ohio, US; abstract no. 317363c, FOSTER, P. ET AL.: "highly stable catalysts for the stereospecific polymerization of styrene" XP002040930 & ORGANOMETALLICS, vol. 15, no. 9, 1996, pages 2404-2409, * |
CHEMICAL ABSTRACTS, vol. 125, no. 25, 16 December 1996 Columbus, Ohio, US; abstract no. 328966y, FOSTER, P. ET AL.: "aromatic substituted group 4 metallocene catalysts for the polymerization of .alpha.-olefins" XP002040929 & ORGANOMETALLICS, vol. 15, no. 23, 1996, pages 4951-4953, * |
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WO1998057975A1 (en) * | 1997-06-17 | 1998-12-23 | Albemarle Corporation | Enhanced production of bridged hafnocenes |
US6743932B2 (en) | 2000-04-07 | 2004-06-01 | Basell Polyolefine Gmbh | Polymerization catalyst |
KR100676302B1 (en) | 2005-01-06 | 2007-01-30 | 주식회사 엘지화학 | Preparation method of ansa-metallocene compounds |
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