US20020123639A1 - Constrained geometry ligands and complexes derived therefrom - Google Patents
Constrained geometry ligands and complexes derived therefrom Download PDFInfo
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- US20020123639A1 US20020123639A1 US09/761,151 US76115101A US2002123639A1 US 20020123639 A1 US20020123639 A1 US 20020123639A1 US 76115101 A US76115101 A US 76115101A US 2002123639 A1 US2002123639 A1 US 2002123639A1
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- 239000003446 ligand Substances 0.000 title claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- -1 titanium(II) diene Chemical class 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000037048 polymerization activity Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000011541 reaction mixture Substances 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910021480 group 4 element Inorganic materials 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 0 C/C=C/C=C\[Ti](C)(C)N(C(C)(C)C)[Si](C)(C)c1c(C)c(C)c(C)c1C Chemical compound C/C=C/C=C\[Ti](C)(C)N(C(C)(C)C)[Si](C)(C)c1c(C)c(C)c(C)c1C 0.000 description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- RJMZIUFNDNYWDU-UHFFFAOYSA-N 3-chloro-2-hydroxy-5-phenylbenzoic acid Chemical compound ClC1=C(O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1 RJMZIUFNDNYWDU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UWUPSGKJVDVRLJ-UHFFFAOYSA-F C.C.C.C.C.C.Cl[Ti](Cl)(Cl)Cl.Cl[Ti](Cl)Cl.[Li]CCCC.[Li]Cl Chemical compound C.C.C.C.C.C.Cl[Ti](Cl)(Cl)Cl.Cl[Ti](Cl)Cl.[Li]CCCC.[Li]Cl UWUPSGKJVDVRLJ-UHFFFAOYSA-F 0.000 description 1
- SWGURCMIDOUYBF-UHFFFAOYSA-N CC[SiH](C)NC Chemical compound CC[SiH](C)NC SWGURCMIDOUYBF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PFGWJXLLXJLZCC-UHFFFAOYSA-N n-[dimethyl-(1,2,3,4-tetramethylcyclopenta-2,4-dien-1-yl)silyl]-2-methylpropan-2-amine Chemical compound CC1=CC(C)([Si](C)(C)NC(C)(C)C)C(C)=C1C PFGWJXLLXJLZCC-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 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
-
- 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
- This invention relates to constrained geometry complexes of group 4 metals and dienes characterized by high olefin polymerization activity, to ligands of such complexes and to methods for the production of such complexes and ligands.
- U.S. Pat. No. 5,470,993 describes the synthesis of constrained ; geometry group 4 metal diene complexes by contacting a reduced form of a group 4 metal tetrahalide, a diene and an appropriate dianion ligand of the desired metal complex.
- the diene complexes may have the formula which appears at lines 20-34 of Column 5 of U.S. Pat. No. 6,015,916 as follows:
- the corresponding dihalo ligand may have the formula also set forth in U.S. Pat. No. 6,015,916 (see Formula II of claim 1 ):
- the ligand may be any corresponding dihalo compound in which the chlorine substituents are replaced by bromine, iodine or fluorine and in which the “t-bu” substituent is replaced by any alkyl group.
- U.S. Pat. No. 6,015/916 describes the synthesis of similar complexes by treatment of a dihalo ligand of a metallocene compound with an alkali metal alkyl and a diene.
- the specification of U.S. Pat. No. 6,015,916 is, by express reference, incorporated herein and made a part of this specification.
- German Application DE 197 39 946 A1 describes a metallocene synthesis in which an appropriate ligand is converted to a metallocene by treatment with an adduct of Formula (I)
- M 1 denotes a metal of groups 3, 4, 5 or 6 of the periodic system of elements (PSB) or an element of the group of lanthanides or actinides, preferably titanium, zirconium, or hafnium, by special preference zirconium;
- X is the same or different, being halogen, a C 1-10 -alkoxy, C 6-10 -aryloxy, C 1-10 -alkylsulfonate such as mesylate, triflate, nonaflate, a C 6-10 arylsulfonate such as tosylate, benzene sulfonate, a C 1-10 -alkylcarboxylate such as acetate, formate, oxalate, or a 1,3-dicarbonylate such as acetylacetonate or a fluorinated 1,3-dicarbonylate; n is an integer and equals 2, 3, 4, 5 or 6 and corresponds to the oxidation number of the metal
- Cyclopentadienyl group means cyclopentadienyl, tetraalkylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
- group 4(II) and group 4(III) mean a is; group 4 metal of valence 2(II) or 3(III).
- a Group 4(II) metallocene compound is a compound comprised of a group 4(II) metal bonded to one or more cyclopontadienyl groups.
- a Group 4(II) metallocene ligand is a chemical precursor which contains a cyclopentadienyl or substituted cyclopentadienyl group from which a group 4(II) metallocene may a synthesized.
- Constrained geometry compound or catalyst means a catalyst in which the metal conter is contained in a ring structure and covalently bonded to a cyclic group via a delocalized n-system and covalently bonded via a sigma-bond to another atom, e.g., carbon, nitrogen, oxygen.
- a small ring size induces constraint about the metal atom center.
- titanium-containing CGCs the incorporated titanium atom can be in the +4, +3, or +2 formal oxidation state. See EP application 90309496.9, WO 95/00526 and U.S. Pat. No. 5,470,993.
- CpSA ligand means (t-butylamino) (tetramethylcyclopentadienyl) dimethylsilane.
- CpSA means doubly-deprotonated CpSA ligand.
- (CpSA)2-TiCl 2 means [(t-butylamido) (tetramethylcyclopentadienyl) dimethylsilan]titanium dichloride.
- Activity means generally the quantity of polymer produced under standard conditions by a defined amount of catalyst per unit time.
- catalyst efficiency or activity is based on ethylene consumption in a batch reactor under standard conditions for temperature, solvent, monomer quantities, hydrogen quantities, monomer pressure and run time.
- the activity of the sample catalyst is reported as the percentage of activity of the sample versus the activity of a standard (“standard activity”).
- standard activity is the CGC group 4(II) diene complex from Boulder Scientific Company Batch 459-0140 of 1997.
- Average means the average of two runs with activities MTS which are the same within plus or minus 5%.
- This process involves making reactant slurries 1 and 2 in separate vessels and then combining these slurries for the final reaction.
- Slurry 1 is produced by charging toluene into a vessel and deoxygenating. Then titanium tetrachloride is added, followed by adding n-butyllithium. This addition is very exothermic. The resulting mixture comprising slurry 1 is stirred for 1 hour. This process is illustrated by equation 1);
- Slurry 2 is made up as follows: Toluene and CpSA ligand are charged to a reaction vessel. After adjusting the pot temperature to 45-50° C., a solution of isopropylmagnesium chloride in ethyl ether is fed into the reaction vessel resulting in gas evolution. Gentle heating is used as needed in order to end up with a pot temperature of 45-50° C. at the end of the Grignard feed. The reaction mixture is slowly heated and solvents begin to distill along with increased gas evolution. The reaction mixture is heated up to 85-90° C., and this temperature is maintained for 2 hours. After allowing the reaction mixture to cool to 60-65° C., TiCl 3 is fed into the reaction vessel. The reaction mixture is then cooled to 20-25° C. This becomes known as Slurry 2. This process is illustrated by equations 2) and 3);
- the agitated Slurry 1 is transferred into the reactor containing the agitated Slurry 2 as quickly as possible resulting in about a temperature increase of about 7-15° C. Methylene chloride is then charred to the reaction vessel, the vessel containing Slurry 1 is then rinsed out with toluene and charged to the Slurry 2 reaction vessel, and this mixture is then agitated for 2 hours. A dark reddish-brown color is noted in the reaction vessel as soon as Slurry 1 is introduced. This reaction is illustrated by equation 4):
- Solvents are removed under reduced pressure (60-80 mm Hg) using a rotary vane vacuum pump to about 1 ⁇ 2 of the starting volume. Toluene is added back, Celite is added, and the mixture is filtered through the large sparkler filter. Solvents are then distilled to concentrate the product. The remaining crude product solution is then used directly in the next step.
- Butylmagnesium chloride in TKF is fed into the reactor.
- the reaction is exothermic.
- the reaction mixture is agitated for an additional 1 ⁇ 2 hour at a pot temperature of 35-40° C.
- This mixture is then distillod atmospherically to a pot temperature of 85° C., cooled to 20-25° C., and then vacuum distilled at ⁇ 65° C.
- One drum of deoxgenated hydrocarbon solvent and Celite is added at 20-25° C., and the resulting mixture is filtered through the large 33 inch sparkler. The filter cake is hydrolyzed. The resulting solution is then vacuum distilled at ⁇ 65° C.
- the invention provides ligands of novel constrained geometry Group 4(II) diene complexes and complexes derived therefrom which have an olefin polymerization activity significantly greater than that demonstrated by known complexes of the same type.
- the invention provides complexes of the formula
- a cyclopentadienyl silyl amine is treated with an alkali metal alkyl and thereafter with a dialkyl silyl dihalide to produce cyclopentadienyl silyl amine ligand (CpSA ligand).
- the ligand is treated with a group 4 metal tetrahalide adduct of a linear ether having at least two oxygen atoms and an alkali metal alkyl to produce a dihalide ligand of the ultimately desired group 4(II) complex having the formula:
- the dihalide ligand is treated with a diene and an alkali metal alkyl used in stoichiometric excess.
- Dienes useful in the invention are described in U.S. Pat. Nos. 5,470,993 and 6,015,916.
- the unreacted alkali metal alkyl in the consequent reaction mixture is quenched, for example, by chlorotrimethyl silane.
- the complex so produced is apparently free or substantially so of impurities which may result in undesirable gel formation and impair single site olefin polymerization functionality.
- DME group 4 metal tetrahalide adduct One method for preparing a DME group 4 metal tetrahalide adduct is described in U.S. Pat. No. 6,015,916, Col. 4, II. 61-66. More generally useful adducts are prepared by treating from any compound of formula X.OYO.OX in which X is a C 1 to C 10 alkyl group, and Y is a C 2 to C 10 alkane.
- Any group 4 tetrahalide-ether adduct may be used. Titanium tetrachloride DME adducts are preferred.
- the adduct is preferably prepared in a hydrocarbon solvent.
- the mol ratio of the reactants is preferably about 1:1 with a small excess of the ether reactant.
- the synthesis of the dihalo metallocene ligand is conducted in a non-interfering medium.
- Suitable media include hydrocarbons, preferably a C 5 to C 8 alkane, and mixtures of an alkane and ethyl ether.
- the synthesis may be performed at any effective reaction temperature. A preferred temperature range is from ⁇ 20° C. to 0° C.
- the reaction mixture contains the dihalo ligand in the non-interfering medium. Upon cooling, the dihalo ligand separates from the reaction mixture as a crystalline solid which may be removed by filtration under an inert atmosphere, preferably nitrogen.
- the isolated dihalo ligand may be recrystallized to further reduce impurity content.
- the alkali metal alkyl is used in stoichiometric excess to reduce substantially all of the group 4(IV) dihalo ligand to the group 4(II) finished catalyst and to reduce any other group 4(IV) compounds which may be present in the reaction mixture to group 4(II) compounds or other compounds of minimal adverse affect on the activity or single site functionality of the finished catalyst.
- the excess alkali metal alkyl is quenched, for example, with chlorotrimethyl silane.
- the product is understood to comprise a single site catalyst composite essentially free of group 4(IV) or group 4(III) compounds and other impurities which may adversely affect single site polymerization activity.
- a cyclopentadienyl compound as defined is charged to a vessel.
- THF is added, preferably at a temperature from about ⁇ 20° C. to ⁇ 10° C., depending upon the cyclopentadienyl compound used.
- Dimethyldichlorosilane is fed in at a low temperature of about ⁇ 10° C. to 0° C.
- the vessel is agitated and the contents warmed to room temperature and aluted thereafter.
- the selected alkylamine preferably a C 1 to C 10 alkyl amine, is fed into the vessel at low temperature, e.g., about ⁇ 10° C.
- THP and unreacted amine are removed.
- a slurry may form. If so, heptane or equivalent hydrocarbon media may be added.
- the slurry is filtered.
- the filtrate contains cyclopentadienyl silyl amine ligand (CPSA ligand) of formula:
- Z is a cyclopentadienyl group and R is an alkyl group derived from the alkyl amine reactant.
- the alkali metal alkyl is used in stoichiometric excess to reduce the group 4(IV) ligand to the group 4(II) finished catalyst and to reduce any other group 4(IV) compounds which may be present in the reaction mixture.
- the excess alkali metal alkyl is quenched, preferably with chlorotrimethylsilane.
- the pot temperature of each of the first and second reactors was adjusted to 15-20° C. Thereafter, the contents of the first reactor were transferred to the second reactor with the pot temperature of the second reactor maintained at 20-25° C. The second reactor contents were then agitated for about 12 hours at 25-28° C.
- a reactions mixture containing the dichloride ligand having the formula set forth on page 13 hereof was produced in the second reactor.
- 47.0 kg of deoxygenated heptane was added to the second reactor.
- the second reactor pot temperature was adjusted to ⁇ 15° C.
- 6 kg of piperylene was charged to the second reactor.
- 23.3 kg of EM butyllithium in hexane were fed into the second reactor.
- the pot temperature was maintained between ⁇ 15° C. and ⁇ 10° C.
- the pot temperature was adjusted to 20-25° C. over 1 hour.
- the reaction mixture was agitated for about three hours at 20-25° C.
- TMSCl trimethylsilicon chloride
- the pot temperature of each of the first and second reactors was adjusted to 15-20° C.
- the agitated contents of the first reactor were transferred to the second reactor with the second reactor pot temperature maintained At 20-25° C.
- the contents of the second reactor were agitated for about 12 hours at 20-28° C.
- the reaction mixture in the second reactor contained the dichloride ligand set forth on page 13 hereof. Solvents were stripped from the reaction mixture.
- the pot temperature of the second reactor was adjusted to 15° C. 2.0 kg of piperylene were charged to the reactor, 8.5 kg of 15% butyllithium in hexane were slowly fed into the second reactor temperature maintained between ⁇ 15° C. and ⁇ 10° C. After the feed was completed, the pot temperature was adjusted to 20-25° C. over a 1 hour time period. The reaction mixture was agitated for 3 hours at 20-25° C.
Abstract
Description
- This invention relates to constrained geometry complexes of group 4 metals and dienes characterized by high olefin polymerization activity, to ligands of such complexes and to methods for the production of such complexes and ligands.
- U.S. Pat. No. 5,470,993 describes the synthesis of constrained ; geometry group 4 metal diene complexes by contacting a reduced form of a group 4 metal tetrahalide, a diene and an appropriate dianion ligand of the desired metal complex.
-
-
- The ligand may be any corresponding dihalo compound in which the chlorine substituents are replaced by bromine, iodine or fluorine and in which the “t-bu” substituent is replaced by any alkyl group.
- U.S. Pat. No. 6,015/916 describes the synthesis of similar complexes by treatment of a dihalo ligand of a metallocene compound with an alkali metal alkyl and a diene. The specification of U.S. Pat. No. 6,015,916 is, by express reference, incorporated herein and made a part of this specification.
- German Application DE 197 39 946 A1 describes a metallocene synthesis in which an appropriate ligand is converted to a metallocene by treatment with an adduct of Formula (I)
- M1XnDa
- in which M1 denotes a metal of groups 3, 4, 5 or 6 of the periodic system of elements (PSB) or an element of the group of lanthanides or actinides, preferably titanium, zirconium, or hafnium, by special preference zirconium; X is the same or different, being halogen, a C1-10-alkoxy, C6-10-aryloxy, C1-10-alkylsulfonate such as mesylate, triflate, nonaflate, a C6-10arylsulfonate such as tosylate, benzene sulfonate, a C1-10-alkylcarboxylate such as acetate, formate, oxalate, or a 1,3-dicarbonylate such as acetylacetonate or a fluorinated 1,3-dicarbonylate; n is an integer and equals 2, 3, 4, 5 or 6 and corresponds to the oxidation number of the metal M1; a is an integer or a fraction number and 0<a≦4; and D is a linear, cyclic, or branched oligoether or polyether containing at least two oxygen atoms or an oligoether or polyether containing at least two sulfur atoms.
- There is a need for group 4(II) diene complexes of high catalytic activity in which these disadvantages are reduced or eliminated and for dihalo ligands of such complexes.
- Accordingly, it is an object of this invention to provide novel cyclopentadienyl group 4 metal diene complexes and dihalo ligands or such complexes which provide uniquely active olefin polymerization catalysts.
- It is a related object of the invention to provide cyclopentadienyl group 4 metal diene complex single site polymerization catalysts and catalyst compositions of low impurity content such that the single site functionality thereof is not significantly impaired.
- It is a specific object of the invention to provide a magnesium-free cyclopentadienyl group 4 metal diene complex metallocene.
- The following expressions have the meaning set forth:
- (1) Cyclopentadienyl group means cyclopentadienyl, tetraalkylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
- (2) The expressions group 4(II) and group 4(III) mean a is; group 4 metal of valence 2(II) or 3(III).
- (3) A Group 4(II) metallocene compound is a compound comprised of a group 4(II) metal bonded to one or more cyclopontadienyl groups.
- (4) A Group 4(II) metallocene ligand is a chemical precursor which contains a cyclopentadienyl or substituted cyclopentadienyl group from which a group 4(II) metallocene may a synthesized.
- (5) Constrained geometry compound or catalyst (CGC) means a catalyst in which the metal conter is contained in a ring structure and covalently bonded to a cyclic group via a delocalized n-system and covalently bonded via a sigma-bond to another atom, e.g., carbon, nitrogen, oxygen. A small ring size induces constraint about the metal atom center. For titanium-containing CGCs, the incorporated titanium atom can be in the +4, +3, or +2 formal oxidation state. See EP application 90309496.9, WO 95/00526 and U.S. Pat. No. 5,470,993.
- (6) CpSA ligand means (t-butylamino) (tetramethylcyclopentadienyl) dimethylsilane.
- (7) (CpSA) means doubly-deprotonated CpSA ligand.
- (8) (CpSA)2-TiCl2 means [(t-butylamido) (tetramethylcyclopentadienyl) dimethylsilan]titanium dichloride.
- (9) Activity means generally the quantity of polymer produced under standard conditions by a defined amount of catalyst per unit time.
- As used in this application, catalyst efficiency or activity is based on ethylene consumption in a batch reactor under standard conditions for temperature, solvent, monomer quantities, hydrogen quantities, monomer pressure and run time.
- The activity of the sample catalyst is reported as the percentage of activity of the sample versus the activity of a standard (“standard activity”). For purposes of this application, the “standard” is the CGC group 4(II) diene complex from Boulder Scientific Company Batch 459-0140 of 1997.
-
- “Average” means the average of two runs with activities MTS which are the same within plus or minus 5%.
- Process Description
- This process involves making reactant slurries 1 and 2 in separate vessels and then combining these slurries for the final reaction. Slurry 1 is produced by charging toluene into a vessel and deoxygenating. Then titanium tetrachloride is added, followed by adding n-butyllithium. This addition is very exothermic. The resulting mixture comprising slurry 1 is stirred for 1 hour. This process is illustrated by equation 1);
- Slurry 2 is made up as follows: Toluene and CpSA ligand are charged to a reaction vessel. After adjusting the pot temperature to 45-50° C., a solution of isopropylmagnesium chloride in ethyl ether is fed into the reaction vessel resulting in gas evolution. Gentle heating is used as needed in order to end up with a pot temperature of 45-50° C. at the end of the Grignard feed. The reaction mixture is slowly heated and solvents begin to distill along with increased gas evolution. The reaction mixture is heated up to 85-90° C., and this temperature is maintained for 2 hours. After allowing the reaction mixture to cool to 60-65° C., TiCl3 is fed into the reaction vessel. The reaction mixture is then cooled to 20-25° C. This becomes known as Slurry 2. This process is illustrated by equations 2) and 3);
- The agitated Slurry 1 is transferred into the reactor containing the agitated Slurry 2 as quickly as possible resulting in about a temperature increase of about 7-15° C. Methylene chloride is then charred to the reaction vessel, the vessel containing Slurry 1 is then rinsed out with toluene and charged to the Slurry 2 reaction vessel, and this mixture is then agitated for 2 hours. A dark reddish-brown color is noted in the reaction vessel as soon as Slurry 1 is introduced. This reaction is illustrated by equation 4):
- Solvents are removed under reduced pressure (60-80 mm Hg) using a rotary vane vacuum pump to about ½ of the starting volume. Toluene is added back, Celite is added, and the mixture is filtered through the large sparkler filter. Solvents are then distilled to concentrate the product. The remaining crude product solution is then used directly in the next step.
- Process Description
- The crude product from the previous steps of this process, equations 1) to 4) which is still contained in the reactor used is agitated at a pot temperature of 20-25° C. and piperylene concentrate (1 ,3-pentadiene) is added.
- Butylmagnesium chloride in TKF is fed into the reactor. The reaction is exothermic. When the Grignard feed is done, the reaction mixture is agitated for an additional ½ hour at a pot temperature of 35-40° C.
- This mixture is then distillod atmospherically to a pot temperature of 85° C., cooled to 20-25° C., and then vacuum distilled at ≦65° C. One drum of deoxgenated hydrocarbon solvent and Celite is added at 20-25° C., and the resulting mixture is filtered through the large 33 inch sparkler. The filter cake is hydrolyzed. The resulting solution is then vacuum distilled at ≦65° C.
- Six drums of deoxygenated Isopar are charged to the reactor, 2 drums at a time, and then vacuum distilled at <65° C. to remove THF and toluene. When the solvent concentrations are appropriate, 1 drum of deoxygenated Isopar and Celite are added. The resulting solution is filtered through a precoated small sparkler filter into a cylinder. The filter cake may be discarded. The reaction is illustrated by the following equation 5).
- The invention provides ligands of novel constrained geometry Group 4(II) diene complexes and complexes derived therefrom which have an olefin polymerization activity significantly greater than that demonstrated by known complexes of the same type.
-
- which have an olefin activity substantially in excess of 100%, e.g., at least about 130%, of the aforesaid “standard activity”.
- Pursuant to one aspect of the invention, a cyclopentadienyl silyl amine is treated with an alkali metal alkyl and thereafter with a dialkyl silyl dihalide to produce cyclopentadienyl silyl amine ligand (CpSA ligand). The ligand is treated with a group 4 metal tetrahalide adduct of a linear ether having at least two oxygen atoms and an alkali metal alkyl to produce a dihalide ligand of the ultimately desired group 4(II) complex having the formula:
- The dihalide ligand is treated with a diene and an alkali metal alkyl used in stoichiometric excess. Dienes useful in the invention are described in U.S. Pat. Nos. 5,470,993 and 6,015,916. The unreacted alkali metal alkyl in the consequent reaction mixture is quenched, for example, by chlorotrimethyl silane. The complex so produced is apparently free or substantially so of impurities which may result in undesirable gel formation and impair single site olefin polymerization functionality.
- Various group 4 metal tatrachoride-ether adducts are known. See, generally, U.S. Pat. No. 5,470,993 and published German application DE 197 30 94 A1. Each of top adducts described in these references is useful in this invention. The 1,2-dimethoxyethane (DME) adducts are preferred.
- One method for preparing a DME group 4 metal tetrahalide adduct is described in U.S. Pat. No. 6,015,916, Col. 4, II. 61-66. More generally useful adducts are prepared by treating from any compound of formula X.OYO.OX in which X is a C1 to C10 alkyl group, and Y is a C2 to C10 alkane.
- Any group 4 tetrahalide-ether adduct may be used. Titanium tetrachloride DME adducts are preferred. The adduct is preferably prepared in a hydrocarbon solvent. The mol ratio of the reactants is preferably about 1:1 with a small excess of the ether reactant.
- Any alkali metal alkyl having the formula A—R, in which A may be any alkali metal, preferably lithium, and R is any alkyl group, preferably a C1 to C10 alkyl group, may be used. N-butyllithium is preferred.
- The synthesis of the dihalo metallocene ligand is conducted in a non-interfering medium. Suitable media include hydrocarbons, preferably a C5 to C8 alkane, and mixtures of an alkane and ethyl ether. The synthesis may be performed at any effective reaction temperature. A preferred temperature range is from −20° C. to 0° C. The reaction mixture contains the dihalo ligand in the non-interfering medium. Upon cooling, the dihalo ligand separates from the reaction mixture as a crystalline solid which may be removed by filtration under an inert atmosphere, preferably nitrogen. The isolated dihalo ligand may be recrystallized to further reduce impurity content.
- The alkali metal alkyl is used in stoichiometric excess to reduce substantially all of the group 4(IV) dihalo ligand to the group 4(II) finished catalyst and to reduce any other group 4(IV) compounds which may be present in the reaction mixture to group 4(II) compounds or other compounds of minimal adverse affect on the activity or single site functionality of the finished catalyst. The excess alkali metal alkyl is quenched, for example, with chlorotrimethyl silane. The product is understood to comprise a single site catalyst composite essentially free of group 4(IV) or group 4(III) compounds and other impurities which may adversely affect single site polymerization activity.
- 1. Synthesis of the Cyclopentadienyl Silyl Amine Ligand
- A cyclopentadienyl compound as defined is charged to a vessel. THF is added, preferably at a temperature from about −20° C. to −10° C., depending upon the cyclopentadienyl compound used. Dimethyldichlorosilane is fed in at a low temperature of about −10° C. to 0° C. The vessel is agitated and the contents warmed to room temperature and aluted thereafter. The selected alkylamine, preferably a C1 to C10 alkyl amine, is fed into the vessel at low temperature, e.g., about −10° C. After agitation and warming to room temperature, the vessel is heated, and THP and unreacted amine are removed. A slurry may form. If so, heptane or equivalent hydrocarbon media may be added. The slurry is filtered. The filtrate contains cyclopentadienyl silyl amine ligand (CPSA ligand) of formula:
- in which Z is a cyclopentadienyl group and R is an alkyl group derived from the alkyl amine reactant.
- 2. Preparation of the Dihalo Ligand
- The dihalo ligand may be synthesized in the manner described in U.S. Pat. No. 6,015,916, Col. 3, I. 60, part (2). In general, the cyclopentadienyl silyl amine may be treated with an unreduced group 4 tetrachloride, preferably in the form of a DME or equivalent adduct in a hydrocarbon solvent. The Ti(IV) of the dihalo intermediate is converted to Ti(II) in the final complex by treatment with an alkali metal alkyl as described, preferably butyllithium, and a diene in a non-interfering, preferably hydrocarbon, medium at a preferred temperature of −10° C. to 0° C. The alkali metal alkyl is used in stoichiometric excess to reduce the group 4(IV) ligand to the group 4(II) finished catalyst and to reduce any other group 4(IV) compounds which may be present in the reaction mixture. The excess alkali metal alkyl is quenched, preferably with chlorotrimethylsilane.
- All apparatus used in this example were clean, dry and nitrogen-purged. Presence of THEF was precluded.
- 21.2 kg of ethyl ether and 6.5 kg of CpSA ligand (assumed 95% purity) were charged into a first reactor. The pot temperature was reduced to −20° C.
- 21.2 kg of 15% n-butyllithium in hexane was slowly added with the pot temperature maintained between −20° C. and −10° C. After the feed was completed, the pot temperature was raised to 20° C. over 1 hour, and the pot contents were agitated for 4 hours at 20-25° C. A reaction mixture containing a CpSA dilithio salt was produced.
- 34.2 kg of deoxygenated heptane and 2.6 kg of dimethoxyethane were charged into a second reactor. The pot temperature was adjusted to about 10-15° C.
- 4.8 kg of titanium tetrachloride were charged to the second reactor at a pot temperature of between 15° C. and 30° C. Upon completion of the feed, the speed of agitation of the second reactor contents was increased. Agitation continued for about 3 hours at a pot temperature of 20-25° C.
- The pot temperature of each of the first and second reactors was adjusted to 15-20° C. Thereafter, the contents of the first reactor were transferred to the second reactor with the pot temperature of the second reactor maintained at 20-25° C. The second reactor contents were then agitated for about 12 hours at 25-28° C.
- A reactions mixture containing the dichloride ligand having the formula set forth on page 13 hereof was produced in the second reactor. After solvent stripping, 47.0 kg of deoxygenated heptane was added to the second reactor. The second reactor pot temperature was adjusted to −15° C. Thereafter, 6 kg of piperylene was charged to the second reactor. 23.3 kg of EM butyllithium in hexane were fed into the second reactor. During this feed, the pot temperature was maintained between −15° C. and −10° C. Upon completion of the food, the pot temperature was adjusted to 20-25° C. over 1 hour. The reaction mixture was agitated for about three hours at 20-25° C.
- 1.5 kg of trimethylsilicon chloride (TMSCl) was added. The pot temperature was adjusted to 40-45° C. with agitation for 2 hours. Thereafter, the pot temperature was adjusted to 20-25° C., and the reaction mixture was filtered. The cake comprising CGC-7 was rinsed with deoxygenated heptane.
- Theory yield—9.1 Kg contained
- Actual yield—7.454 Kg contained.
- Activity (determined as described above)—170%.
- All apparatus used in this example were clean, dry and nitrogen-purged. Presence of THF was precluded.
- 8.5 kg of ethyl ether and 2.6 kg of CpSA ligand (95% purity assumed) were charged into a clean, Isopar-rinsed, nitrogen-purged first reactor. The pot temperature was −20° C.
- 13.7 kg of deoxygenated Isopar E and 1.0 kg of dimethoxymethane were charged into a dry, nitrogen-purged second reactor. The pot temperature was adjusted to 10-15° C.
- 1.9 kg of titanium tetrachloride were fed into the second reactor with slow agitation of the reactor contents and with the pot temperature maintained between 15° C. and 30° C. Upon completion of the feed, the agitation was increased, and the contents of the second reactor were agitated for about 3 hours at 20-25° C.
- The pot temperature of each of the first and second reactors was adjusted to 15-20° C. The agitated contents of the first reactor were transferred to the second reactor with the second reactor pot temperature maintained At 20-25° C. The contents of the second reactor were agitated for about 12 hours at 20-28° C. The reaction mixture in the second reactor contained the dichloride ligand set forth on page 13 hereof. Solvents were stripped from the reaction mixture.
- The pot temperature of the second reactor was adjusted to 15° C. 2.0 kg of piperylene were charged to the reactor, 8.5 kg of 15% butyllithium in hexane were slowly fed into the second reactor temperature maintained between −15° C. and −10° C. After the feed was completed, the pot temperature was adjusted to 20-25° C. over a 1 hour time period. The reaction mixture was agitated for 3 hours at 20-25° C.
- 600 g of TMSCl were added, and the reaction mixture was agitated for 1 hour. The reaction mixture which contained the desired group 4(II) diene complex was filtered, and the cake was rinsed with deoxygenated Isopar.
- Theory yield of CGC-7 (contained)—3.65 kg.
- Actual yield of CGC-7 (contained)—2.59 (71% yield)
- Activity (as determined in the manner described above)—140%.
- Synthesis procedures substantially as described in Examples 1 and 2 yielded Group 4(II) diene complex products having activities, when determined as described above, of 165% and 130%.
Claims (6)
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JP2002557949A JP2004517899A (en) | 2001-01-17 | 2002-01-16 | Geometrically constrained ligands and complexes derived from them |
CA002402622A CA2402622A1 (en) | 2001-01-17 | 2002-01-16 | Constrained geometry ligands and complexes derived therefrom |
PCT/US2002/001421 WO2002057272A2 (en) | 2001-01-17 | 2002-01-16 | Constrained geometry ligands and complexes derived therefrom |
EP02723060A EP1303524A4 (en) | 2001-01-17 | 2002-01-16 | Constrained geometry ligands and complexes derived therefrom |
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US5470993A (en) * | 1993-06-24 | 1995-11-28 | The Dow Chemical Company | Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom |
US5512693A (en) * | 1994-12-07 | 1996-04-30 | The Dow Chemical Company | Preparation of titanium (II) or zirconium (II) complexes |
US5491246A (en) * | 1995-04-24 | 1996-02-13 | The Dow Chemical Company | Synthesis of group 4 metal diene complexes |
US5688880A (en) * | 1995-12-11 | 1997-11-18 | The Dow Chemical Company | Readily supportable metal complexes |
DE19739946A1 (en) * | 1997-09-11 | 1999-03-18 | Targor Gmbh | Process for the production of metallocenes |
US6015916A (en) * | 1999-02-02 | 2000-01-18 | Boulder Scientific Company | Constrained geometry metallocene catalyst complexes |
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