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US5441920A
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Silicon-bridged transition metal compounds
Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1993-12-02
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Granted: 1995-08-15
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Expires: 2013-12-02
Abstract
Abstract Silicon-bridged transition metal compounds and their use as alpha-olefin polymerization catalysts are disclosed. The polymerization catalyst comprises a chiral silicon-bridged metallocene of the following structure: ##STR1## where M is a transition metal, X' and X" are the same or different hydride, halogen, hydrocarbyl or halohydrocarbyl groups having up to about 6 carbon atoms, A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene, and oxasilaalkylene, and may include an alumoxane. Specifically, the transition metals are titanium, zirconium, and hafnium.
Inventors
- 👤 Howard C. Welborn, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 19:10
CPC Classifications
C; C07; C07F; C07F17/00; C08; C08F; C08F10/00; C08F2420/00; C08F2420/09; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65912; C08F4/65916; C08F4/6592; C08F4/65922; C08F4/65927
Claims Analysis
Total Claims: 43
Claim 1
Independent Claim
99 words
A method for producing a compound represented by the formula: ##STR7## wherein M' is a Group IVB transition metal; X' and X" are the same or different hydride, halogen, or hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene, and oxasilaalkylene, a) combining: i) a bridged bis-(substituted cyclopentadienide) dialkali metal compound; and ii) a transition metal halide, and b) recovering the represented stereorigid chiral compound.
Claim 2
Independent Claim
99 words
A method for producing a compound represented by the formula: ##STR7## wherein M' is a Group IVB transition metal; X' and X" are the same or different hydride, halogen, or hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene, and oxasilaalkylene, a) combining: i) a bridged bis-(substituted cyclopentadienide) dialkali metal compound; and ii) a transition metal halide, and b) recovering the represented stereorigid chiral compound.
Claim 3
Dependent Claim
144 words
A process for the preparation of a chiral, stereo-rigid metallocene compound of the formula I [R.sup.1 R.sup.2 Si(indenyl).sub.2 ]Y.sup.2 X.sub.2 in which R 1 and R 2 are identical or different and denote a selection from the group consisting of silanylene, silaalkylene, oxasilanylene, and ocasilaalkylene, Y 2 is titanium, zirconium or hafnium, and X denotes a halogen atom, which comprises reacting a compound of formula II [R.sup.1 R.sup.2 Si(indenyl).sub.2 ]Y.sub.2.sup.1 in which R 1 and R 2 have the above mentioned meaning and Y 1 is an alkali metal, with a compound of the formula III Y.sup.2 X.sub.4 in which Y 2 and X have the above mentioned meaning, at a temperature of from -78° C. to 25° C. in an inert solvent for a reaction time ranging from 10 to 1000 minutes, and recovering said compound of formula I from the inert solvent.
Claim 4
Dependent Claim
144 words
A process for the preparation of a chiral, stereo-rigid metallocene compound of the formula I [R.sup.1 R.sup.2 Si(indenyl).sub.2 ]Y.sup.2 X.sub.2 in which R 1 and R 2 are identical or different and denote a selection from the group consisting of silanylene, silaalkylene, oxasilanylene, and ocasilaalkylene, Y 2 is titanium, zirconium or hafnium, and X denotes a halogen atom, which comprises reacting a compound of formula II [R.sup.1 R.sup.2 Si(indenyl).sub.2 ]Y.sub.2.sup.1 in which R 1 and R 2 have the above mentioned meaning and Y 1 is an alkali metal, with a compound of the formula III Y.sup.2 X.sub.4 in which Y 2 and X have the above mentioned meaning, at a temperature of from -78° C. to 25° C. in an inert solvent for a reaction time ranging from 10 to 1000 minutes, and recovering said compound of formula I from the inert solvent.
Claim 5
Dependent Claim
83 words
A catalyst system for the polymerization of olefins, comprising, as a component, a transition metal compound represented by the formula: ##STR8## wherein M' is a transition metal; X' and X" are the same of different hydride, halogen, hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene.
Claim 6
Dependent Claim
83 words
A catalyst system for the polymerization of olefins, comprising, as a component, a transition metal compound represented by the formula: ##STR8## wherein M' is a transition metal; X' and X" are the same of different hydride, halogen, hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene.
Claim 7
Dependent Claim
93 words
A catalyst system, at least one component of which is on a support, for the polymerization of olefins, comprising, as a component, a transition metal compound represented by the formula: ##STR9## wherein M' is a transition metal; X' and X" are the same or different hydride, halogen, hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene.
Claim 8
Dependent Claim
93 words
A catalyst system, at least one component of which is on a support, for the polymerization of olefins, comprising, as a component, a transition metal compound represented by the formula: ##STR9## wherein M' is a transition metal; X' and X" are the same or different hydride, halogen, hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene.
Claim 9
Dependent Claim
84 words
A catalyst system for the polymerization of olefins, comprising: (a) A transition metal compound represented by the formula: ##STR10## wherein M' is a transition metal; X' and X" are the same or different hydride, halogen, hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene; and (b) alumoxane.
Claim 10
Dependent Claim
84 words
A catalyst system for the polymerization of olefins, comprising: (a) A transition metal compound represented by the formula: ##STR10## wherein M' is a transition metal; X' and X" are the same or different hydride, halogen, hydrocarbyl or halohydrocarbyl having up to about 6 carbon atoms; A' and A" are each the same or different asymmetrical mononuclear or polynuclear hydrocarbyl or silahydrocarbyl moieties; and S' is a bridge of 1-4 atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene; and (b) alumoxane.
Claim 11
Dependent Claim
13 words
The catalyst system of claim 5, wherein M' is titanium, zirconium, or hafnium.
Claim 12
Dependent Claim
16 words
The catalyst system of claim 5, wherein X' and X" are independently chlorine, bromine, or iodine.
Claim 13
Dependent Claim
19 words
The catalyst system of claim 5, wherein X' and X" are independently alkyl or haloalkyl of 1-6 carbon atoms.
Claim 14
Dependent Claim
57 words
The catalyst system of claim 5, wherein A' and A" are represented by the formula: ##STR11## wherein n is an integer of from 1 to 4 and each R' is the same or different hydrocarbyl or silahydrocarbyl of 1-20 carbon atoms or taken together, two or more of R' are hydrocarbylene or silahydrocarbylene of 1-20 carbon atoms.
Claim 15
Dependent Claim
19 words
The catalyst system of claim 5, wherein each silicon atom is disubstituted with the same or different lower hydrocarbyl.
Claim 16
Dependent Claim
9 words
The catalyst system of claim 5 in racemic mixture.
Claim 17
Dependent Claim
150 words
A catalyst system for the polymerization of olefins; comprising: A. A chiral transition metal compound substantially free of achiral forms thereof, said compound having the formula: ##STR12## wherein M' is titanium, zirconium or hafnium; X' and X" are the same or different hydride, chlorine, bromine, iodine, or 1-6 carbon-atom alkyl, haloalkyl, aryl, or haloaryl; n and m are the same or different integers from 1 to 4; R' and R" are the same or different hydrocarbyl or silahydrocarbyl of 1-20 carbon atoms, and 0-2 silicon atoms, or taken together, two or more of R' or of R" are hydrocarbylene or silahydrocarbylene of 1-20 carbon atoms and 0-2 silicon atoms; and S' is a chain of 0-4 carbon atoms and 1-2 silicon atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene, in which each silicon atom is disubstituted with the same or different lower hydrocarbyl, and B. alumoxane.
Claim 18
Dependent Claim
150 words
A catalyst system for the polymerization of olefins; comprising: A. A chiral transition metal compound substantially free of achiral forms thereof, said compound having the formula: ##STR12## wherein M' is titanium, zirconium or hafnium; X' and X" are the same or different hydride, chlorine, bromine, iodine, or 1-6 carbon-atom alkyl, haloalkyl, aryl, or haloaryl; n and m are the same or different integers from 1 to 4; R' and R" are the same or different hydrocarbyl or silahydrocarbyl of 1-20 carbon atoms, and 0-2 silicon atoms, or taken together, two or more of R' or of R" are hydrocarbylene or silahydrocarbylene of 1-20 carbon atoms and 0-2 silicon atoms; and S' is a chain of 0-4 carbon atoms and 1-2 silicon atoms selected from the group consisting of silanylene, silaalkylene, oxasilanylene and oxasilaalkylene, in which each silicon atom is disubstituted with the same or different lower hydrocarbyl, and B. alumoxane.
Claim 19
Dependent Claim
10 words
The catalyst system of claim 12, wherein M' is titanium.
Claim 20
Dependent Claim
12 words
The catalyst system of claim 12, wherein X' and X" are chlorine.
Claim 21
Dependent Claim
17 words
The catalyst system of claim 12, wherein R' and R" are butylene, butadienylene, methyl, isobutyl or trimethylsilanyl.
Claim 22
Dependent Claim
23 words
The catalyst system of claim 12, wherein S' is dialkylsilanylene, 1-sila-1,1-dialkyl ethylene, tetraalkyldisilanylene, 2-sila-2,2-dialkyl propylene, 1,3-disila-1,1,3,3-tetraalkyl propylene, dialkylsiloxy (dialkyl) silanylene or 1,4-disila-1,1,4,4-tetraalkyl butylene.
Claim 23
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-dimethylsilanylene-bis(3methylcyclopentadienyl)] zirconium dichloride.
Claim 24
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-dimethylsilanylene-bis(indenyl)] zirconium dichloride.
Claim 25
Dependent Claim
17 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-dimethylsilanylene-bis(4,5,6, 7-tetrahydroindenyl)] zirconium dichloride.
Claim 26
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(3-methylcyclopentadienyl)] zirconium dichloride.
Claim 27
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)] zirconium dichloride.
Claim 28
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)] zirconium dichloride.
Claim 29
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(3-trimethylsilanylcyclopentadienyl)] zirconium dichloride.
Claim 30
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,3,3-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)] zirconium dichloride.
Claim 31
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)] zirconium dichloride.
Claim 32
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)] zirconium dichloride.
Claim 33
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-dimethylsilanylene-bis(3-methylcyclopentadienyl)] hafnium dichloride.
Claim 34
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-Odimethylsilanylene-bis(indenyl)] hafnium dichloride.
Claim 35
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)] hafnium dichloride.
Claim 36
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(3-methylcyclopentadienyl)] hafnium dichloride.
Claim 37
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)] hafnium dichloride.
Claim 38
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)] hafnium dichloride.
Claim 39
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(3-trimethylsilanylcyclopentadienyl)] hafnium dichloride.
Claim 40
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)] hafnium dichloride.
Claim 41
Dependent Claim
16 words
The catalyst system of claim 12, wherein the transition metal compound is racemic [1,1'-(1,1,2.2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)] hafnium dichloride.
Claim 42
Dependent Claim
16 words
The catalyst system in accordance with claim 5 which further comprises an inorganic oxide porous support.
Claim 43
Dependent Claim
16 words
The catalyst system in accordance with claim 12 which further comprises an inorganic oxide porous support.
References Cited (Backward Citations)
EP0129368B1
Cited
US4794096A
Cited
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