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Patent US5057475 - Mono-Cp heteroatom containing group IVB transition metal complexes with MAO ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe invention is a supported catalyst system including an inert support material, a Group IV B transition metal component and an alumoxane component which may be employed to polymerize olefins to produce a high molecular weight polymer....http://www.google.com/patents/US5057475?utm_source=gb-gplus-sharePatent US5057475 - Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerizationAdvanced Patent SearchPublication numberUS5057475 APublication typeGrantApplication numberUS 07/581,869Publication dateOct 15, 1991Filing dateSep 13, 1990Priority dateSep 13, 1989Fee statusPaidAlso published asCA2090972A1, CA2090972C, DE69116157D1, DE69116157T2, DE69116157T3, EP0548257A1, EP0548257B1, EP0548257B2, WO1992005203A1Publication number07581869, 581869, US 5057475 A, US 5057475A, US-A-5057475, US5057475 A, US5057475AInventorsJo Ann M. Canich, Gary F. LicciardiOriginal AssigneeExxon Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (2), Referenced by (493), Classifications (50), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetMono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization
US 5057475 AAbstract
The invention is a supported catalyst system including an inert support material, a Group IV B transition metal component and an alumoxane component which may be employed to polymerize olefins to produce a high molecular weight polymer.
1. A catalyst system comprising:(A) an inert support; (B) a transition metal compound of the formula: ##STR7## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C5 H5 -y-x Rx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals; substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing a Lewis acidic or basic functionality; C1 -C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality; or (C5 H5-Y-x Rx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C4 -C2 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR'z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, each R' is, independently a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals; substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing a Lewis acidic or basic functionality; and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand provided that where Q is a hydrocarbyl ligand such Q is different from (C5 H5-y-x Rx) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and (C) an alumoxane. 2. The catalyst system of claim 1 wherein the heteroatom ligand group J element is nitrogen, phosphorous, oxygen or sulfur.
3. The catalyst system of claim 1 wherein Q is a halogen or hydrocarbyl radical.
4. The catalyst system of claim 2 wherein the heteroatom ligand group J element is nitrogen.
5. The catalyst system of claim 1 wherein M is titanium or zirconium.
6. The catalyst system of claim 1 wherein the aluminum atom to transition metal atom mole ratio is from about 10:1 to about 1,000:1.
7. The catalyst system of claim 1 wherein the support is an inorganic support selected from the group consisting of talc, silica, alumina, silica-alumina, magnesia, titania, zirconia, or mixtures thereof.
8. The catalyst system of claim 7, wherein said support is dehydrated.
9. The catalyst system of claim 8, wherein said support is treated with an alumoxane or a trialkylaluminum.
10. The catalyst system of claim 9, wherein said support is dehydrated silica treated with methylalumoxane or triethylaluminum.
11. The catalyst system of claim 1 further comprising a modifier compound containing a Lewis acidic or basic functionality.
12. The catalyst system of claim 2, further comprising a modifier compound containing a Lewis acidic or basic functionality.
13. The catalyst system of claim 12, wherein the aluminum atom to transition metal atom mole ratio is about 10:1 to about 20,000:1.
14. The catalyst system of claim 13, wherein the aluminum atoms to molecules of modifier compound ratio is from about 1:1 to about 20,000:1.
15. The catalyst system of claim 14, wherein the modifier compound is tetraethoxysilane.
16. The catalyst system of claim 1, wherein the alumoxane is formed on the support by reaction of a hydrated support with a trialkylaluminum.
17. The catalyst system of claim 16, wherein the hydrated support is an inorganic oxide selected from the group consisting of talc, silica, alumina, silica-alumina, magnesia, titania, zirconia, or mixtures thereof.
18. The catalyst system of claim 17, wherein the hydrated support is silica containing from about 6 to about 20 weight percent water and is reacted with trimethylaluminum.
19. A process for producing a supported catalyst system comprising the steps of:dissolving in a hydrocarbon solvent a Group IV B transition metal component of the formula: ##STR8## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C5 H5-Y-x Rx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals, substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; C1 -C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality; or (C5 H5-y-x Rx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C4 -C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR'z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, each R' is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals; substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand provided that where Q is a hydrocarbyl ligand such Q is different from (C5 H5-y-x Rx) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and mixing with the dissolved transition metal component an alumoxane and an inert support material; and recovering from the mixture a supported catalyst. 20. The process of claim 19, further comprising adding a modifier compound containing a Lewis acidic or basic functionality during the mixing of the dissolved transition metal component with the alumoxane and inert support.
21. A process for producing a supported catalyst system comprising the steps of:dissolving an alumoxane in a hydrocarbon solvent; mixing the alumoxane with an inert support material; adding to the mixture of alumoxane and support material, a Group IV B transition metal component of the formula: ##STR9## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C5 H5-y-x Rx) is a cyclopentadienyl ring which is substituted with from zero to five substitutent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radials; substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; C1 -C20 hydrocarbyl-substituted metalloid radicals wherein metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality, or (C5 H5-Y-x Rx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C4 -C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR'z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, each R' is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals; substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality, and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand, provided that where Q is a hydrocarbyl ligand such Q is different from (C5 H5-y-x Rx) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and recovering from the mixture a supported catalyst. Description
This application is a Continuation-in-Part of U.S. patent application Ser. No. 533,245 filed June 4, 1990 which in turn is a continuation-in-part of U.S. patent application Ser. No. 406,945 filed Sept. 13, 1989 and now abandoned.
This invention relates to a supported catalyst system comprising an inert support, a monocyclopentadienyl Group IV B transition metal compound and an alumoxane, and to a process using such supported catalyst system for the production of high molecular weight polyolefins, particularly polyethylene and higher poly-α-olefins, and copolymers of ethylene and/or α-olefins with other unsaturated monomers, including diolefins, acetylenically unsaturated monomers and cyclic olefins. The supported catalyst system is highly active at low ratios of aluminum to the Group IV B transition metal, hence catalyzes the production of a polyolefin product containing low levels of catalyst metal residue.
As is well known, various processes and catalysts exist for the homopolymerization or copolymerization of olefins. For many applications it is of primary importance for a polyolefin to have a high weight average molecular weight while having a relatively narrow molecular weight distribution. A high weight average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-α-olefin copolymer with high strength properties.
Traditional Ziegler-Natta catalysts system--a transition metal compound cocatalyzed by an aluminum alkyl--are capable of producing polyolefins having a high molecular weight but a broad molecular weight distribution.
More recently a catalyst system has been developed wherein the transition metal compound has two or more cyclopentadienyl ring ligands--such transition metal compound being referred to as a metallocene--which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of a Group IV B metal, particularly, titanocenes and zirconocenes, have been utilized as the transition metal component in such "metallocene" containing catalyst system for the production of polyolefins and ethylene-α-olefin copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl--as is the case with a traditional type Ziegler-Natta catalyst system--the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.
It has since become known that such metallocenes may be cocatalyzed with an alumoxane--rather than an aluminum alkyl--to provide a metallocene catalyst system of high activity for the production of polyolefins.
The zirconium metallocene species, as cocatalyzed or activated with an alumoxane, are commonly more active than their hafnium or titanium analogues for the polymerization of ethylene alone or together with an α-olefin comonomer. When employed in a non-supported form--i.e., as a homogeneous or soluble catalyst system--to obtain a satisfactory rate of productivity even with the most active zirconium species of metallocene typically requires the use of a quantity of alumoxane activator sufficient to provide an aluminum atom to transition metal atom ratio (Al:TM) of at least greater than 1000:1; often greater than 5000:1, and frequently on the order of 10,000:1. Such quantities of alumoxane impart to a polymer produced with such catalyst system an undesirable content of catalyst metal residue, i.e., an undesirable "ash" content (the nonvolatile metal content). In high pressure polymerization procedures using soluble catalyst systems wherein the reactor pressure exceeds about 500 bar only the zirconium or hafnium species of metallocenes may be used. Titanium species of metallocenes are generally unstable at such high pressures unless deposited upon a catalyst support.
A wide variety of Group IV B transition metal compounds have been named as possible candidates for an alumoxane cocatalyzed catalyst system. Although bis(cyclopentadienyl) Group IV B transition metal compounds have been the most preferred and heavily investigated for use in alumoxane activated catalyst systems for polyolefin production, suggestions have appeared that mono and tris(cyclopentadienyl) transition metal compounds may also be useful. See, for example U.S. Pat. Nos. 4,522,982; 4,530,914 and 4,701,431. Such mono(cyclopentadienyl) transition metal compounds as have heretofore been suggested as candidates for an alumoxane activated catalyst system are mono(cyclopentadienyl) transition metal trihalides and trialkyls.
More recently, International Publication No. WO 87/03887 describes the use of a composition comprising a transition metal coordinated to at least one cyclopentadienyl and at least one heteroatom ligand as a transition metal component for use in an alumoxane activated catalyst system for α-olefin polymerization. The composition is broadly defined as a transition metal, preferably of Group IV B of the Periodic Table, which is coordinated with at least one cyclopentadienyl ligand and one to three heteroatom ligands, the balance of the transition metal coordination requirement being satisfied with cyclopentadienyl or hydrocarbyl ligands. Catalyst systems described by this reference are illustrated solely with reference to transition metal compounds which are metallocenes, i.e., bis(cyclopentadienyl) Group IV B transition metal compounds.
Even more recently, at the Third Chemical Congress of North American held in Toronto, Canada in June 1988, John Bercaw reported upon efforts to use a compound of a Group III B transition metal coordinated to a single cyclopentadienyl heteroatom bridged ligand as a catalyst system for the polymerization of olefins. Although some catalytic activity was observed under the conditions employed, the degree of activity and the properties observed in the resulting polymer product were discouraging of a belief that such monocyclopentadienyl transition metal compound could be usefully employed for commercial polymerization processes.
The new metallocene catalyst of the copending application is, however, a homogeneous catalyst and generally cannot be practically used for gas phase polymerization. The use of a supported catalyst offers the possibility of gas phase compatibility. Control of the particle size distribution of the polymeric product in the various polymerization processes eliminates or reduces the extent of reactor fouling.
Supported catalysts for olefin polymerization are well known in the art. These catalysts offer, among others, the advantages of being usable in gas or slurry phase reactors allowing the control of polymer particle size and thereby the control of product bulk density. Gas phase reactors also eliminate the need for a solvent and the equipment for solvent handling and separation. However, the known Ziegler-Natta olefin polymerization supported catalysts also present disadvantages which include broad MWD and composition distribution (CD), inefficient incorporation of comonomers, poor sequence distribution and, in the case of lower activity catalysts, the need for a product deashing step.
Supported metallocene-alumoxane catalysts for olefin polymerization are described in U.S. Pat. No. 4,701,432 of Welborn. These supported metallocene-alumoxane catalysts are obtained by reacting a metallocene and an alumoxane in the presence of the solid support material. The supported catalyst may then be employed either as the sole catalyst component or may be employed in combination with an organometallic cocatalyst. The supported metallocene-alumoxane catalyst, however, still produced polymers of generally lower molecular weight and comonomer incorporation than desired for certain applications.
A need still exists for discovering catalyst systems that permit the production of higher molecular weight polyolefins and desirably with a narrow molecular weight distribution. It is also desirable that a catalyst be discovered which, within reasonable ranges of ethylene to α-olefin monomer ratios, will catalyze the incorporation of higher contents of α-olefin comonomers in the production of ethylene-α-olefins copolymers. It is highly desirable that such a catalyst system be available and active in a supported form for process applications which require a supported catalyst, such as gas phase polymerization processes and certain slurry polymerization processes, and for purposes of reducing metal residue left in the final product.
The supported catalyst system of this invention comprises an inert support, a transition metal component from the Group IV B of the Periodic Table of the Elements, CRC Handbook of Chemistry and Physics, 68th ed. 1987-1988) and an alumoxane component which may be employed in solution, slurry, gas-phase, or bulk phase polymerization procedures, or combinations thereof, to produce a polyolefin of high average molecular weight and relatively narrow molecular weight distribution.
The "Group IV B transition metal component" of the catalyst system is represented by the formula: ##STR1## wherein: M is Zr, Hf or Ti in its highest formal oxidation state (+4, d0 complex);
(C2 H5-y-x Rx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals, substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, alkylborido radicals, or any other radical containing a Lewis acidic or basic functionality, C1 -C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing a Lewis acidic or basic functionality, or (C5 H5 -y-xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C4 -C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
(JR'z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur, and each R' is, independently a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals, substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, or any other radical containing a Lewis acidic or basic functionality, and "z" is the coordination number of the element J;
each Q may be independently any univalent anionic ligand such as a halide, hydride, or substituted or unsubstituted C1 -C20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q is a hydrocarbyl such Q is different from (C5 H5-y-x Rx), or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand;
"y" is 0 or 1 when w is greater than 0; y is 1 when w is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like;
L is a neutral Lewis base such as diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and "w" is a number from 0 to 3. L can also be a second transition metal compound of the same type such that the two metal centers M and M' are bridged by Q and Q', wherein M' has the same meaning as M and Q' has the same meaning as Q. Such dimeric compounds are represented by the formula: ##STR2## The alumoxane component of the catalyst may be represented by the formulas: (R3 -Al-O)m; R4 (R5 -Al-O)mAlR6 or mixtures thereof, wherein R3 -R6 are, independently, a C1 -C5 alkyl group or halide and "m" is an integer ranging from 1 to about 50 and preferably is from about 13 to about 25.
The inert support component may be any finely divided solid porous support, including, but not limited to inorganic oxides such as talc, silica, alumina, silica-alumina, or resinous support materials such as polyolefins or mixtures thereof.
Supported catalyst systems of the invention may be prepared by several methods. The "Group IV B transition metal component" and the alumoxane component can be mixed together before the addition of the support material, or the mixture can be added to the support material. The mixture may be prepared in common solution in a normally liquid alkane or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the slurry or bulk phase polymerization of an olefin monomer. Alternatively, the alumoxane can be placed on the support material followed by the addition of the transition metal component or conversely, the transition metal may be applied to the support material followed by the addition of the alumoxane. The alumoxane can be used as commercially supplied, or may be generated in situ on the solid support, for example, by the addition of a trialkylaluminium to a wet support, for example by the addition of trimethylaluminum to wet silica. The supported catalyst may be prepolymerized. In addition, third components can be added in any stage of the preparation of the supported catalyst. Third components can be defined as compounds containing Lewis acidic or basic functionalities exemplified but not limited to compounds such as N,N-dimethylanaline, tetraethoxysilane, phenyltriethoxysilane, bis-tert-butylhydroxy toluene (BHT) and the like.
Those species of the Group IV B transition metal component wherein the metal is titanium have been found to impart beneficial properties to a catalyst system which are unexpected in view of what is known about the properties of bis(cyclopentadienyl) titanium compounds which are cocatalyzed by alumoxanes. Whereas titanocenes in their soluble form are generally unstable in the presence of aluminum alkyls, the monocyclopentadienyl titanium metal components of this invention, particularly those wherein the heteroatom is nitrogen, generally exhibit greater stability in the presence of aluminum alkyls, higher catalyst activity rates and higher α-olefin comonomer incorporation.
Further, the titanium species of the Group IV B transition metal component catalyst of this invention generally produce polymers of greater molecular weight and of higher α-olefin comonomer content than catalyst systems prepared with the zirconium species of the Group IV B transition metal component.
A typical polymerization process of the invention such as for the polymerization or copolymerization of ethylene comprises the steps of contacting ethylene or C3 -C20 α-olefins alone, or with other unsaturated monomers including C3 -C20 α-olefins, C5 -C20 diolefins, and/or acetylenically unsaturated monomers either alone or in combination with other olefins and/or other unsaturated monomers, with a supported catalyst comprising, an inert support material, the Group IV B transition metal component illustrated above; and a methylalumoxane in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1 or more; and reacting such monomer in the presence of such supported catalyst system at a temperature of from about -100� C. to about 300� C. for a time of from about 1 second to about 10 hours to produce a polyolefin having a weight average molecular weight of from about 1,000 or less to about 5,000,000 or more and a molecular weight distribution of from about 1.5 to about 15.0.
The Group IV B transition metal component of the catalyst system is represented by the general formula: ##STR3## wherein M is Zr, Hf or Ti in its highest formal oxidation state (+4, d0 complex);
(C5 H5-y-x Rx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals, substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkyborido radical, or any other radical containing a Lewis acidic or basic functionality, C1 -C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or any other radical containing a Lewis acidic or basic functionality, or (C5 H5-y-x Rx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C4 -C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
(JR'z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen being preferred, and each R' is, independently a radical selected from a group consisting of C1 -C20 hydrocarbyl radicals, substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or any other radical containing a Lewis acidic or basic functionality, and "z" is the coordination number of the element J;
each Q is, independently, any univalent anionic ligand such as a halide, hydride, or substituted or unsubstituted C1 -C20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q is a hydrocarbyl such Q is different from (C5 H5-y-x Rx), or both Q together may be an alkylidene or a cyclometallated e or any other divalent anionic chelating ligand;
"y" is 0 or 1 when w is greater than 0, and y is 1 when w equals 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like; and
L is a neutral Lewis base such as diethylether, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and "w" is a number from 0 to 3; L can also be a second transition metal compound of the same type such that the two metal centers M and M' are bridged by Q and Q', wherein M' has the same meaning as M and Q' has the same meaning as Q. Such compounds are represented by the formula: ##STR4##
Examples of the T group which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in column 1 of Table 1 under the heading "T".
Exemplary hydrocarbyl radicals for Q are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl being preferred. Exemplary halogen atoms for Q include chlorine, bromine, fluorine and iodine, with chlorine being preferred. Exemplary alkoxides and aryloxides for Q are methoxide, phenoxide and substituted phenoxides such as 4-methylphenoxide. Exemplary amides of Q are dimethylamide, diethylamide, methylethylamide, di-t-butylamide, diisoproylamide and the like. Exemplary aryl amides are diphenylamide and any other substituted phenyl amides. Exemplary phosphides of Q are diphenylphosphide, dicyclohexylphosphide, diethylphosphide, dimethylphosphide and the like. Exemplary alkyldiene radicals for both Q together are methylidene, ethylidene and propylidene. Examples of the Q group which are suitable as a constituent group or element of the Group IV B transition metal component of the catalyst system are identified in column 4 of Table 1 under the heading "Q".
Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, will contain from 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals, alkyl-substituted aromatic radicals, amido-substituted hydrocarbyl radicals, phosphido-substituted hydrocarbyl radicals, and alkoxy-substituted hydrocarbyl radicals and cyclopentadienyl rings containing one or more fused saturated or unsaturated rings. Suitable organometallic radicals, which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like. Other suitable radicals that may be substituted for one or more hydrogen atoms in the cyclopentadienyl ring include halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylboride radicals, and the like. Examples of cyclopentadienyl ring groups (C5 H5-y-x Rx) Which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column 2 of Table 1 under the heading (C5 H5-y-x Rx).
Syuitable R' radicals o the heteroatom J ligand are independently a hydrocarbyl radical selected from a group consisting of 1 to about 20 carbon atoms and include straight and branches alkyl radicals, cyclic hydrocarbon radicals, alkyl=substituted cyclic hydrocarbon radicals, aromatic radicals and the like; substituted C1 -C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, and alkylborido radical, or a radical containing a Lewis acidic or basic functionality, and the like. Examples of heteroatom ligand groups (JR'z-1-y) which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in column 3 of Table 1 under the heading (JR'z- 1-y).
Table 1 depicts representative constituent moieties for the "Group IV B transition metal component", the list is for illustrative purposes only and should not be construed to be limiting in any way. A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other. Illustrative compounds are: dimethylsilyltetramethylcyclopentadienyl-tertbutylamido zirconium dichloride, methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido titanium dichloride, and dimethylsilyltetramethylcyclopentadienylcyclododecylamido titanium dichloride, and the like.
For illustrative purposes, the above compounds and those permuted from Table 1 do not include the neutral Lewis base ligand (L). The conditions under which complexes containing neutral Lewis base ligands such as ether or those which form dimeric compounds is determined by the steric bulk of the ligands about the metal center. For example, the t-butyl group in Me2 Si(Me4 C5)(N-t-Bu)ZrCl2 has greater steric requirements than the phenyl group in Me2 Si(Me4 C5)(NPh)ZrCl2.Et2 O thereby not permitting ether coordination in the former compound. Similarly, due to the decreased steric bulk of the trimethylsilylcyclopentadienyl group in [Me2 Si(Me3 SiC5 H3)(N-t-Bu)ZrCl2 ]2 versus that of the tetramethylcyclopentadienyl group in Me2 Si(Me4 C5)(N-t-Bu)ZrCl2, the former compound is dimeric and the latter is not.
TABLE 1__________________________________________________________________________ ##STR5##T (when y = 1)      (C5 H5-y-x Rx)                            (JR'z-1-y)                                         Q          M__________________________________________________________________________dimethylsilyl      cyclopentadienyl       -t-butylamide                                         hydride    zirconiumdiethylsilyl      methylcyclopentadienyl                            phenylamido  chloro     hafniumdi- -n-propylsilyl      1,2-dimethylcyclopentadienyl                            p- -n-butylphenylamido                                         methyl     titaniumdiisopropylsilyl      1,3-dimethylcyclopentadienyl                            cyclohexylamido                                         ethyldi- -n-butylsilyl      indenyl               perflurophenylamido                                         phenyldi- -t-butylsilyl      1,2-diethylcyclopentadienyl                             -n-butylamido                                         fluorodi- -n-hexylsilyl      tetramethylcyclopentadienyl                            methylamido  bromomethylphenylsilyl      ethylcyclopentadienyl ethylamido   iodoethylmethylsilyl       -n-butylcyclopentadienyl                             -n-propylamido                                          -n-propyldiphenylsilyl      cyclohexylmethylcyclopentadienyl                            isopropylamido                                         isopropyldi(p- -t-butylphenethyl-       -n-octylcyclopentadienyl                            benzylamido   -n-butylsilyl) -n-hexylmethylsilyl      &#946;-phenylpropylcyclopentadienyl                             -t-butylphosphido                                         amylcyclopentamethylene-      tetrahydroindenyl     ethylphosphido                                         isoamylsilylcyclotetramethylene-      propylcyclopentadienyl                            phenylphosphido                                         hexylsilylcyclotrimethylenesilyl       -t-butylcyclopentadienyl                            cyclohexylphosphido                                         isobutyldimethylgermanyl      benzylcyclopentadienyl                            oxo (when y = 1)                                         heptyldiethylgermanyl      diphenylmethylcyclopentadienyl                            sulfido (when y = 1)                                         octylphenylamido      trimethylgermylcyclopentadienyl                            methoxide (when y = 0)                                         nonyl -t-butylamido      trimethylstannylcyclopentadienyl                            ethoxide (when y = 0)                                         decylmethylamido      triethylplumbylcyclopentadienyl                            methylthio (when y = 0)                                         cetyl -t-butylphosphido      trifluromethylcyclopentadienyl                            ethylthio (when y = 0)                                         methoxyethylphosphido      trimethylsilylcyclopentadienyl     ethoxyphenylphosphido      pentamethylcyclcopentadienyl (when y = 0)                                         propoxymethylene  fluorenyl                          butoxydimethylmethylene      octahydrofluorenyl                 phenoxydiethylmethylene      N,N-dimethylamidocyclopentadienyl  dimethylamidoethylene   dimethylphosphidocyclopentadienyl  diethylamidodimethylethylene      methoxycyclopentadienyl            methylethylamidodiethylethylene      dimethylboridocyclopentadienyl     di- -t-butylamidodipropylethylene      (N,N-dimethylamidomethyl)cyclopentadienyl                                         diphenylamidopropylene                                     diphenylphosphidodimethylpropylene                             dicyclohexylphosphidodiethylpropylene                              dimethylphosphido1,1-dimethyl-3,3-di-                          methylidene (both Q)methylpropylenetetramethyldisiloxane                         ethylidene (both Q)1,1,4,4-tetramethyldi-                        propylidene (both Q)silylethylene                                 ethyleneglycoldianion                                         (both Q)__________________________________________________________________________
Generally the bridged species of the Group IV B transition metal compound ("y"=1) are preferred. These compounds can be prepared by reacting a cyclopentadienyl lithium compound with a dihalo compound whereupon a lithium halide salt is liberated and a monohalo substituent becomes covalently bound to the cyclopentadienyl compound. The so substituted cyclopentadienyl reaction product is next reacted with a lithium salt of a phosphide, oxide, sulfide or amide (for the sake of illustrative purposes, a lithium amide) whereupon the halo element of the monohalo substituent group of the reaction product reacts to liberate a lithium halide salt and the amine moiety of the lithium amide salt becomes covalently bound to the substituent of the cyclopentadienyl reaction product. The resulting amine derivative of the cyclopentadienyl product is then reacted with an alkyl lithium reagent whereupon the labile hydrogen atoms, at the carbon atom of the cyclopentadienyl compound and at the nitrogen atom of the amine moiety covalently bound to the substituent group, react with the alkyl of the lithium alkyl reagent to liberate the alkane and produce a dilithium salt of the cyclopentadienyl compound. Thereafter the bridged species of the Group IV B transition metal compound is produced by reacting the dilithium salt cyclopentadienyl compound with a Group IV B transition metal preferably a Group IV B transition metal halide.
Unbridged species of the Group IV B transition metal compound can be prepared from the reaction of a cyclopentadienyl lithium compound and a lithium salt of an amine with a Group IV B transition metal halide.
Suitable, but not limiting, Group IV B transition metal compounds which may be utilized in the catalyst system of this invention include those bridged species ("y"=1) wherein the T group bridge is a dialkyl, diaryl or alkylaryl silane, or methylene or ethylene. Exemplary of the more preferred species of bridged Group IV B transition metal compounds are dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl, ethylene or methylene bridged compounds. Most preferred of the bridged species are dimethylsilyl, diethylsilyl and methylphenylsilyl bridged compounds.
Suitable Group IV B transition metal compounds which are illustrative of the unbridged ("y"=0) species which may be utilized in the catalyst systems of this invention are exemplified by pentamethylcyclopentadienyldi-t-butylphosphinodimethyl hafnium; pentamethylcyclopentadienyldi-t-butylphosphinomethylethyl hafnium; cyclopentadienyl-2-methylbutoxide dimethyl titanium.
To illustrate members of the Group IV B transition metal component, select any combination of the species in Table 1. An example of a bridged species would be dimethylsilyclopentadienyl-t-butylamidodichloro zirconium; an example of an unbridged species would be cyclopentadienyldi-t-butylamidodichloro zirconium.
Generally, wherein it is desired to produce an α-olefin copolymer which incorporates a high content of α-olefin, the species of Group IV B transition metal compound preferred is one of titanium. The most preferred species of titanium metal compounds are represented by the formula: ##STR6## wherein Q, L, R', R, "x" and "w" are as perviously defined and R1 and R2 are each independently a C1 to C20 hydrocarbyl radicals, substituted C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring which incorporates the silicon bridge.
The alumoxane component of the catalyst system is an oligomeric compound which may be represented by the general formula (R3 -Al-O)m which is a cyclic compound, or may be R4 (R5 -Al-O-)m -AlR6 2 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R3, R4, R5 and R6 are, independently a C1 -C5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "m" is an integer from 1 to about 50. Most preferably, R3, R4, R5 and R6 are each methyl and "m" is at least 4. When an alkyl aluminum halide is employed in the preparation of the alumoxane, one or more R3-6 groups may be halide.
As is now well known, alumoxanes can be prepared by various procedures. For example, a trialkyl aluminum may be reacted with water, in the form of a moist inert organic solvent; or the trialkyl aluminum may be contacted with a hydrated salt, such as hydrated copper sulfate suspended in an inert organic solvent, to yield an alumoxane. In another method, non-dehydrated or wet gels, such as wet silica gels may be reacted with trialkyl aluminums. Generally, however prepared, the reaction of a trialkyl aluminum with a limited amount of water yields a mixture of both linear and cyclic species of alumoxane.
Suitable alumoxanes which may be utilized in the supported catalyst systems of this invention are those prepared by the hydrolysis of a trialkylaluminum; such as trimethylaluminum, triethyaluminum, tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride, diisobutylaluminumchloride, diethylaluminumchloride, and the like. The most preferred alumoxane for use is methylalumoxane (MAO). Methylalumoxanes having an average degree of oligomerization of from about 4 to about 25 ("m"=4 to 25), with a range of 13 to 25, are the most preferred.
Inert Support
The normally hydrocarbon soluble transition metal component and alumoxane are prepared as a supported catalyst by deposition on a support material. The support material for preparing the supported catalyst may be any resinous support material such as a polyolefin or any finely divided inorganic solid porous support, such as talc, silica, alumina, silica-alumina, or mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with silica or silica-alumina alumina are magnesia, titania, zirconia, and the like. The inorganic oxides may be dehydrated, as is well known in the art, to remove water. If desired, the residual surface hydroxyl groups in the inorganic solid porous support may be removed by additional heating or by reaction with chemical dehydrating agents such as lithium alkyl, silylchloride, aluminum aklyls, or preferably with alumoxane. Preferred catalyst supports include dehydrated inorganic oxide treated with an alumoxane, more preferably with methylalumoxane. A suitable support material of this type is a dehydrated silica gel treated with methylalumoxane. When such a alumoxane-treated support is utilized in the production of the supported catalyst, it may not be necessary to include additional alumoxane in the catalyst composition. Also preferred as a catalyst support is a wet gel, more preferably a wet silica gel, containing up to approximately 20% by weight absorbed water. Wet gels may be directly mixed with trialkyl aluminums to form the alumoxane component of the catalyst system.
The specific particle size, surface area and pore volume of the inorganic support material determine the amount of inorganic support material that is desirable to employ in preparing the catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions. These properties must frequently be taken into consideration in choosing an inorganic support material for use in a particular aspect of the invention. A suitable inorganic support such as silica would have a particle diameter in the range of 0.1-600 microns, preferably 0.3-100 microns; a surface area of 50-1000 m2 /g, preferably 100-500 m2 /g; and a pore volume of 0.5-3.5 cm3 /g. To insure its use in dehydrated form the support material may be heat treated at 100�-1000� C. for a period of 1-100 hours, preferably 3-24 hours. The treatment may be carried out in a vacuum or while purging with a dry inert gas such as nitrogen. As an alternative, the support material may be chemically dehydrated. The chemical dehydration is accomplished by slurrying the support in an inert low boiling solvent such as, for example, heptane, in the presence of the dehydrating agent such as for example, triethylaluminum in a moisture and oxygen-free atmosphere.
Catalyst Systems-Method and Use
The Supported Catalyst - Preparation Method 1.
The supported catalyst of this invention can be prepared by combining in any order the Group IV B transition metal component, an alumoxane component, and the support in one or more suitable solvents or diluent. Suitable solvents and/or diluents include, but are not necessarily limited to, straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and the like; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclopentane and the like; and aromatic and alky-substituted aromatic compounds such as benzene, toluene, xylene and the like.
It is preferred that the catalyst components be handled in an inert, moisture-free, oxygen free environment such as argon, nitrogen or helium because of the sensitivity of the catalyst components to moisture and oxygen.
In a preferred method, the Group IV B transition metal component and alumoxane are combined in a first step in a suitable solvent such as an aromatic solvent to produce a solution of the reaction product. This reaction may be carried out in the temperature range of -100� C. to about 300� C., preferably about 0� C. to about 100� C. Holding times to allow for the completion of the reaction may range from about 10 seconds to about 60 minutes depending on the reaction variables.
The solution produced by combining the Group IV B transition metal component and alumoxane is then contacted with the support. The method of contact may vary, but it is preferred that the support be added to the catalyst solution with vigorous stirring. Again contact temperatures may range from about 0� C. to about 100� C. depending upon the solvents used. Contact times may vary from about 10 seconds to about 60 minutes or longer.
The solvent can then be removed, typically by applying a vacuum. The solution may or may not be heated in order to aid in the removal of the solvent.
Regardless of the method used in the preparation, the active supported catalyst can be recovered by evaporation of the solvent to obtain a free-flowing solid or alternatively, the active supported catalyst can be maintained in its slurry state for direct use.
In accordance with this invention, optimum results are generally obtained wherein the alumoxane to Group IV B transition metal compound molar ratio is from about 1:1 to about 20,000:1, preferably for about 10:1 to about 1000:1. The Group IV B transition metal compound concentration on the support is typically between 0.01 wt % to about 100 wt %, preferably about 0.1 wt % to about 20 wt % based upon the weight of the support.
The Modified Supported Catalyst-Preparation Method 2
The modified supported catalyst of this invention can be prepared by combining in any order the Group IV B transition metal component, an alumoxane component, a modifier and the support in one or more suitable solvents or diluent. A modifier may be defined as a compound containing a Lewis acid or basic functionality, such as, for example, tetraethoxysilane, phenytriethyoxysilane, bis-tert-butylhydroxytoluene (BHT), N,N-dimethylanaline and the like. Suitable solvents and/or diluents are the same as those described above.
In a preferred method, the alumoxane and the modifier are combined in a first step in a suitable solvent such as an aromatic solvent to produce a solution. The Group IV B transition metal compound is then added to this solution. These combined steps may be carried out in the temperature range of -100� C. to about 300� C., preferably about 0� C. to about 100� C. Holding times to allow for the completion of the reaction may range from about 10 seconds to about 60 minutes depending on the reaction variables.
The solution produced by combining the Group IV B transition metal component, the alumoxane and the modifier is then contacted with the support. The method of contact may vary, but it is preferred that the support be added to the catalyst solution without vigorous stirring. Again contact temperatures may range from about 0� C. to about 100� C. depending upon the solvents used. Contact times may vary from about 10 seconds to about 60 minutes or longer.
Regardless of the method used in preparation, the active supported catalyst can be recovered by evaporation of the solvent to obtain a free-flowing solid or alternatively, the active supported catalyst can be maintained in its slurry state for direct use.
In accordance with this invention, optimum results are generally obtained wherein the alumoxane to Group IV B transition metal compound molar ratio is from about 1.1 to about 20,000:1, preferably from about 10:1 to about 1000:1 and the alumoxane to modifier molar ratio is from about 1:1 to about 20,000:1, preferably from about 10:1 to about 1000:1. The Group IV B transition metal compound concentration on the support is typically between 0.01 wt % to about 100 wt %, preferably about 0.1 wt % to about 20 wt % based upon the weight of the support.
The Supported Catalyst - Preparation Method 3
In an alternative procedure the alumoxane component of the catalyst complex is prepared by direct reaction of a trialkyl aluminum or trialkyl aluminum mixtures with the material utilized as the catalyst support, such as an undehydrated silica gel. Silica useful as the catalyst support is that which has a surface area in the range of about 10 to about 700m2 / g, preferably about 100-500 and desirably about 200-400m2, a pore volume of about 3 to about 0.5 cc/g and preferably 2-1 cc/g, and an adsorbed water content of from about 6 to about 20 weight percent, preferably from about 9 to about 15 weight percent. The average particle size (APS) of the silica may be from about 0.3μ to about 100μ, and for a gas phase catalyst preferably from about 30μ to about 60μ (1μ=10-6 m). For a catalyst intended for high pressure polymerization the particle size of the silica should range from about 0.3 to no greater than about 10μ. Hereafter, silica having the above identified properties is referred to as undehydrated silica gel.
Undehydrated silica gel, as defined above, is added over time, about a few minutes, to a stirred solution of trialkyl aluminum, in an amount sufficient to provide a mole ratio of trialkyl aluminum to water of from about 3:1to 1:2, preferably about 1.2:1 to 0.8:1. The trialkyl aluminum preferred for use in forming the alumoxane is trimethylaluminum. Next in order of preference, is triethylaluminum.
Upon addition of the undehydrated silica gel to the solution of trialkyl aluminum, the water content of the silica gel controllably reacts with the trialkyl aluminum to produce an alumoxane which is deposited onto the surface of the silica gel particles. Although the reaction of the trialkyl aluminum with the water content of the silica gel proceeds relatively quickly, that is, it is generally completed within the time of about 5 minutes, it does not occur with the explosive quickness of that which occurs with free water. The reaction may be safely conducted in conventional mixing equipment under a mantle of inert gas.
Thereafter a transition metal component is added to the stirred suspension of alumoxane silica gel product in an amount sufficient to provide a mole ratio of aluminum to transition metal of from about 1000:1 to about 1:1, preferably from about 300:1 to about 10:1 and most preferably from about 150:1 to about 30:1. The mixture is stirred for about 30 minutes to about one hour at ambient or an elevated temperature to permit the transition metal component to undergo complete reaction with the adsorbed alumoxane. Thereafter, the solvent is removed and the residual solids are dried, preferably at a temperature of 25� C. or greater, to a free flowing powder. The free flowing powder comprises a silica gel supported transition metal alumoxane catalyst complex of sufficiently high catalytic activity for use in the polymerization of olefins by conventional gas phase or liquid phase polymerization procedures.
The Prepolymerized Supported Catalyst
Upon completion of the deposition of the transition metal component, alumoxane and optionally a modifier on the support, the solid material can be treated with a small amount of monomer, e.g. ethylene, to form an amount of polymer on the solid catalyst materials to increase the catalyst weight at least 50%, desirably from about 100 to about 500% based on the total weight of catalyst and support material. Such treatment is hereafter referred to as prepolymerization of the catalyst. Then the solid material, as such or as prepolymerized, can be recovered by any well-known technique. For example, the solid catalyst material can be recovered from the liquid by filtration, by vacuum evaporation, or by decantation. The solid is thereafter dried under a stream of pure dry nitrogen or dried under vacuum.
Prepolymerization of the prepolymerized solid catalyst material aids in obtaining a polyolefin produced therefrom during slurry polymerization in well-defined particle form. The prepolymerized catalyst may be rinsed with a hydrocarbon to provide the good granular particle form. Prepolymerization also greatly reduces the requirement for alumoxane. For example, an Al:Transition Metal Component ratio of about 1000:1 or greater for alumoxane:Transition Metal Component is needed for high activity when the alumoxane is added to the liquid phase of the reactor, but a ratio less than 1000:1 is sufficient when the alumoxane is incorporated into the prepolymerized catalyst. For a prepolymerized catalyst the ratio of aluminum to transition metal may range from about 1:1 to 500:1, preferably from about 20:1 to 100:1, and high activities will still be obtained.
Most preferably, the prepolymerized supported catalyst is prepared in the following manner 1) forming a slurry by the addition of the alumoxane dissolved in a suitable solvent, toluene for example, to the support; 2) stirring the slurry at 60�-80� C. for 30-60 minutes; 3) removal of solvent under vacuum with heating sufficient to produce a dry powder; 4) adding a light hydrocarbon, pentane for example, to slurry the powder; 5) adding a solution of the transition metal component in pentane or a minimum amount of toluene and stirring for 15-60 minutes at 20�-60� C.; 6) prepolymerizing with ethylene or other olefin in the pentane slurry; and 7) then collecting, rinsing and drying the supported catalyst. For best particle form, it is preferred to add no alumoxane to the reactor beyond what is on the prepolymerized catalyst. Sufficient aluminum alkyl, such as triethylaluminum or triisobutylaluminum, to scavenge impurities in the feeds may be added, but not an excess.
The supported catalysts may be most usefully employed in gas or slurry phase processes, both of which are known to those of skill in the art. Thus, polymerizations using the invention supported catalysts may be conducted by either of these processes, generally at a temperature in the range of about 0� -160� C. or even higher, and under atmospheric, subatmospheric or superatmospheric pressure conditions.
A slurry polymerization process can utilize sub-or super-atmospheric pressures and temperatures in the range of -80�--250� C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization medium to which ethylene, α-olefin, diolefin, cyclic olefin or acetylenically unsaturated comonomer, hydrogen and catalyst are added. Alkanes and cycloalkanes, such as butane, pentane, hexane, or cyclohexane, are preferred with C4 to C10 alkanes especially preferred. Preferred solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene and the like.
A gas-phase polymerization process utilizes superatmospheric pressure and temperatures in the range of about 50� C.-20� C. Gas-phase polymerization can be performed in a stirred or fluidized bed of catalyst and product particles in a pressure vessel adapted to permit the separation of product particles from unreacted gases. Thermostated ethylene, comonomer, including α-olefins, diolefins, cyclic olefins or acetylenically unsaturated comonomer, hydrogen and an inert diluent gas such as nitrogen can be introduced or recirculated so as to maintain the particles at a temperature of 50�-120� C. Polymer product can be withdrawn continuously or semi-continuously at a rate such as to maintain a constant product inventory in the reactor. After polymerization and deactivation of the catalyst, the product polymer can be recovered by any suitable means. In commercial practice, the polymer product can be recovered directly from the gas phase reactor, freed of residual monomer with a nitrogen purge, and used without further deactivation or catalyst removal. The polymer obtained can be extruded into water and cut into pellets or other suitable comminuted shapes. Pigments, antioxidants and other additives, as is know in the art, may be added to the polymer.
While it is a characteristic of the invention supported catalyst that the produced polymers have a narrow molecular weight distribution, broad molecular weight distribution polymers may be produced by using two or more metallocenes or two or more activators.
In the examples which illustrate the practice of the invention the analytical techniques described below were employed for the analysis of the resulting polyolefin products. Molecular weight determinations for polyolefin products were made by Gel Permeation Chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector and a Chromatix KMX-6 on-line light scattering photometer. The system was used at 135� C. with 1,2,4-trichlorobenzene as the mobile phase. Shodex (Showa Denko America, Inc.) polystyrene gel columns 802, 803, 804 and 805 were used. This technique is discussed in "Liquid Chromatography of Polymers and Related Materials III", J. Cazes editor, Marcel Dekker. 198, p. 207, which is incorporated herein by reference. No corrections for column spreading were employed; however, data on generally accepted standards, e.g. National Bureau of Standards Polyethylene 1484 and anionically produced hydrogenated polyisoprenes (an alternating ethylene-propylene copolymer) demonstrated that such corrections on Mw/Mn (=MWD) were less than 0.05 units. Mw/Mn was calculated from elution times. The numerical analyses were performed using the commercially available Beckman/CIS customized LALLS software in conjunction with the standard Gel Permeation package, run on a HP 1000 computer.
The following examples are intended to illustrate specific embodiments of the invention and are not intended to limit the scope of the invention.
All procedures were performed under an inert atmosphere of nitrogen. Solvent choices are often optional, for example, in most cases either pentane or 30-60 petroleum ether can be interchanged. The lithiated amides were prepared from the corresponding amines and either n-BuLi or MeLi. Published methods for preparing LiHC5 Me4 include C. M. Fendrick et. al., Organometallics, 3:819 (1984) and F. H. Kohler and K. H. Doll, Z. Naturforich, 376:144 (1982). Other lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by reaction of MeLi with the proper fulvene. TiCl4 and ZrCl4 were purchased from either Aldrich Chemical Company or Cerac. TiCl4 was typically used in its etherate form. The etherate, TiCl4.2Et2 O can be prepared by gingerly adding TiCl4 to diethylether. Amines, silanes, and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane (MAO) solutions were either toluene or heptane based and were supplied by either Schering or Ethyl Corp. The silica used was Davidson 948 grade, and was dried at 800� C. Triethylalumina (TEAL), supplied by Texas Alkyls as a 1.6M solution in heptane, was used as a scavenger in the polymerizations.
Preparation of Group IV B Transition Metal Components
Part 1. Me4 HC5 Li (10.0 g, 0.078 mol) was slowly added to a Me2 SiCl2 ([11.5 ml, 0.095 mol, in 225 ml of tetrahydrofuran (THF) solution. The solution was stirred for 1 hour to assure complete reaction. The thf solvent was then removed via a vacuum to a cold trap held at -196� C. Pentane was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me4 HC5 SiMe2 Cl (15.34 g, 0.071 mol) was recovered as a pale yellow liquid.
Part 2. Me4 HC5 SiMe2 Cl (10.0 g, 0.047 mol) was slowly added to a suspension of LiHN-t-Bu (3.68 g, 0.047 mol, ˜100 ml THF). The mixture was stirred overnight. The thf was then removed via a vacuum to a cold trap held at -196� C. Petroleum ether (˜100 ml) was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2 Si(Me4 HC5)(HN-t-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.
Part 3. Me2 Si(Me4 HC5)(HN-t-Bu) (11.14 g, 0.044 mol) was diluted with ˜100 ml of Et2 O. MeLi (1.4M, 64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for 0.5 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2 Si(Me4 C5)(N-t-Bu)]Li2 was washed with several small portions of ether, then vacuum dried.
Part 4. [Me2 Si(Me4 C5)(N-t-Bu)]Li2 (3.0 g, 0.011 mol) was suspended in ˜150 ml of Et2 O. ZrCl4 (2.65 g, 0.011 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at -196� C. Pentane was added to precipitate the LiCl. The mixture was filtered through Celite twice. The pentane was significantly reduced in volume and the pale yellow solid was filtered off and washed with solvent. Me2 Si(Me4 C5)(N-t-Bu)ZrCl2 (1.07 g, 0.0026 mole) was recovered. Additional Me2 Si(Me4 C5)(N-t-Bu)ZrCl2 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol.
Part 1. MePhSiCl2 (14.9 g, 0.078 mol) was diluted with 250 ml of thf. Me4 HC5 Li (10.0 g, 0.078 mol) was slowly added as a solid. The reaction solution was allowed to stir overnight. The solvent was removed via a vacuum to a cold trap held at -196� C. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite and the pentane was removed from the filtrate. MePhSi(Me4 C5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in ˜100 ml of thf. MePhSi(C5 Me4 H)Cl (15.0 g, 0.054 mol) was added dropwise. The yellow solution was allowed to stir overnight. The solvent was removed in vacuo. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated. MePhSi(C5 Me4 H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered as an extremely viscous liquid.
Part 3. MePhSi(C5 Me4 H)(NH-t-Bu)(17.2 g, 0.055 mol) was diluted with ˜20 ml of ether. n-BuLi (60 ml in hexane, 0.096 mol, 1.6 M) was slowly added and the reaction mixture was allowed to stir for ˜3 hours. The solvent was removed in vacuo to yield 15.5 g (0.48 mol) of a pale tan solid formulated as Li2 [MePhSi(C5 Me4)(N-t-Bu)].
Part 4. Li2 [MePhSi(C5 Me4)(N-t-Bu)](8.75 g, 0.027 mol) was suspended in ˜125 ml of cold ether (-30� C.). TiCl4.2Et2 O (9.1 g, 0.027 mol) was slowly added. The reaction was allowed to stir for several hours prior to removing the ether via vacuum. A mixture of toluene and dichloromethane was then added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The solvent was largely removed via vacuum and petroleum ether was added. The mixture was cooled to maximize product precipitation. The crude product was filtered off and redissolved in toluene. The toluene insolubles were filtered off. The toluene was then reduced in volume and petroleum ether was added. The mixture was cooled to maximize precipitation prior to filtering off 3.34 g (7.76 mmol) of the yellow solid MePhSi(C5 Me4)(N-t-Bu)TiCl2.
Part 1. (C5 Me4 H)SiMe2 Cl was prepared as described in Example A for the preparation of Compound A, Part 1.
Part 2. (C5 Me4 H)SiMe2 Cl (8.0 g, 0.037 mol) was slowly added to a suspension of LiHNC12 H23 (C12 H23 =cyclododecyl, 7.0 g, 0.037 mol, ˜80 ml THF). The mixture was stirred overnight. The THF was then removed via a vacuum to a cold trap held at -196� C. Petroleum ether and toluene were added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2 Si(C5 Me4 H)(NHC12 H23)(11.8 g, 0.033 mol) was isolated as a pale yellow liquid.
Part 3. Me2 Si(C5 Me4 H)(NHC12 H23)(11.9 g, 0.033 mol) was diluted with ˜150 ml of ether. MeLi (1.4 M, 47 ml, 0.066 mol) was slowly added. The mixture was allowed to stir for 2 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2 Si(C5 Me4)(NC12 H23)]Li2, was washed with several small portions of ether, then vacuum dried to yield 11.1 g (0.030 mol) of product.
Part 4. [Me2 Si(C5 Me4)(NC12 H23)]Li2 (3.0 g, 0.008 mol) was suspended in cold ether. TiCl4.2Et2 O (2.7 g, 0.008 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at -196� C. Methylene chloride was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate the product. This mixture was refrigerated prior to filtration in order to maximize precipitation. The solid collected was recrystallized from methylene chloride and Me2 Si(C5 Me4)(NC12 H23)TiCl2 was isolated (1.0 g, 2.1 mmol).
Supported Catalyst Preparation and Use in Polymerization Procedures
Dried silica (2.5 g) was slurried with 10 ml of 1.0M methylalumoxane (MAO) in toluene, and stirred for 0.5 hours. The slurry was then filtered and washed five times with 10 ml portions of pentane. The washed slurry was then dried under vacuum.
The transition metal compound, A, Me2 Si(Me4 C5)(N-t-Bu)ZrCl2 (0.063 g, 0.-53 mmole) prepared as described for Example A, was combined with 35 ml of 1.0M MAO in toluene. The solution was stirred for five minutes prior to the addition of the treated silica (2.5 g). The mixture was then stirred for 5 minutes, after which time the toluene was removed via vacuum, and the prepared supported catalyst was recovered.
A polymerization run was performed in a 1 liter autoclave reactor equipped with a paddle stirrer, an external water jacket for temperature control, a regulated supply of dry nitrogen, ethylene, propylene, 1-butene and hexane, and a septum inlet for introduction of other solvents or comonomers, transition metal compound, and alumoxane solutions. The reactor was dried and degassed thoroughly prior to use.
A typical run consisted of injecting 400 ml of hexane, 0.2 ml TEAL (1.6 M in heptane), and 0.5 g of the prepared supported catalyst into the reactor. The reactor was heated to 80� C. and 65 psi of ethylene was introduced prior to the injection of the prepared supported catalyst. The polymerization reaction was limited to 30 minutes. The reaction was stopped by rapidly cooling and venting the system. A mass of 20.2 g of polyethylene was recovered, having a molecular weight (MW) of 231,200, and a molecular weight distribution (MWD)=3.26.
Dried silica (5.0 g) was slurried in 25 ml of toluene. MAO (12.5 ml, 1.0 M) was added and the mixture was permitted to stir for five minutes. The transition metal compound A, Me2 Si(Me4 C5)(N-t-Bu)ZrCl2 (0.100 g, 0.243 mmole) prepared as described for Example A, was then added and the mixture was stirred for five minutes. Toluene was removed from the mixture via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure as described for Example 1, 400 ml of hexane, 0.20 ml of triethylaluminum (TEAL) (1.6M in heptane), 0.50 g of the prepared supported catalyst, and 60 psi of ethylene were added to the reactor at 80� C. and allowed to react for 20 minutes. A mass of 1.9 g of polyethylene was recovered having a molecular weight of 170,900, and a MWD of 2.992.
Dried silica was pretreated with methylalumoxane as described for Example 1. The transition metal compound B, MePhSi(Me4 C5)(N-t-Bu)TiCl2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 7.5 ml of 1.0 M MAO in toluene and stirred for five minutes. Pretreated silica (0.5 g) was then added to this mixture with stirring for 5 minutes. The toluene was then removed via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure as described for Example 1, 400 ml of hexane, 0.20 ml of TEAL (1.6M in heptane), 0.50 g of the prepared supported catalyst and 65 psi of ethylene were added to the reactor at 80� C. and allowed to react for 10 minutes. A mass of 10.7 g of polyethylene was recovered, having a molecular weight of 189,900, and a MWD of 3.652.
The transition metal compound B, MePhSi(Me4 C5)(N-t-Bu)TiCl2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 5.0 ml of 1.5M MAO in heptane and stirred for five minutes. Dried silica, which had not been pretreated (0.5 g) was then added to this mixture with stirring for 5 minutes. The heptane was removed via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure as described for Example 1, 400 ml of hexane, 0.20 ml of TEAL (1.6M in heptane), 0.50 g of the prepared supported catalyst and 65 psi of ethylene were added to the reactor at 80� C. and allowed to react for 15 minutes. A mass of 0.5 g of polyethylene was recovered having a molecular weight of 175,600 and a MWD of 2.801.
The transition metal compound B, MePhSi(Me4 C5) (N-t-Bu)TiCl2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 7.5 ml of 1.0 M MAO in toluene and stirred for five minutes. Dried silica (0.5 g), which had not been pretreated, was then added to this mixture with stirring for 5 minutes. The toluene was then removed via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure as described for Example 1, 400 ml of hexane, 0.20 ml of TEAL (1.6M in heptane), 0.50 g of the prepared supported catalyst and 65 psi of ethylene were added to the reactor at 80� C. and allowed to react for 10 minutes. A mass of 3.1 g of polyethylene was recovered having a molecular weight of 313,900 and a MWD of 3.175.
Dried silica (2.5 g) was slurried with 10 ml of 1.5M MAO in heptane and stirred for 0.5 hours. This slurry was then filtered, and washed five times with 10 ml portions of pentane, followed by drying in vacuo.
The transition metal compound B, MePhSi(Me4 C5)(N-t-Bu)TiCl2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 5.0 ml of 1.5M MAO in heptane and stirred for five minutes. Pretreated silica (0.5 g) was then added to this mixture with stirring for 5 minutes. The heptane was removed via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure as described for Example 1, 400 ml of hexane, 0.20 ml of TEAL (1.6M in heptane), 0.50 g of the prepared supported catalyst and 65 psi of ethylene were added to the reactor at 80� C. and allowed to react for 10 minutes. A mass of 2.0 g of polyethylene was recovered having a molecular weight of 365,900 and a MWD of 4.845.
Dried silica (2.5 g) was slurried with 10 ml of 1.5M MAO in heptane and stirred for 0.5 hours. This slurry was then filtered, and washed five times with 10 ml portions of pentane. The washed slurry was dried under vacuum.
The transition metal compound C, Me2 Si(Me4 C5)(NC12 H23)TiCl2 (40 mg, 0.084 mmol), prepared as described for Example C, was dissolved in 12.3 ml of 1.5M MAO in heptane and was permitted to stir 0.5 hours. Pretreated silica (2.5 g) was added, and the mixture stirred for an additional 0.5 hours. Toluene was then thoroughly removed via vacuum and the prepared supported catalyst was recovered.
The prepared supported catalyst (0.60 g), was placed in a 30 ml serum vial equipped with a magnetic stirring bar. While stirring, ethylene (5 psi) was allowed to flow into the vial forming a static pressure, and the reaction was permitted to proceed for 2.8 days. The vial was then vented and weighed. A mass of 5.5 g of polyethylene was recovered, having a molecular weight of 732,900 and an MWD of 2.980.
A solution of 1.4M trimethylaluminum (TMA) in heptane (200 ml) was placed into a IL flask equipped with a magnetic stirring bar. Untreated silica gel (50 g), containing 9.6% water, was slowly added to the flask. After the addition of the silica was completed, the mixture was stirred at ambient temperature for one hour. The transition metal compound B, MePhSi(Me4 C5)(N-t-Bu)TiCl2 (1.35 g, 3.1 mmol), prepared as described for Example B, was slurried in 50 ml of heptane, and then added to the flask containing the treated silica. The mixture was permitted to react for one hour, and was then heated to 65� C. while a nitrogen stream was passed through the flask to remove the solvent. The nitrogen stream was stopped when the mixture in the flask turned into a free flowing powder.
A gas phase laboratory reactor was utilized with the following reactor conditions: 74� C., 300 psi, 50 mole % ethylene, 1 mole % hexene, 400 ppm hydrogen, cycle gas velocity 0.7 feet/sec, and TEAL feed rate (1% in isopentane) of 1 ml/hr. Polyethylene was recovered, (productivity 49 g/g) having the following properties: a molecular weight of 153,000, MWD of 4.817, 9 mole % hexene (as determined by 1 H NMR), and density of 0.916.
Dried silica (2.5 g) was slurried in 10 ml of 1.6M triethylaluminum (TEAL) in heptane and stirred for 0.50 hours. The slurry was then filtered and washed five times with 20 ml portions of pentane. The washed slurry was then dried under vacuum.
The transition metal compound, C, Me2 Si(Me4 C5)N-C12 H23 Ticl2 (0.010 g, 0.021 mmole) prepared as described for Example C, was dissolved in 5.0 mol of 1 M MAO in toluene, which contained tetraethoxysilane (TEOS) (40 mg, 0.192 mmole) as a modifier, and was permitted to stir for 5 minutes. Pretreated silica (0.50 g) was added to this mixture with stirring for 5 additional minutes. Toluene was removed from the mixture via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure described for Example 1, 400 ml of hexane, 0.50 g of the prepared supported catalyst and 65 psi of ethylene were added to the reactor at 80� C. and allowed to react for 0.50 hours. A mass of 13.2 g of polyethylene in fine particulate matter, was recovered, having a molecular weight of 221,055, and an MWD or 2.670.
The transition metal compound, C, Me2 Si(Me4 C5)N-C12 H23 TiCl2 (0.010 g, 0.021 mmole) prepared as described for Example C, was dissolved in 5.0 ml of 1 M MAO in toluene, and was permitted to stir for 5 minutes. Pretreated silica (0.50 g) was added to this mixture with stirring for 5 additional minutes. Toluene was removed from the mixture via vacuum and the prepared supported catalyst was recovered.
Using the same general polymerization procedure described for Example 1, 400 ml of hexane, 0.50 g of the prepared supported catalyst and 65 psi of ethylene were added to the reactor at 80� C. and allowed to react for 0.50 hours. A mass of 7.2 g of polyethylene in clusters of fine particles was recovered, having a molecular weight of 169,340, and a MWD of 4.999.
Table 2 summarizes the polymerization conditions employed and the properties obtained in the polymer products.
TABLE 2__________________________________________________________________________Summary of Polyethylene Polymerization ResultsTransition  AT   Molar                 RXN    ActivityMetal (TM)  (MAO)            AL/TM                 Time                    Yield                        g/mmoleExampleType   mmole       mmole            Ratio                 (hr)                    (g) TM. hr                             MW  MWD__________________________________________________________________________1    A  0.031       7.0  230  0.50                    20.2                        1,300                             231,200                                 3.262    A  0.024       1.25  50  0.33                    1.9 240  170,900                                 2.993    B  0.035       7.5  210  0.17                    10.7                        1,800                             189,900                                 3.654    B  0.035       7.5  210  0.25                    0.5  60  175,600                                 2.805    B  0.035       7.5  210  0.17                    3.1 520  313,900                                 3.186    B  0.035       7.5  210  0.17                    2.0 340  365,900                                 4.85.sup. 7aC  0.020       4.4  220  66.5                    5.5  4   732,900                                 2.98.sup. 9bB  0.021       5.0  240  0.50                    13.2                        1,260                             221,100                                 2.6710   B  0.021       5.0  240  0.50                    7.2 690  169,300                                 5.00__________________________________________________________________________ a Gas Phase Polymerization b TEOS Modifier Used
By appropriate selection of (1) Group IV B transition metal component for use in the catalyst system; (2) the type and amount of alumoxane used whether preformed or generated in situ; (3) the choice of support material; (4) the method of support; (5) the choice of a modifier if used; (6) the polymerization diluent type and amount if used; (7) the reaction temperature; (8) the reaction pressure and (9) the process used whether it be slurry, bulk or gas phase, polymers of a desired combination of properties are produced.
The invention has been described with reference to its preferred embodiments. Those of ordinary skill in the art may, upon reading this disclosure, appreciate changes or modifications which do not depart from the scope and spirit of the invention as described above or claimed hereafter.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS4701432 *Jun 9, 1986Oct 20, 1987Exxon Chemical Patents Inc.Supported polymerization catalystWO1987003887A1 *Dec 25, 1986Jul 2, 1987Mitsui Petrochemical Industries, Ltd.Process for polymerization of alpha-olefins* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5317036 *Oct 16, 1992May 31, 1994Union Carbide Chemicals & Plastics Technology CorporationGas phase polymerization reactions utilizing soluble unsupported catalystsUS5322728 *Nov 24, 1992Jun 21, 1994Exxon Chemical Patents, Inc.Fibers of polyolefin polymersUS5332706 *Dec 28, 1992Jul 26, 1994Mobil Oil CorporationProcess and a catalyst for preventing reactor foulingUS5380810 *Apr 7, 1993Jan 10, 1995The Dow Chemical CompanyElastic substantially linear olefin polymersUS5391529 *Feb 1, 1993Feb 21, 1995Albemarle CorporationSiloxy-aluminoxane compositions, and catalysts which include such compositions with a metalloceneUS5414180 *Jul 14, 1993May 9, 1995Phillips Petroleum CompanyOrgano-aluminoxy product and useUS5420220 *Mar 25, 1993May 30, 1995Mobil Oil CorporationLLDPE filmsUS5427991 *Mar 12, 1993Jun 27, 1995Exxon Chemical Patents Inc.Polyionic transition metal catalyst compositionUS5455741 *Oct 26, 1993Oct 3, 1995Pulse Engineering, Inc.Wire-lead through hole interconnect deviceUS5486632 *Jun 28, 1994Jan 23, 1996The Dow Chemical CompanyGroup 4 metal diene complexes and addition polymerization catalysts therefromUS5491246 *Apr 24, 1995Feb 13, 1996The Dow Chemical CompanySynthesis of group 4 metal diene complexesUS5495036 *Sep 12, 1994Feb 27, 1996The Dow Chemical CompanyMetal (III) complexes containing conjugated, non-aromatic anionic II-bound groups and addition polymerization catalysts therefromUS5496781 *May 16, 1994Mar 5, 1996Phillips Petroleum CompanyMetallocene catalyst systems, preparation, and useUS5512693 *Dec 7, 1994Apr 30, 1996The Dow Chemical CompanyPreparation of titanium (II) or zirconium (II) complexesUS5525678 *Sep 22, 1994Jun 11, 1996Mobil Oil CorporationProcess for controlling the MWD of a broad/bimodal resin produced in a single reactorUS5525695 *Jan 9, 1995Jun 11, 1996The Dow Chemical CompanyElastic linear interpolymersUS5534595 *Jun 6, 1995Jul 9, 1996Mitsui Toatsu Chemicals, Inc.Syndiotactic propylene copolymer, preparation of the same, and resin composition containing the sameUS5539068 *Apr 27, 1995Jul 23, 1996The Dow Chemical CompanyGroup 4, metal-conjugated diene metallocyclopentene complexes, and addition polymerization catalysts therefromUS5541349 *Sep 12, 1994Jul 30, 1996The Dow Chemical CompanyMetal complexes containing partially delocalized II-bound groups and addition polymerization catalysts therefromUS5554310Jun 9, 1994Sep 10, 1996Exxon Chemical Patents Inc.Trisubstituted unsaturated polymersUS5554704 *Jul 1, 1994Sep 10, 1996Exxon Chemical Patents, Inc.Controlled particle size polyolefins from silica supported prepolymerized matallocene catalystUS5556821 *Jul 19, 1994Sep 17, 1996Nippon Oil Company, LimitedCatalyst component for the polymerization of olefinsUS5558802 *Sep 14, 1995Sep 24, 1996Exxon Chemical Patents IncMultigrade crankcase lubricants with low temperature pumpability and low volatilityUS5565128 *Oct 12, 1994Oct 15, 1996Exxon Chemical Patents IncLubricating oil mannich base dispersants derived from heavy polyamineUS5583189 *May 16, 1995Dec 10, 1996Phillips Petroleum CompanyPolymerization processesUS5594078 *Sep 13, 1994Jan 14, 1997Phillips Petroleum CompanyProcess for producing broad molecular weight polyolefinUS5602067 *Nov 3, 1994Feb 11, 1997Mobil Oil CorporationProcess and a catalyst for preventing reactor foulingUS5604043 *Sep 20, 1993Feb 18, 1997W.R. Grace & Co.-Conn.Heat shrinkable films containing single site catalyzed copolymers having long chain branchingUS5614455 *Jun 7, 1995Mar 25, 1997Hoechst AktiengesellschaftOlefin polymerization catalyst, process for its preparation, and its useUS5614456 *Nov 3, 1994Mar 25, 1997Mobil Oil CorporationCatalyst for bimodal molecular weight distribution ethylene polymers and copolymersUS5621126 *Oct 15, 1993Apr 15, 1997Exxon Chemical Patents Inc.Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsUS5629059 *Dec 7, 1993May 13, 1997W.R. Grace & Co.-Conn.Multi-layer packaging film and receptacles made therefromUS5631391 *Aug 19, 1993May 20, 1997Canich; Jo Ann M.Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalystsUS5643847 *Jun 7, 1995Jul 1, 1997Exxon Chemical Patents Inc.Supported ionic catalyst compositionUS5648310 *Jun 26, 1995Jul 15, 1997Union Carbide Chemicals & Plastics Technology CorporationSpray dried, filled metallocene catalyst composition for use in polyolefin manufactureUS5652202 *Aug 15, 1995Jul 29, 1997Exxon Chemical Patents Inc.Lubricating oil compositionsUS5672669 *Jun 7, 1995Sep 30, 1997Union Carbide Chemicals & Plastics Technology CorporationSpray dried, filled metallocene catalyst composition for use in polyolefin manufactureUS5674795 *Jun 7, 1995Oct 7, 1997Union Carbide Chemicals & Plastics Technology CorporationSpray dried, filled metallocene catalyst composition for use in polyolefin manufactureUS5674950 *Feb 27, 1995Oct 7, 1997Exxon Chemical Patents Inc.Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents and derivatives thereofUS5691422 *Jun 12, 1996Nov 25, 1997Exxon Chemical Patents Inc.Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereofUS5723402 *May 30, 1996Mar 3, 1998Pq CorporationSilicas with specific contents of cations as supports for olefin polymerization catalystsUS5731253 *Jul 27, 1995Mar 24, 1998Albemarle CorporationHydrocarbylsilloxy - aluminoxane compositionsUS5747594Jan 27, 1997May 5, 1998The Dow Chemical CompanyPolyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulusUS5763547 *Apr 1, 1996Jun 9, 1998The Dow Chemical CompanySupported catalyst complexes for olefin in polymerizationUS5767209 *Jul 29, 1997Jun 16, 1998Bp Chemicals LimitedCatalyst compositions and process for preparing polyolefinsUS5770538 *Feb 20, 1996Jun 23, 1998The Dow Chemical CompanyGroup 4 metal diene complexes and addition polymerization catalysts therefromUS5773106Jun 7, 1995Jun 30, 1998The Dow Chemical CompanyPolyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulusUS5777041 *Jan 22, 1997Jul 7, 1998Exxon Chemical Patents IncSaturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereofUS5780554 *Nov 1, 1996Jul 14, 1998Exxon Chemical Patents Inc.Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereofUS5783638 *Aug 18, 1995Jul 21, 1998The Dow Chemical CompanyElastic substantially linear ethylene polymersUS5792534Jun 7, 1995Aug 11, 1998The Dow Chemical CompanyPolyolefin film exhibiting heat resistivity, low hexane extractives and controlled modulusUS5792730 *Jul 16, 1997Aug 11, 1998Exxon Chemical Patents, Inc.Lubricating oil succinimide dispersants derived from heavy polyamineUS5801113 *Jun 7, 1995Sep 1, 1998Exxon Chemical Patents, Inc.Polymerization catalyst systems, their production and useUS5804667 *Nov 12, 1997Sep 8, 1998Exxon Chemical Patents Inc.Dispersant additives and processUS5814574 *Aug 5, 1996Sep 29, 1998Bp Chemicals LimitedCatalyst compositions and process for preparing polyolefinsUS5817725 *Nov 25, 1996Oct 6, 1998Solvay Polyolefins Europe-Belgium (Societe Anonyme)Process for the preparation of a catalytic system, process for the (CO) polymerization of olefins and (CO) polymers of at least one olefinUS5817849 *Jul 18, 1997Oct 6, 1998The Dow Chemical CompanyMetal complexes containing bridged non-aromatic, anionic, dienyl groups and addition polymerization catalysts therefromUS5824620 *Oct 27, 1997Oct 20, 1998Repsol Quimica S.A.Heterogeneous metallocene catalysts and use thereof in olefin polymerization processUS5834077 *Nov 5, 1996Nov 10, 1998W. R. Grace & Co.-Conn.High shrink multilayer film which maintains optics upon shrinkingUS5834393 *Mar 4, 1996Nov 10, 1998The Dow Chemical CompanyAdduct of an organometal compound and a compatible anion, supported catalyst component supported catalyst processes for the preparation thereofUS5837335 *Jul 29, 1996Nov 17, 1998Cryovac, Inc.High shrink multilayer film which maintains optics upon shrinkingUS5844045 *Nov 12, 1996Dec 1, 1998The Dow Chemical CompanyEthylene interpolymerizationsUS5847177 *Oct 10, 1996Dec 8, 1998Albemarle CorporationProduction of hydrocarbon-soluble hydrocarbylaluminoxanesUS5851945 *Feb 7, 1997Dec 22, 1998Exxon Chemical Patents Inc.Olefin polymerization catalyst compositions comprising group 5 transition metal compounds stabilized in their highest metal oxidation stateUS5856255 *Jan 22, 1996Jan 5, 1999Albemarle CorporationPreparation of supported auxiliary catalysts at elevated temperature and pressure in a closed vesselUS5859159 *Mar 14, 1997Jan 12, 1999Exxon Chemical Patents Inc.Dilute process for the polymerization of non-ethylene α-olefin homopolymers and copolymers using metallocene catalyst systemsUS5863853 *Feb 24, 1997Jan 26, 1999Exxon Chemical Patents, Inc.Polymerization catalyst systems, their production and useUS5869575 *Nov 24, 1997Feb 9, 1999The Dow Chemical CompanyEthylene interpolymerizationsUS5880219 *Apr 8, 1997Mar 9, 1999Exxon Chemical Patents Inc.Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereofUS5882750 *Jul 3, 1995Mar 16, 1999Mobil Oil CorporationSingle reactor bimodal HMW-HDPE film resin with improved bubble stabilityUS5895770 *Mar 21, 1997Apr 20, 1999Pq CorporationOlefin polymerization catalysts with specific silica supportsUS5902766 *Sep 21, 1995May 11, 1999Exxon Chemical Patents Inc.Alumoxanes, catalysts utilizing alumoxanes and polymers therefromUS5919869 *Mar 6, 1998Jul 6, 1999Exxon Chemical Patents, Inc.Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereofUS5932514 *Feb 3, 1997Aug 3, 1999Borealis AgProcess for preparing catalyst supports and supported polyolefin catalysts and also their use for the preparation of polyolefinsUS5936041 *Dec 27, 1995Aug 10, 1999Exxon Chemical Patents IncDispersant additives and processUS5936050 *Feb 21, 1997Aug 10, 1999Albemarle CorporationHydrocarbylsiloxy-aluminoxane compositionsUS5939347 *Oct 17, 1995Aug 17, 1999W.R. Grace & Co. -Conn.Supported catalytic activatorUS5955625 *Jun 7, 1995Sep 21, 1999Exxon Chemical Patents IncMonocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsUS5959044 *Jul 8, 1996Sep 28, 1999Villar; Juan CarlosMethod of controlling continuous ethylene-limited metallocene-catalyzed copolymerization systemsUS5965477 *May 14, 1997Oct 12, 1999Council Of Scientific & Industrial ResearchProcess for the preparation of supported metallocene catalystUS5965756 *Oct 14, 1997Oct 12, 1999The Dow Chemical CompanyFused ring substituted indenyl metal complexes and polymerization processUS5972823 *Jul 28, 1995Oct 26, 1999Exxon Chemical Patents IncSupported ionic catalyst compositionUS5977392 *Oct 30, 1997Nov 2, 1999Respol Quimica S.A.Organometallic catalysts for the polymerization and copolymerization of alpha-olefinsUS5993707 *Dec 4, 1998Nov 30, 1999The Dow Chemical CompanyEnlarged cell size foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymersUS6001764 *May 8, 1998Dec 14, 1999Pq CorporationOlefin polymerization catalysts with specific silica supportsUS6005463 *Jan 30, 1997Dec 21, 1999Pulse EngineeringThrough-hole interconnect device with isolated wire-leads and component barriersUS6015868 *Oct 3, 1996Jan 18, 2000The Dow Chemical CompanySubstituted indenyl containing metal complexes and olefin polymerization processUS6017842 *Jul 18, 1997Jan 25, 2000The Dow Chemical CompanyOlefin polymerization catalyst composition comprising group 13 compoundUS6025448Jun 3, 1996Feb 15, 2000The Dow Chemical CompanyGas phase polymerization of olefinsUS6034021 *Jul 10, 1998Mar 7, 2000The Dow Chemical CompanyMetal complexes containing bridged, non-aromatic, anionic, dienyl groups and addition polymerization catalysts therefromUS6034022 *Jun 3, 1999Mar 7, 2000The Dow Chemical CompanyFused ring substituted indenyl metal complexes and polymerizationUS6037296 *Apr 24, 1998Mar 14, 2000Mobil Oil CorporationComonomer pretreated bimetallic catalyst for blow molding and film applicationsUS6043180 *Aug 11, 1997Mar 28, 2000The Dow Chemical CompanySupported catalyst component, supported catalyst, their preparation, and addition polymerization processUS6048909 *Dec 4, 1998Apr 11, 2000The Dow Chemical CompanyFoams having increased heat distortion temperature made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymersUS6051525 *Jul 14, 1997Apr 18, 2000Mobil CorporationCatalyst for the manufacture of polyethylene with a broad or bimodal molecular weight distributionUS6060418 *Apr 28, 1999May 9, 2000Albemarle CorporationSupported hydrocarbylsiloxy-aluminoxane catalyst compositionsUS6063725 *Nov 4, 1996May 16, 2000Mitsui Chemicals, Inc.Olefin polymerization catalyst systemUS6093752 *Mar 15, 1999Jul 25, 2000The Dow Chemical CompanyOpen-cell foam and method of makingUS6111020 *Jul 15, 1998Aug 29, 2000The Dow Chemical CompanyCrosslinked foams from blends of ethylene vinyl acetate and ethylene-styrene interpolymersUS6117962 *Feb 6, 1998Sep 12, 2000Exxon Chemical Patents Inc.Vinyl-containing stereospecific polypropylene macromersUS6124487 *Mar 6, 1998Sep 26, 2000Nova Chemicals (International) S.A.Olefin polymerization catalyst having a bridged phosphole-heteroatom ligandUS6133187 *Oct 19, 1998Oct 17, 2000Repsol Quimica S.A.Hetergeneous metallocene catalysts and use thereof in olefin polymerization processUS6136930 *May 26, 1998Oct 24, 2000Exxon Chemical Patents, Inc.Polymerization catalysts, their production and useUS6143685 *Apr 18, 1997Nov 7, 2000Respsol Quimica S.A.Process for obtaining a catalytic system for the polymerization of . .alpha-olefins in suspension in gas phase at low and high temperature or in a mass at high pressure and high or low temperaturesUS6143686 *Nov 2, 1998Nov 7, 2000Exxon Chemical Patents, Inc.Supported ionic catalyst compositionsUS6153551Jul 14, 1997Nov 28, 2000Mobil Oil CorporationPreparation of supported catalyst using trialkylaluminum-metallocene contact productsUS6153776 *Aug 28, 1998Nov 28, 2000The Dow ChemicalBimetallic complexes and polymerization catalysts therefromUS6156842 *Mar 10, 1999Dec 5, 2000The Dow Chemical CompanyStructures and fabricated articles having shape memory made from α-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic vinyl or vinylidene interpolymersUS6160029 *Mar 8, 2000Dec 12, 2000The Dow Chemical CompanyOlefin polymer and α-olefin/vinyl or α-olefin/vinylidene interpolymer blend foamsUS6160066 *Feb 3, 1999Dec 12, 2000Exxon Chemical Patents, Inc.Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsUS6174471Apr 20, 2000Jan 16, 2001The Dow Chemical CompanyOpen-cell foam and method of makingUS6174930Nov 4, 1999Jan 16, 2001Exxon Chemical Patents, Inc.Foamable polypropylene polymerUS6177375Mar 9, 1998Jan 23, 2001Pq CorporationHigh activity olefin polymerization catalystsUS6184294Sep 4, 1997Feb 6, 2001The Dow Chemical CompanyBlends of α-olefin/vinylidene aromatic monomer or hindered aliphatic vinylidene monomer interpolymers with polyolefinsUS6184327Feb 6, 1998Feb 6, 2001Exxon Chemical Patents, Inc.Elastomeric propylene polymersUS6187424Aug 5, 1998Feb 13, 2001The Dow Chemical CompanySheet materials suitable for use as a floor, wall or ceiling covering material, and processes and intermediates for making the sameUS6190768Mar 10, 1999Feb 20, 2001The Dow Chemical CompanyFibers made from α-olefin/vinyl or vinylidene aromatic and/or hindered cycloaliphatic or aliphatic vinyl or vinylidene interpolymersUS6194340Mar 2, 2000Feb 27, 2001Albemarle CorporationMethod of stabilizing hydrocarbylaluminoxanesUS6197910Feb 6, 1998Mar 6, 2001Exxon Chemical Patents, Inc.Propylene polymers incorporating macromersUS6207750Apr 16, 1999Mar 27, 2001Exxon Chemical Patents, Inc.Propylene homopolymers and methods of making the sameUS6218330 *Apr 21, 1999Apr 17, 2001Fina Research, S. A.Process for preparing and using a supported metallocene-alumoxane catalystUS6225252 *Feb 8, 1999May 1, 2001Borealis AgProcess for preparing catalyst supports and supported polyolefin catalysts and also their use for the preparation of polyolefinsUS6225432Aug 17, 1999May 1, 2001Exxon Chemical Patents Inc.Branched polypropylene compositionsUS6228795Nov 2, 1998May 8, 2001Exxon Chemical Patents, Inc.Polymeric supported catalystsUS6231795Dec 4, 1998May 15, 2001The Dow Chemical CompanySoft and flexible foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymersUS6232410Aug 26, 1998May 15, 2001The Dow Chemical CompanyElastomers with improved processabilityUS6232416Oct 23, 1998May 15, 2001Exxon Mobil Chemical Patents Inc.Olefin polymerization comprising group 5 transition metal compounds in their highest metal oxidation stateUS6235917Jan 20, 1999May 22, 2001The Dow Chemical CompanyDinuclear complexes and polymerization catalysts therefromUS6245856Jun 15, 1998Jun 12, 2001Exxon Chemical Patents, Inc.Thermoplastic olefin compositionsUS6262161Aug 12, 1999Jul 17, 2001The Dow Chemical CompanyCompositions having improved ignition resistanceUS6265339 *Jun 17, 1997Jul 24, 2001Basf AktiengesellschaftProcess for preparing carrier-borne transition metal catalystsUS6268444Jul 28, 1997Jul 31, 2001Dow Chemical Company3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization processUS6271322 *Jul 20, 1999Aug 7, 2001Mccullough Laughlin GerardMonocyclopentadienyl transition metal catalyst and olefin polymerization processUS6278009Jan 30, 1998Aug 21, 2001Repsol Quimica S.A.Heterogeneous catalyst components for olefins polymerization, preparation process and use thereofUS6284698Mar 17, 2000Sep 4, 2001The Dow Chemical CompanyHighly activated bimetallic complexes and polymerization processUS6287613Dec 12, 1994Sep 11, 2001Cryovac IncPatch bag comprising homogeneous ethylene/alpha-olefin copolymerUS6291611 *Nov 4, 1994Sep 18, 2001Borealis Holding A/SSupported olefin polymerization catalyst, its preparation and useUS6294625May 25, 1995Sep 25, 2001Exxonmobil Chemical Patents Inc.Catalyst system of enhanced productivity and its use in polymerization processUS6300398Apr 14, 1998Oct 9, 2001The Dow Chemical CompanyPolymer compositions having improved elongationUS6306960Nov 4, 1999Oct 23, 2001Exxonmobil Chemical Patents Inc.Articles formed from foamable polypropylene polymerUS6319969Aug 12, 1999Nov 20, 2001The Dow Chemical CompanyInterpolymer compositions for use in sound managementUS6329450Mar 2, 1999Dec 11, 2001The Dow Chemical CompanyThermoplastic compositions of interpolymers of alpha-olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers blended with engineering thermoplasticsUS6329466Oct 12, 2000Dec 11, 2001The Dow Chemical CompanyBlends of α-olefin/vinylidene aromatic monomer or hindered aliphatic vinylidene interpolymers with polyolefinsUS6342565May 12, 2000Jan 29, 2002Exxonmobil Chemical Patent Inc.Elastic fibers and articles made therefrom, including crystalline and crystallizable polymers of propyleneUS6342574Mar 26, 2001Jan 29, 2002Exxonmobil Chemical Patents IncPropylene polymers incorporating macromersUS6344515Sep 4, 1997Feb 5, 2002The Dow Chemical CompanyCompositions comprising a substantially random interpolymer of at least one α-olefin and at least one vinylidene aromatic monomer or hindered aliphatic vinylidene monomerUS6355592May 31, 1995Mar 12, 2002Exxonmobil Chemical Patents IncCatalyst system of enhanced productivity and its use in polymerization processUS6355742Apr 9, 1999Mar 12, 2002Lg Chemical, Ltd.Method of recycling cocatalyst for olefin polymerization conducted with metallocene catalystUS6362270Aug 12, 1999Mar 26, 2002The Dow Chemical CompanyThermoplastic compositions for durable goods applicationsUS6369120Oct 12, 2000Apr 9, 2002The Dow Chemical CompanyAcoustical insulation foamsUS6369176Aug 14, 2000Apr 9, 2002Dupont Dow Elastomers LlcProcess for preparing in a single reactor polymer blends having a broad molecular weight distributionUS6376620Jan 8, 2001Apr 23, 2002The Dow Chemical CompanyElastomers with improved processabilityUS6380294Oct 15, 1998Apr 30, 2002The Dow Chemical CompanyCOMPOSITIONS OF INTERPOLYMERS OF α-OLEFIN MONOMERS WITH ONE OR MORE VINYL OR VINYLIDENE AROMATIC MONOMERS AND/OR ONE OR MORE HINDERED ALIPHATIC OR CYCLOALIPHATIC VINYL OR VINYLIDENE MONOMERS BLENDED WITH A CONDUCTIVE ADDITIVEUS6384158Sep 13, 2000May 7, 2002Exxonmobil Chemical Patents Inc.Polymerization catalysts, their production and useUS6388014Apr 27, 2001May 14, 2002The Dow Chemical CompanyBlends of α-olefin/vinylidene aromatic monomer or hindered aliphatic vinylidene monomer interpolymers with polyolefinsUS6388029May 31, 2000May 14, 2002Repsol Quimica S.A.Process for obtaining polyolefinsUS6403773Sep 29, 1999Jun 11, 2002Exxon Mobil Chemical Patents Inc.Cationic group 3 catalyst systemUS6410124Mar 30, 1999Jun 25, 2002Exxonmobil Oil CorporationFilms with improved metallizable surfacesUS6413900Nov 20, 2000Jul 2, 2002Exxonmobil Chemical Patents Inc.Metallocene stabilized alumoxaneUS6417130Mar 25, 1996Jul 9, 2002Exxonmobil Oil CorporationOne pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerizationUS6417276Dec 20, 2000Jul 9, 2002The Dow Chemical CompanyThermoformable ethylene/styrene interpolymer-based polymer blend film for three-dimensional transfer finish foilUS6420299May 10, 2000Jul 16, 2002Dow Global Technologies Inc.Boron-substituted cyclopentadienes and metal complexes thereofUS6420300 *Jul 14, 2000Jul 16, 2002Nova Chemicals (International) S.A.Catalyst having a ketimide ligandUS6420507May 1, 1998Jul 16, 2002The Dow Chemical CompanyOlefin polymers prepared with substituted indenyl containing metal complexesUS6423793Aug 3, 2000Jul 23, 2002Exxonmobil Chemical Patents Inc.Elastomeric propylene polymersUS6423795Jun 6, 1995Jul 23, 2002Exxonmobil Chemical Patents Inc.Tetramethylcyclopentadienyl titanium compounds for ethylene-α-olefin-copolymer production catalystsUS6444302Sep 1, 2000Sep 3, 2002Exxonmobil Chemical Patents Inc.Breathable films and method for makingUS6462154 *Jun 14, 1994Oct 8, 2002Idemitsu Kosan Co., Ltd.Process for preparing olefin polymer and catalyst for polymerization of olefinUS6469113Apr 9, 1999Oct 22, 2002Lg Chemical Ltd.Method for producing supported metallocene catalyst and olefin polymerization process using the sameUS6476173Nov 7, 2000Nov 5, 2002Exxon Mobil Chemical Patents Inc.Propylene homopolymers and methods of making the sameUS6482896Aug 27, 2001Nov 19, 2002Dow Global Technologies Inc.Polypropylene/ethylene polymer fiber having improved bond performance and composition for making the sameUS6486089Nov 9, 1995Nov 26, 2002Exxonmobil Oil CorporationBimetallic catalyst for ethylene polymerization reactions with uniform component distributionUS6486284Jul 10, 1998Nov 26, 2002Dow Global Technologies Inc.Films produced from substantially linear homogeneous olefin polymer compositionsUS6492473Aug 8, 2000Dec 10, 2002Exxonmobil Chemical Patents Inc.Mixed transition metal catalyst systems for olefin polymerizationUS6500563May 11, 2000Dec 31, 2002Exxonmobil Chemical Patents Inc.Elastic films including crystalline polymer and crystallizable polymers of propyleneUS6506866May 16, 1997Jan 14, 2003Dow Global Technologies Inc.Ethylene copolymer compositionsUS6514583Sep 17, 1997Feb 4, 2003Cryovac, Inc.High impact strength film containing single site catalyzed copolymerUS6518215Nov 17, 2000Feb 11, 2003Exxonmobil Chemical Patents Inc.Polymerization catalysts, their production and useUS6524702Aug 12, 1999Feb 25, 2003Dow Global Technologies Inc.Electrical devices having polymeric membersUS6538080Feb 4, 2000Mar 25, 2003Bp Chemicals LimitedGas phase polymerization of olefinsUS6545088Jul 12, 1996Apr 8, 2003Dow Global Technologies Inc.Metallocene-catalyzed process for the manufacture of EP and EPDM polymersUS6555632Jul 8, 1998Apr 29, 2003Solvay Polyolefins Europe-Belgium (Societe Anonyme)Process for the preparation of a catalytic system, process for the (CO)polymerization of olefins and (CO)polymers of at least one olefinUS6555634Mar 17, 2000Apr 29, 2003The Dow Chemical CompanyDi- and tri-heteroatom substituted indenyl metal complexesUS6559230Sep 21, 2001May 6, 2003Dupont Dow Elastomers L.L.C.Thermosetting ethylene/alpha-olefin composition and safety glass interlayer film made from the compositionUS6605560 *Mar 13, 1997Aug 12, 2003Univation Technologies, LlcPolymerization catalyst systems, their production and useUS6608000Sep 13, 2000Aug 19, 2003Exxonmobil Chemical Patents Inc.Polymerization catalysts, their production and useUS6610800Jan 3, 2002Aug 26, 2003Dupont Dow Elastomers LlcProcess for preparing in a single reactor polymer blends having a broad molecular weight distributionUS6617407Mar 17, 2000Sep 9, 2003The Dow Chemical CompanyBis(n,n-dihydrocarbylamino)-substituted cyclopentadienes and metal complexes thereofUS6632898Jun 7, 1995Oct 14, 2003Exxonmobil Chemical Patents Inc.Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalystsUS6635715Aug 12, 1997Oct 21, 2003Sudhin DattaThermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymersUS6635778Oct 30, 1997Oct 21, 2003Repsol Quimica S.A.Catalysts systems for the polymerization and copolymerization of alpha-olefinsUS6638887Aug 2, 2000Oct 28, 2003Exxonmobil Chemical Patents Inc.Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsUS6642316Jun 29, 1999Nov 4, 2003Exxonmobil Chemical Patents Inc.Elastic blends comprising crystalline polymer and crystallizable polymUS6646071Mar 17, 2000Nov 11, 2003The Dow Chemical CompanyMetal complexes containing bridging heteroatom for olefin-polymerization-processUS6660809Feb 6, 1998Dec 9, 2003Exxonmobil Chemical Patents Inc.Propylene polymers incorporating polyethylene macromersUS6677441Nov 29, 2001Jan 13, 2004Exxonmobil Chemical Patents Inc.Cationic group 3 catalyst systemUS6686488Nov 6, 2001Feb 3, 2004The Dow Chemical CompanyConstrained geometry addition polymerization catalystsUS6713425Jun 3, 2002Mar 30, 2004Univation Technologies, LlcOne pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerizationUS6734267 *May 6, 2003May 11, 2004Univation Technologies, LlcPolymerization catalyst systems, their production and useUS6740617Jun 3, 2002May 25, 2004Univation Technologies, LlcOne pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerizationUS6750284May 15, 2000Jun 15, 2004Exxonmobil Chemical Patents Inc.Thermoplastic filled membranes of propylene copolymersUS6750307Nov 14, 2002Jun 15, 2004Exxon Mobil Chemical Patents Inc.Propylene polymers incorporating polyethylene macromersUS6767931Jul 10, 2001Jul 27, 2004Dow Global Technologies Inc.Foam compositions from blend of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic interpolymersUS6774191Aug 13, 2003Aug 10, 2004Exxonmobil Chemical Patents Inc.Propylene polymers incorporating polyethylene macromersUS6777510Sep 12, 2001Aug 17, 2004California Institute Of TechnologyInternal Lewis acid single site catalyst family for polymerization of polar monomersUS6784269Jun 20, 2002Aug 31, 2004Exxonmobil Chemical Patents Inc.Polypropylene compositions methods of making the sameUS6806326Nov 6, 2001Oct 19, 2004The Dow Chemical CompanyConstrained geometry addition polymerization catalystsUS6809168Apr 2, 2003Oct 26, 2004Exxonmobil Chemical Patents Inc.Articles formed from propylene diene copolymersUS6812289Jul 22, 2002Nov 2, 2004Dow Global Technologies Inc.Cast stretch film of interpolymer compositionsUS6825369 *Mar 10, 1994Nov 30, 2004The Dow Chemical CompanyMetal complex compoundsUS6855654Sep 16, 2002Feb 15, 2005Exxonmobil Oil CorporationBimetallic catalyst for ethylene polymerization reactions with uniform component distributionUS6864206Feb 5, 2003Mar 8, 2005Univation Technologies, LlcCatalyst support method and polymerization with supported catalystsUS6867260Apr 22, 2004Mar 15, 2005Exxonmobil Chemical Patents, Inc.Elastic blends comprising crystalline polymer and crystallizable polymers of propyleneUS6875816Mar 15, 2002Apr 5, 2005Dow Global Technologies Inc.High melt strength polymers and method of making sameUS6884857 *Apr 13, 1998Apr 26, 2005The Dow Chemical CompanyOlefin polymerization process using supported constrained geometry catalystsUS6906160Nov 5, 2002Jun 14, 2005Dow Global Technologies Inc.Isotactic propylene copolymer fibers, their preparation and useUS6916892Nov 15, 2002Jul 12, 2005Fina Technology, Inc.Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropyleneUS6919407Aug 15, 2003Jul 19, 2005Dow Global Technologies Inc.Blends and sealant compositions comprising isotactic propylene copolymersUS6921794Jan 23, 2003Jul 26, 2005Exxonmobil Chemical Patents Inc.Blends made from propylene ethylene polymersUS6924342Mar 15, 2002Aug 2, 2005Dow Global Technologies Inc.Method of making interpolymers and products made therefromUS6927256Nov 5, 2002Aug 9, 2005Dow Global Technologies Inc.Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agentUS6927258Jul 3, 2003Aug 9, 2005Exxonmobil Chemical Patents Inc.Elastic blends comprising crystalline polymer and crystallizable polymers of propyleneUS6943215Nov 5, 2002Sep 13, 2005Dow Global Technologies Inc.Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiersUS6946520Feb 27, 2002Sep 20, 2005Dow Global Technologies, Inc.Fabricated articles prepared from blends of substantially random ethylene/propylene/vinyl aromatic interpolymers with polypropyleneUS6946535Oct 18, 2004Sep 20, 2005Dow Global Technologies Inc.Films comprising isotactic propylene copolymersUS6953501Aug 8, 2002Oct 11, 2005Inventions & Discoveries, LlcWood treatment composition and method of useUS6960635May 5, 2002Nov 1, 2005Dow Global Technologies Inc.Isotactic propylene copolymers, their preparation and useUS6977287Jun 24, 2003Dec 20, 2005Exxonmobil Chemical Patents Inc.Propylene diene copolymersUS6982310May 6, 2005Jan 3, 2006Exxonmobil Chemical Patents Inc.Alpha-olefin/propylene copolymers and their useUS6982311Jul 31, 2002Jan 3, 2006Dow Global Technologies, Inc.Films produced from substantially linear homogeneous olefin polymer compositionsUS6984722Nov 29, 2001Jan 10, 2006Exxonmobil Chemical Patents Inc.Cationic group 3 catalyst systemUS6992158May 6, 2005Jan 31, 2006Exxonmobil Chemical Patents Inc.Alpha-olefin/propylene copolymers and their useUS6992159May 6, 2005Jan 31, 2006Exxonmobil Chemical Patents Inc.Alpha-olefin/propylene copolymers and their useUS6992160May 6, 2005Jan 31, 2006Exxonmobil Chemical Patents Inc.Polymerization processes for alpha-olefin/propylene copolymersUS7005491Jun 24, 2003Feb 28, 2006Exxonmobil Chemical Patents Inc.Propylene diene copolymerized polymersUS7019081Jul 3, 2003Mar 28, 2006Exxonmobil Chemical Patents Inc.Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymersUS7026403Apr 5, 2004Apr 11, 2006Exxonmobil Chemical Patents Inc.Thermoplastic filled membranes of propylene copolymersUS7026404Jan 14, 2005Apr 11, 2006Exxonmobil Chemical Patents Inc.Articles made from blends made from propylene ethylene polymersUS7026405Feb 2, 2005Apr 11, 2006Exxonmobil Chemical Patents Inc.Blends made from propylene ethylene polymersUS7034078Feb 2, 2005Apr 25, 2006Exxonmobil Chemical Patents Inc.Blends made from propylene ethylene polymersUS7037989May 27, 2003May 2, 2006Exxonmobil Chemical Patents Inc.Copolymers of ethylene and/or α-olefins and vicinally disubstituted olefinsUS7041765Nov 5, 2002May 9, 2006Dow Global Technologies Inc.Films comprising isotactic propylene copolymersUS7053157Jul 19, 2002May 30, 2006University Of Maryland, College ParkMethod for production of multimodal polyolefins of tunable composition, molecular weight, and polydispersityUS7053164Aug 26, 2005May 30, 2006Exxonmobil Chemical Patents Inc.Thermoplastic polymer blends of isotactic polypropropylene and alpha-olefin/propylene copolymersUS7056982Aug 26, 2005Jun 6, 2006Exxonmobil Chemical Patents Inc.Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymersUS7056992Dec 9, 2005Jun 6, 2006Exxonmobil Chemical Patents Inc.Propylene alpha-olefin polymersUS7056993Dec 9, 2005Jun 6, 2006Exxonmobil Chemical Patents Inc.Process for producing propylene alpha-olefin polymersUS7060754Aug 10, 2004Jun 13, 2006Dow Global Technologies Inc.Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agentUS7084218Aug 26, 2005Aug 1, 2006Exxonmobil Chemical Patents Inc.Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymersUS7101939Oct 11, 2002Sep 5, 2006Exxonmobil Chemical Patents Inc.Ethylene/α-olefin copolymer made with a non-single-site/single-site catalyst combination, its preparation and useUS7105609Feb 9, 2006Sep 12, 2006Exxonmobil Chemical Patents Inc.Alpha-olefin/propylene copolymers and their useUS7109269Jul 2, 2004Sep 19, 2006Dow Global Technologies Inc.Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiersUS7122603Feb 9, 2006Oct 17, 2006Exxonmobil Chemical Patents Inc.Alpha-Olefin/propylene copolymers and their useUS7129197Aug 29, 2002Oct 31, 2006Shell Oil CompanySynthesis of poly-alpha olefin and use thereofUS7135528Feb 16, 2005Nov 14, 2006Exxonmobil Chemical Patents Inc.Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymersUS7148173Apr 26, 1999Dec 12, 2006Repsol Quimica, S.A.Catalytic systems for the polymerization and copolymerization of alpha-olefinsUS7148305Mar 21, 2005Dec 12, 2006Dow Global Technologies Inc.Method of making interpolymers and products made therefromUS7153571Jul 25, 2003Dec 26, 2006Exxonmobil Chemical Patents Inc.Silane crosslinkable polyethyleneUS7153909Jun 13, 2002Dec 26, 2006Dow Global Technologies Inc.High density ethylene homopolymers and blend compositionsUS7157522Feb 9, 2006Jan 2, 2007Exxonmobil Chemical Patents Inc.Alpha-olefin/propylene copolymers and their useUS7166674Feb 13, 2006Jan 23, 2007Exxonmobil Chemical Patents Inc.Elastic blends comprising crystalline polymer and crystallizable polymers of propyleneUS7166676Jun 7, 2002Jan 23, 2007Dow Global Technologies, Inc.Process for preparing copolymers and blend compositions containing the sameUS7169864Dec 1, 2004Jan 30, 2007Novolen Technology Holdings, C.V.Metallocene catalysts, their synthesis and their use for the polymerization of olefinsUS7195806Jan 20, 2004Mar 27, 2007Fina Technology, Inc.High gloss polyethylene articlesUS7199203Jun 9, 2005Apr 3, 2007Dow Global Technologies, Inc.Isotactic propylene copolymer fibers, their preparation and useUS7202305Dec 9, 2005Apr 10, 2007Exxonmobil Chemical Patents Inc.Elastic blends comprising crystalline polymer and crystallizable polymers of propyleneUS7205364 *Mar 28, 1991Apr 17, 2007Exxonmobil Chemical Patents Inc.Olefin polymerization catalystsUS7205371Jan 20, 2006Apr 17, 2007Exxonmobil Chemical Patents Inc.Blends made from propylene ethylene polymersUS7211538 *Jul 16, 2004May 1, 2007Repsol Quimica S.A.Catalytic systems for the polimerization and copolimerization of alpha-olefinsUS7214638Nov 17, 2003May 8, 2007Dow Global Technologies Inc.Olefin polymerization catalyst composition comprising group 13 amide derivativesUS7214744Jun 22, 2005May 8, 2007Nova Chemicals (International) S.A.Borate activatorUS7220801Jun 11, 2002May 22, 2007Exxonmobil Chemical Patents Inc.Metallocene-produced very low density polyethylenes or linear low density polyethylenes as impact modifiersUS7220804Oct 13, 2000May 22, 2007Univation Technologies, LlcMethod for preparing a catalyst system and its use in a polymerization processUS7232869May 17, 2005Jun 19, 2007Novolen Technology Holdings, C.V.Catalyst composition for olefin polymerizationUS7232871Apr 2, 2002Jun 19, 2007Exxonmobil Chemical Patents Inc.Propylene ethylene polymers and production processUS7235607Aug 18, 2003Jun 26, 2007Exxonmobil Chemical Patents Inc.Shrink filmUS7250470Feb 22, 2006Jul 31, 2007Dow Global Technologies Inc.Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agentUS7250471Feb 22, 2006Jul 31, 2007Dow Global Technologies Inc.Impact resistance polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiersUS7271221Mar 21, 2005Sep 18, 2007Dow Global Technologies Inc.Method of making interpolymers and products made therefromUS7294679Jan 14, 2005Nov 13, 2007Univation Technologies, LlcCatalyst support method and polymerization with supported catalystsUS7300983Aug 17, 2004Nov 27, 2007Dow Global Technologies Inc.High melt strength polymers and method of making sameUS7316833Jul 30, 1999Jan 8, 2008Penchiney Emballage Flexible EuropeMulti-layer thermoplastic films and packages made therefromUS7335696Oct 17, 2003Feb 26, 2008Dow Global Technologies, Inc.Highly filled polymer compositionsUS7344775Jan 31, 2007Mar 18, 2008Dow Global Technologies Inc.Isotactic propylene copolymer fibers, their preparation and useUS7365137 *Jul 11, 2002Apr 29, 2008Basell Polyolefine GmbhMultistep process for the (co) polymerization of olefinsUS7459500May 5, 2003Dec 2, 2008Dow Global Technologies Inc.Thermoplastic elastomer compositionsUS7468416May 16, 2007Dec 23, 2008Lummus Technology Inc.Catalyst composition for olefin polymerizationUS7482418Dec 9, 2005Jan 27, 2009Exxonmobil Chemical Patents Inc.Crystalline propylene-hexene and propylene-octene copolymersUS7521507Nov 24, 2003Apr 21, 2009Exxonmobil Chemical Patents Inc.Polypropylene-based adhesive compositionsUS7521518Jan 13, 2003Apr 21, 2009Dow Global Technologies, Inc.Ethylene copolymer compositionsUS7579407May 3, 2003Aug 25, 2009Dow Global Technologies Inc.Thermoplastic elastomer compositionsUS7588830Feb 21, 2003Sep 15, 2009Cryovac, Inc.Heat shrinkable films containing single site catalyzed copolymersUS7601409Oct 13, 2009Exxonmobil Chemical Patents Inc.Stretch filmUS7645835Jan 12, 2010Dow Global Technologies, Inc.High density ethylene homopolymers and blend compositionsUS7683146Apr 23, 2007Mar 23, 2010Basell Polyolefine GmbhSupported metal alkyl compound and process for the polymerization of olefins in its presenceUS7705095 *Dec 8, 2004Apr 27, 2010Ineos Europe LimitedPolymerisation processUS7714073Jun 28, 2006May 11, 2010Jacobsen Grant BEthylene copolymers and blend compositionsUS7727638Dec 9, 2005Jun 1, 2010Exxonmobil Chemical Patents Inc.Films of propylene copolymersUS7750104Jul 6, 2010Dow Global Technologie Inc.Shear thinning ethylene/α-olefin interpolymers and their preparationUS7776977Aug 17, 2010Univation Technologies, LlcMethod for preparing a catalyst system and its use in a polymerization processUS7781510Aug 24, 2010Dow Global Technologies Inc.Highly filled polymer compositionsUS7795365Oct 1, 2003Sep 14, 2010Dow Global Technologies Inc.Liquid and gel-like low molecular weight ethylene polymersUS7855258Feb 13, 2006Dec 21, 2010Exxonmobil Chemical Patents Inc.Propylene olefin copolymersUS7858701Apr 3, 2008Dec 28, 2010Exxonmobil Chemical Patents Inc.Soft homogeneous isotactic polypropylene compositionsUS7906588Mar 15, 2011Exxonmobil Chemical Patents Inc.Soft heterogeneous isotactic polypropylene compositionsUS7951873May 31, 2011Exxonmobil Chemical Patents Inc.Linear low density polymer blends and articles made therefromUS7985811Jul 10, 2008Jul 26, 2011Univation Technologies, LlcMethod for controlling sheeting in gas phase reactorsUS7985817 *Sep 8, 2006Jul 26, 2011Sk Energy Co., Ltd.Homogeneous catalyst system for producing ethylene homopolymer or ethylene copolymers with alpha-olefinsUS7989549Aug 2, 2011Union Carbide Chemicals & Plastics Technology LlcPolymer compositions and method of making pipesUS7999039Aug 16, 2011Dow Global Technologies LlcHigh melt strength polymers and method of making sameUS8017231Sep 13, 2011Cryovac, Inc.Heat shrinkable films containing single site catalyzed copolymers having long chain branchingUS8021759Sep 20, 2011Cryovac Inc.Heat shrinkable films containing single site catalyzed copolymersUS8026323Sep 27, 2011Exxonmobil Chemical Patents Inc.Propylene ethylene polymers and production processUS8039562Jan 29, 2009Oct 18, 2011Univation Technologies, LlcMethod for seed bed treatment before a polymerization reactionUS8080616Sep 29, 2008Dec 20, 2011Basell Poliolefine Italia S.R.L.Heterophasic polyolefin compositions having improved tensile propertiesUS8093341Oct 18, 2005Jan 10, 2012Dow Global Technologies LlcMethod of controlling a polymerization reactorUS8101693Dec 6, 2010Jan 24, 2012Nova Chemicals (International) S.A.Multi reactor processUS8124557 *Sep 6, 2005Feb 28, 2012Lg Chem, Ltd.Supported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalystUS8263206Jul 7, 2006Sep 11, 2012Dow Global Technologies LlcLayered film compositions, packages prepared therefrom, and methods of useUS8383731Feb 24, 2009Feb 26, 2013Exxonmobil Chemical Patents Inc.Polypropylene-based adhesive compositionsUS8431657Nov 23, 2011Apr 30, 2013Nova Chemicals (International) S.A.Catalyst activation in a dual reactor processUS8487033May 16, 2007Jul 16, 2013Exxonmobil Chemical Patents Inc.Thermoplastic elastomer compositions, methods for making the same, and articles made therefromUS8501892Aug 26, 2011Aug 6, 2013Exxonmobil Chemical Patents Inc.Propylene ethylene polymers and production processUS8524844Jul 22, 2011Sep 3, 2013Nova Chemicals (International) S.A.Method of controlling polymer architectureUS8664129Nov 14, 2008Mar 4, 2014Exxonmobil Chemical Patents Inc.Extensible nonwoven facing layer for elastic multilayer fabricsUS8668975Nov 5, 2010Mar 11, 2014Exxonmobil Chemical Patents Inc.Fabric with discrete elastic and plastic regions and method for making sameUS8742035Dec 12, 2012Jun 3, 2014Dow Global Technologies LlcMethod of controlling a polymerization reactorUS8748693Sep 24, 2009Jun 10, 2014Exxonmobil Chemical Patents Inc.Multi-layer nonwoven in situ laminates and method of producing the sameUS8841379Nov 7, 2011Sep 23, 2014E I Du Pont De Nemours And CompanyMethod to form an aqueous dispersion of an ionomer-polyolefin blendUS8846835Sep 28, 2012Sep 30, 2014Nova Chemicals (International) S.A.Adjusting polymer compositionUS8846991Jun 17, 2010Sep 30, 2014Dow Global Technologies LlcLiquid and gel-like low molecular weight ethylene polymersUS8865847Apr 19, 2012Oct 21, 2014Nova Chemicals (International) S.AReactor operability in a gas phase polymerization processUS8962755Aug 31, 2012Feb 24, 2015Nova Chemicals (International) S.A.Polyethylene compositions and closures for bottlesUS8962762Apr 14, 2008Feb 24, 2015Exxonmobil Chemical Patents Inc.Thermoplastic polymer compositions, methods for making the same, and articles made therefromUS9012347 *Sep 28, 2011Apr 21, 2015Lg Chem, Ltd.Method for preparing supported hybrid metallocene catalystUS9012563Jul 10, 2006Apr 21, 2015Dow Global Technologies LlcSilane-grafted olefin polymers, compositions and articles prepared therefrom, and methods for making the sameUS9074082Dec 6, 2013Jul 7, 2015Nova Chemicals (International) S.A.Polyethylene compositions having high dimensional stability and excellent processability for caps and closuresUS9079991Jun 14, 2013Jul 14, 2015Nova Chemicals (International) S.A.Ethylene copolymers, film and polymerization processUS9096745Dec 16, 2013Aug 4, 2015Nova Chemicals (International) S.A.Polyethylene blend compositions and filmUS9115233Dec 12, 2013Aug 25, 2015Nova Chemicals (International) S.A.Ethylene copolymer compositions, film and polymerization processesUS9127151Feb 3, 2012Sep 8, 2015Exxonmobil Chemical Patents Inc.Polymer compositions having improved properties as viscosity index improvers and use thereof in lubricating oilsUS9133284Nov 21, 2012Sep 15, 2015Nova Chemicals (International) S.A.Passivated supports for use with olefin polymerization catalystsUS9139794Feb 3, 2012Sep 22, 2015Exxonmobil Chemical Patents Inc.Process for the production of polymeric compositions useful as oil modifiersUS9168718Mar 12, 2010Oct 27, 2015Exxonmobil Chemical Patents Inc.Method for producing temperature resistant nonwovensUS9168720Sep 24, 2009Oct 27, 2015Exxonmobil Chemical Patents Inc.Biaxially elastic nonwoven laminates having inelastic zonesUS9194060May 18, 2012Nov 24, 2015Exxonmobil Chemical Patents Inc.Polyolefin-based elastic meltblown fabricsUS9221966Dec 2, 2014Dec 29, 2015Nova Chemicals (International) S.A.Polyethylene compositions and closures for bottlesUS20020032294 *Aug 8, 2001Mar 14, 2002Repsol Quimica S.A.Heterogeneous catalyst components for olefins polymerization, preparation process and use thereofUS20020065191 *Nov 29, 2001May 30, 2002Christopher Joseph N.Cationic group 3 catalyst systemUS20020132905 *Mar 5, 2002Sep 19, 2002Babinee Susan J.Compositions of interpolymers of alpha-olefin monomers with one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers blended with a conductive additiveUS20030055176 *Jun 7, 2002Mar 20, 2003Jacobsen Grant B.Process for preparing copolymers and blend compositions containing the sameUS20030055184 *Aug 29, 2002Mar 20, 2003Pennzoil-Quaker State CompanySynthesis of poly-alpha olefin and use thereofUS20030065097 *Mar 15, 2002Apr 3, 2003The Dow Chemical CompanyHigh melt strength polymers and method of making sameUS20030088021 *Jun 13, 2002May 8, 2003The Dow Chemical CompanyHigh density ethylene homopolymers and blend compositionsUS20030088037 *Mar 15, 2002May 8, 2003The Dow Chemical CompanyMethod of making interpolymers and products made therefromUS20030114608 *Nov 15, 2002Jun 19, 2003Fina Technology, Inc.Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polyproyleneUS20030120013 *Jan 13, 2003Jun 26, 2003Dow Global Technologies, Inc.Ethylene copolymer compositionsUS20030130430 *Jan 23, 2003Jul 10, 2003Cozewith Charles C.Blends made from propylene ethylene polymersUS20030162852 *Jan 6, 2003Aug 28, 2003Chaudhary Bharat I.Acoustical insulation foamsUS20030166457 *Feb 5, 2003Sep 4, 2003Peterson Thomas HenryCatalyst support method and polymerization with supported catalystsUS20030176611 *Nov 5, 2002Sep 18, 2003Stevens James C.Isotactic propylene copolymer fibers, their preparation and useUS20030194575 *Nov 5, 2002Oct 16, 2003Li-Min TauFilms comprising isotactic propylene copolymersUS20030195299 *Nov 5, 2002Oct 16, 2003Stevens James C.Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiersUS20030195300 *Nov 5, 2002Oct 16, 2003Stevens James C.Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agentUS20030204017 *May 5, 2002Oct 30, 2003Stevens James C.Isotactic propylene copolymers, their preparation and useUS20030236365 *Jun 24, 2002Dec 25, 2003Fina Technology, Inc.Polyolefin production with a high performance support for a metallocene catalyst systemUS20040009314 *Feb 21, 2003Jan 15, 2004Ahlgren Kelly R.Heat shrinkable films containing single site catalyzed copolymersUS20040024138 *Jul 25, 2003Feb 5, 2004Allermann Gerd ArthurSilane crosslinkable polyethyleneUS20040034169 *Jun 4, 2003Feb 19, 2004Union Carbide Chemicals & Plastics Technology CorporationPolymer compositions and method of making pipesUS20040048019 *Aug 22, 2003Mar 11, 2004Ohlsson Stefan BertilStretch filmUS20040048984 *Aug 13, 2003Mar 11, 2004Weiging WengPropylene polymers incorporating polyethylene macromersUS20040053022 *Aug 18, 2003Mar 18, 2004Ohlsson Stefan BertilShrink filmUS20040077787 *Feb 27, 2002Apr 22, 2004Karande Seema V.Fabricated articles prepared from blends of substantially random ethylene/propylene/vinyl aromatic interpolymers with polypropyleneUS20040077806 *Jun 24, 2003Apr 22, 2004Weiqing WengPropylene diene copolymerized polymersUS20040087749 *Apr 2, 2003May 6, 2004Agarwal Pawan KumarArticles formed from propylene diene copolymersUS20040087750 *Jun 24, 2003May 6, 2004Agarwal Pawan KumarPropylene diene copolymersUS20040106739 *Feb 19, 2002Jun 3, 2004Cheung Yunwa WilsonBlends of substantially random interpolymers with enhanced thermal performanceUS20040110886 *Nov 24, 2003Jun 10, 2004Karandinos Anthony G.Polypropylene-based adhesive compositionsUS20040116609 *Jul 3, 2003Jun 17, 2004Sudhin DattaElastic blends comprising crystalline polymer and crystallizable polymers of propyleneUS20040152842 *Jun 11, 2002Aug 5, 2004Dunaway David B.Metallocene-produced bery low density polyethylenes or linear low density polyethylenes as impact modifiersUS20040198912 *Apr 5, 2004Oct 7, 2004Dharmarajan N. RajaThermoplastic filled membranes of propylene copolymersUS20040198930 *Jul 19, 2002Oct 7, 2004Sita Lawrence R.Method for production of multimodal polyolefins of tunable composition, molecular weight, and polydispersityUS20040236025 *Jan 20, 2004Nov 25, 2004Fina Technology, Inc.High gloss polyethylene articlesUS20040242784 *May 3, 2003Dec 2, 2004Lin-Min TauThermoplastic elastomer compositionsUS20040242814 *May 27, 2003Dec 2, 2004Smita KackerCopolymers of ethylene and/or alpha-olefins and vicinally disubstituted olefinsUS20040242815 *Jul 11, 2002Dec 2, 2004Luigi ResconiMultistep process for the (co) polymerization of olefinsUS20050020778 *Aug 16, 2004Jan 27, 2005Degroot Alexander W.High melt strength polymers and method of making sameUS20050065018 *Jun 7, 2004Mar 24, 2005(1) Repsol Quimica S.A.Preparation and use of heterogeneous catalyst components for olefins polymerizationUS20050065019 *Jul 16, 2004Mar 24, 2005Repsol Quimica S.A.Catalytic systems for the polimerisation and copolimerisation of alpha-olefinsUS20050065286 *Aug 17, 2004Mar 24, 2005Degroot Alexander W.High melt strength polymers and method of making sameUS20050131155 *Feb 2, 2005Jun 16, 2005Cozewith Charles C.Blends made from propylene ethylene polymersUS20050131169 *Jan 14, 2005Jun 16, 2005Sun-Chueh KaoMethod for preparing a catalyst system and its use in a polymerization processUS20050148742 *Dec 14, 2004Jul 7, 2005Hagerty Robert O.Method for controlling sheeting in gas phase reactorsUS20050159302 *Jan 14, 2005Jul 21, 2005Peterson Thomas H.Catalyst support method and polymerization with supported catalystsUS20050159553 *Jan 14, 2005Jul 21, 2005Charles CozewithArticles made from blends made from propylene ethylene polymersUS20050187351 *Mar 21, 2005Aug 25, 2005Dow Global Technologies, Inc.Method of making interpolymers and products made therefromUS20050234198 *Apr 20, 2004Oct 20, 2005Fina Technology, Inc.Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst systemUS20060009596 *Jun 22, 2005Jan 12, 2006Nova Chemicals (International) S.A.Novel borate activatorUS20060025640 *Oct 1, 2003Feb 2, 2006Teresa KarjalaLiquid and del-like low molecular weight ethylene polymersUS20060041073 *Aug 12, 2005Feb 23, 2006Union Carbide Chemicals & Plastics Technology CorporationPolymer compositions and method of making pipesUS20060052238 *Sep 6, 2005Mar 9, 2006Lee Eun JSupported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalystUS20060100335 *Oct 17, 2003May 11, 2006Selim YalvacHighly filled polymer compositionsUS20060116490 *Dec 1, 2004Jun 1, 2006Paczkowski Nicola SMetallocene catalysts, their synthesis and their use for the polymerization of olefinsUS20060264587 *May 17, 2005Nov 23, 2006Thorsten SellCatalyst composition for olefin polymerizationUS20060276593 *Jun 21, 2006Dec 7, 2006Van Dun Jozef JHigh density ethylene homopolymers and blend compositionsUS20070055031 *Nov 17, 2003Mar 8, 2007Romer Duane ROlefin polymerization catalyst composition comprising group 13 amide derivativesUS20070066773 *Dec 8, 2004Mar 22, 2007Innovene Europe LimitedPolymerisation processUS20070082806 *Dec 6, 2006Apr 12, 2007Paczkowski Nicola SMetallocene catalysts, their synthesis and their use for the polymerization of olefinsUS20070088129 *Jun 28, 2006Apr 19, 2007Dow Global Technologies Inc.Process for preparing copolymers and blend compositions containing the sameUS20070203314 *Feb 20, 2007Aug 30, 2007Dupont Dow Elastomers, LlcShear thinning ethylene/alpha-olefin interpolymers and their preparationUS20070249799 *May 16, 2007Oct 25, 2007Thorsten SellCatalyst composition for olefin polymerizationUS20070260016 *Apr 18, 2007Nov 8, 2007Best Steven ALinear low density polymer blends and articles made therefromUS20080167421 *Jul 10, 2006Jul 10, 2008Selim YalvacSilane-Grafted Olefin Polymers, Compositions and Articles Prepared Therefrom, and Methods For Making the SameUS20080202075 *Jul 7, 2006Aug 28, 2008Kurt KronawittleithnerLayered Film Compositions, Packages Prepared Therefrom, and Methods of UseUS20080249231 *Apr 3, 2008Oct 9, 2008Sudhin DattaSoft homogeneous isotactic polypropylene compositionsUS20080262174 *Sep 8, 2006Oct 23, 2008Sk Energy Co., Ltd.Homogeneous Catalyst System For Producing Ethylene Homopolymer or Ethylene Copolymers With Alpha-OlefinsUS20080287588 *May 16, 2007Nov 20, 2008Danny Van HoyweghenThermoplastic elastomer compositions, methods for making the same, and articles made therefromUS20080293853 *Jul 30, 2007Nov 27, 2008Bayer Materialscience AgMethod for producing carbon nanotube/polymer mixtures by gas-phase polymerizationUS20090018279 *Jul 10, 2008Jan 15, 2009Hagerty Robert OMethod for controlling sheeting in gas phase reactorsUS20090053959 *Aug 15, 2008Feb 26, 2009Sudhin DattaSoft and Elastic Nonwoven Polypropylene CompositionsUS20090054861 *Jun 28, 2005Feb 26, 2009Dow Global Technoligies Inc.Adhesion promoters for multistructural laminatesUS20090111946 *Oct 6, 2008Apr 30, 2009Sudhin DattaSoft Heterogeneous Isotactic Polypropylene CompositionsUS20090153546 *Feb 24, 2009Jun 18, 2009Sharp Kabushiki KaishaDriving circuit for display device, and display deviceUS20090198025 *Jan 29, 2009Aug 6, 2009Pannell Richard BMethod for seed bed treatment before a polymerization reactionUS20090270545 *Oct 29, 2009Abdelhadi SahnounePropylene Copolymers In Soft Thermoplastic BlendsUS20100137521 *Apr 14, 2008Jun 3, 2010Ravishankar Periagaram SThermoplastic Polymer Compositions, Methods for Making the Same, and Articles Made TherefromUS20100222518 *Sep 29, 2008Sep 2, 2010Basell Poliolefine Italia S.R.L.Heterophasic polyolefin compositions having improved tensile propertiesUS20110144289 *Dec 6, 2010Jun 16, 2011Nova Chemicals (International) S.A.Multi reactor processUS20110209897 *Nov 11, 2009Sep 1, 2011David DentonOlefin-Based Polymers, a Process for Making the Same, and a Medium Voltage Cable Sheath Comprising the SameUS20130253154 *Sep 28, 2011Sep 26, 2013Lg Chem ,Ltd.Method for preparing supported hybrid metallocene catalystUSRE37400 *Aug 27, 1998Oct 2, 2001Exxon Chemical Patents Inc.Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalystsUSRE37788 *Aug 27, 1998Jul 9, 2002Exxon Chemical Patents, Inc.Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsUSRE42276Apr 5, 2011Dow Global Technologies LlcHigh melt strength polymers and method of making sameUSRE43004Dec 6, 2011Dow Global Technologies LlcHigh melt strength polymers and method of making sameCN1117101C *Jan 31, 1997Aug 6, 2003Pcd聚合物有限公司Process for preparing catalyst supports and supported polyolefin catalystsand also their use for prepaation of polyolefinsEP0600425A1Nov 29, 1993Jun 8, 1994W.R. Grace &amp; Co.-Conn.Heat shrinkable films containing single site catalyzed copolymers having long chain branchingEP0683179A1May 15, 1995Nov 22, 1995Phillips Petroleum CompanyMetallocene catalyst systems, preparation, and useEP0701897A2Sep 8, 1995Mar 20, 1996W.R. GRACE &amp; CO.-CONN.Thermoplastic multilayer film for use in packaging waterEP0764653A2 *Aug 30, 1990Mar 26, 1997The Dow Chemical CompanyConstrained geometry addition polymerization catalysts, processes for their preparation, precursors therefor, methods of use, and novel polymers formed therewithEP1624000A1Apr 14, 2000Feb 8, 2006Univation Technologies, LLCA polymerization process for producing easier processing polymersEP1634919A1Sep 5, 2005Mar 15, 2006Advanced Elastomer Systems, L.P.Improved thermoplastic vulcanizatesEP1803747A1Dec 30, 2005Jul 4, 2007Borealis Technology OySurface-modified polymerization catalysts for the preparation of low-gel polyolefin filmsEP1905807A2Sep 17, 2004Apr 2, 2008Dow Gloval Technologies Inc.Interpolymers suitable for use in hot melt adhesives and processes to prepare sameEP1964884A1Oct 17, 2003Sep 3, 2008Dow Global Technologies, Inc.Highly filled polymer compositionsEP2045304A2Dec 21, 2000Apr 8, 2009ExxonMobil Chemical Patents Inc.Polypropylene-Based Adhesive CompositionsEP2112173A1Apr 16, 2008Oct 28, 2009ExxonMobil Chemical Patents Inc.Catalyst compounds and use thereofEP2172490A1Oct 3, 2008Apr 7, 2010Ineos Europe LimitedControlled polymerisation processEP2261292A2Oct 15, 2003Dec 15, 2010ExxonMobil Chemical Patents Inc.Polyolefin adhesive compositionsEP2277928A1Nov 2, 1999Jan 26, 2011Dow Global Technologies Inc.Shear thinning ethylene/alpha-olefin interpolymers and their preparationEP2277941A1Aug 16, 2000Jan 26, 2011Dow Global Technologies Inc.Free-flowing polymer compositionEP2357035A1Jan 13, 2010Aug 17, 2011Ineos Europe LimitedPolymer powder storage and/or transport and/or degassing vesselsEP2363420A1Jun 11, 2007Sep 7, 2011Dow Global Technologies LLCFunctionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the sameEP2363444A1Jun 11, 2007Sep 7, 2011Dow Global Technologies LLCFunctionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the sameEP2363445A1Jun 11, 2007Sep 7, 2011Dow Global Technologies LLCFunctionalized propylene interpolymers, compositions and articles prepared therefrom, and methods for making the sameEP2368896A1Apr 8, 2010Sep 28, 2011ExxonMobil Chemical Patents Inc.Mono-indenyl transition metal compounds and polymerization therewithEP2383298A1Apr 30, 2010Nov 2, 2011Ineos Europe LimitedPolymerization processEP2383301A1Apr 30, 2010Nov 2, 2011Ineos Europe LimitedPolymerization processEP2407495A1Jul 10, 2006Jan 18, 2012Dow Global Technologies LLC (formerly Known As Dow Global Technologies Inc.)Silane-Grafted Olefin Polymers, Compositions and Articles Prepared Therefrom, and Methods For Making The sameEP2407496A1Jul 10, 2006Jan 18, 2012Dow Global Technologies LLC (formerly Known As Dow Global Technologies Inc.)Silane-grafted olefin polymers, compositions and articles prepared therefrom, and methods for making the sameEP2573091A1Sep 23, 2011Mar 27, 2013Lummus Novolen Technology GmbhProcess for recycling of free ligand from their corresponding metallocene complexesEP3006487A1Aug 16, 2000Apr 13, 2016Dow Global Technologies LLCFree flowing polymer compositionWO1995007939A1Aug 29, 1994Mar 23, 1995Exxon Chemical Patents Inc.Polymerization catalyst systems, their production and useWO1995013317A1 *Nov 7, 1994May 18, 1995Mobil Oil CorporationA composition comprising a blend of an ethylene polymer or copolymer with sorbitol or a sorbitol derivativeWO1996016093A2Nov 22, 1995May 30, 1996Exxon Chemical Patents Inc.Method for making supported catalyst systems, and catalyst systems therefromWO1998001481A1 *Jun 17, 1997Jan 15, 1998Basf AktiengesellschaftProcess for preparing carrier-borne transition metal catalystsWO2001068550A2Mar 13, 2001Sep 20, 2001Dow Global Technologies Inc.Reinforcing polymer containing concrete and process to make sameWO2002045854A2 *Nov 30, 2001Jun 13, 2002Univation Technologies, LlcMethod for preparing a catalyst support and polymerization with supported catalystsWO2002045854A3 *Nov 30, 2001Oct 17, 2002Univation Tech LlcMethod for preparing a catalyst support and polymerization with supported catalystsWO2004055067A1Nov 17, 2003Jul 1, 2004Dow Global Technologies Inc.Olefin polymerization catalyst composition comprising group 13 amide derivativesWO2005113622A1Apr 13, 2005Dec 1, 2005Exxonmobil Chemical Patents Inc.Multiple catalyst and reactor system for olefin polymerization and polymers produced therefromWO2005118605A1May 23, 2005Dec 15, 2005Exxonmobil Chemical Patents, Inc.Transition metal compounds for olefin polymerization and oligomerizationWO2007124877A1 *Apr 23, 2007Nov 8, 2007Basell Polyolefine GmbhSupported metal alkyl compound and process for the polymerization of olefins in its presenceWO2008079483A1Oct 17, 2007Jul 3, 2008Exxonmobil Chemical Patents Inc.Process of making polymer blendsWO2008079509A1Oct 26, 2007Jul 3, 2008Exxonmobil Chemical Patents Inc.Process of making polymer blendsWO2008124040A1Apr 3, 2008Oct 16, 2008Exxonmobil Chemical Patents Inc.Soft heterogeneous isotactic polyroplene compositionsWO2009026207A1Aug 18, 2008Feb 26, 2009Exxonmobil Chemical Patents Inc.Soft and elastic nonwoven polypropylene compositionsWO2009131747A1Feb 26, 2009Oct 29, 2009Exxonmobil Chemical Patents Inc.Propylene copolymers in soft thermoplastic blendsWO2009146167A2 *Apr 14, 2009Dec 3, 2009Fina Technology, Inc.Fluorinated impregnated catalyst systems and methods of forming the sameWO2009146167A3 *Apr 14, 2009Feb 25, 2010Fina Technology, Inc.Fluorinated impregnated catalyst systems and methods of forming the sameWO2011017092A1Jul 27, 2010Feb 10, 2011Univation Technologies, LlcPolymerization process using a supported constrained geometry catalystWO2011078923A1Nov 16, 2010Jun 30, 2011Univation Technologies, LlcMethods for producing catalyst systemsWO2011079042A2Dec 17, 2010Jun 30, 2011Exxonmobil Chemical Patents Inc.Process for producing novel synthetic basestocksWO2011085937A1Dec 24, 2010Jul 21, 2011Ineos Europe LimitedPolymer powder storage and/or transport and/or degassing vesselsWO2011134797A1Apr 13, 2011Nov 3, 2011Ineos Commercial Services Uk LimitedPolymerization processWO2011134798A1Apr 13, 2011Nov 3, 2011Ineos Commercial Services Uk LimitedPolymerization processWO2011159400A1May 3, 2011Dec 22, 2011Exxonmobil Chemical Patents Inc.Nonwoven fabrics made from polymer blends and methods for making sameWO2012072417A1Nov 16, 2011Jun 7, 2012Ineos Commercial Services Uk LimitedPolymerisation control processWO2013025351A1Aug 1, 2012Feb 21, 2013Ineos Usa LlcApparatus for stirring polymer particlesWO2013041619A1Sep 20, 2012Mar 28, 2013Lummus Novolen Technology GmbhProcess for recycling of free ligand from their corresponding metallocene complexesWO2013056979A1Oct 3, 2012Apr 25, 2013Ineos Europe AgPolymer degassing process controlWO2013070340A1Oct 1, 2012May 16, 2013E. I. Du Pont De Nemours And CompanyMethod to form an aqueous dispersion of an ionomer-polyolefin blendWO2013115912A1Dec 13, 2012Aug 8, 2013Exxonmobil Chemical Patents Inc.Process for the production of polymeric compositions useful as oil modifiersWO2016046709A1Sep 18, 2015Mar 31, 2016Nova Chemicals (International) S.A.Shrink film from single site catalyzed polyethylene* Cited by examinerClassifications U.S. Classification502/104, 526/129, 526/943, 502/125, 502/116, 502/114, 502/120, 502/115, 502/113, 502/103, 502/117, 502/121International ClassificationC08F4/655, C08F4/652, C08F4/60, C08F4/6592, C08F4/64, C08F110/06, C08F210/16, C08F4/659, C08F10/06, C08F10/00, C07F7/10, C08F110/02, C08F4/642, C07F7/00, B01J31/18, C08F210/06, C08F4/00, C07F17/00, C08F210/18Cooperative ClassificationY10S526/943, C08F210/16, C08F4/65912, C08F4/6592, C08F110/02, C08F110/06, C08F210/18, C08F210/06, C08F4/65908, C08F4/65916, C07F17/00, C08F10/00, C08F10/06, C07F7/10European ClassificationC08F10/06, C08F10/00, C07F7/10, C07F17/00, C08F210/16Legal EventsDateCodeEventDescriptionJan 16, 1991ASAssignmentOwner name: EXXON CHEMICAL PATENTS INC., A CORP. OF DEFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CANICH, JO ANN M.;LICCIARDI, GARY F.;REEL/FRAME:005568/0388Effective date: 19900913Mar 31, 1995FPAYFee paymentYear of fee payment: 4Mar 18, 1999FPAYFee paymentYear of fee payment: 8May 11, 1999REMIMaintenance fee reminder mailedMar 28, 2003FPAYFee paymentYear of fee payment: 12RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services