# US 5,346,872 A · Cocatalyst for vanadium/titanium containing polymerization catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,346,872 A - Document ID: US5346872A - Status: Granted - Kind: A - Application number: 08/010,737 - Filed: 1993-01-29 - Granted: 1994-09-13 - Earliest claimed: 1993-01-29 - Assignees: Quantum Chemical Corporation - Inventors: Raghu Menon; Albert P. Masino; Mark K. Reinking - Web page: https://patentgrep.com/patent/US5346872A ## CPC - B01J 31/2226: {Anionic ligands, i.e. the overall ligand carries at least one formal negative charge} - B01J 31/0212: {Alkoxylates} - B01J 31/128: {Mixtures of organometallic compounds} - B01J 31/143: {of aluminium} - B01J 31/1616: {Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00)} - C08F 110/02: Ethene - B01J 2531/46: Titanium - B01J 2531/56: Vanadium - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract The present invention relates to a novel catalyst component for ethylene polymerization comprising vanadium and titanium. Moreover, when the vanadium/titanium containing catalyst of the present invention is employed with an aluminum-containing cocatalyst enhanced activity as well as melt index is obtained. The present invention is directed to a novel halosilane cocatalyst component which, when used in conjunction with an aluminum containing cocatalyst, is effective in increasing the activity of a silica supported titanium/vanadium containing solid catalyst component in the polymerization of ethylene and/or .alpha.-olefins. In addition to the increased catalytic activity, the polymers produced by the present invention exhibit improved melt index values compared with melt index values typically obtained using prior art catalyst systems. Thus, the catalyst system of the instant invention represent an advancement in the art in view of the combination of increased activity, i.e., yield of polymer produced, and physical properties of the polyolefin product. In another aspect of the present invention, a process for polymerizing ethylene and/or .alpha.-olefins is disclosed. In this process at least one olefin is polymerized under olefin polymerization conditions utilizing the catalyst system of the present invention, which includes the solid catalyst component of the present invention, along with the first cocatalyst, an aluminum-containing compound, and the second cocatalyst, a halosilane. ## Claims ### Claim 1 A catalyst component for ethylene polymerization consisting essentially of a solid product obtained by the steps of: (a) pretreating a silica support to remove surface hydroxyl groups; (b) contacting said pretreated silica support with a magnesium-containing compound selected from the group consisting of magnesium compounds havng the formula ROMgX, where R is a C.sub.1 to C.sub.12 hydrocarbyl and X is a halogen; dihydrocarbyloxy magnesium, alkylmagnesium halides; magnesium aluminum-complexes having the formula (MgRR').sub.m (AlR.sub.3).sub.n where R, R' and R" are the same or different and are alkyl groups and the ratio of m/n is from about 0.5 to 10; and mixtures thereof; (c) drying the reaction mixture obtained in step (b) to form a solid product; (d) contacting said dried solid product of step (c) with at least one modifying compound selected from the group consiting of silicon halides, boron halides, aluminum halides, alkyl silicon halides, and mixtures thereof; (e) washing said product of step (d) with a hydrocarbon solvent; and (f) reacting the product of step (e) interchangeably or simultaneously with a vanadium-containing compound having the formula V(OR).sub.x (O).sub.y (X.sup.2).sub.z wherein R is a hydrocarbyl having from 1 to 18 carbon atoms; X.sup.2 is halogen; x is 0 or an integer from 1 to 5; y is 0 or 1; and z=(5-x-2y) or 4 or 3 when x=0, y=0; and titanium-containing compound having the structural formula TiX.sup.1.sub.p (OR.sup.1).sub.q where X is halogen; R.sup.1 is aryl, alkyl, aralkyl, cycloalkyl or alkylsilyl; p is an integer from 1 to 4; q is 0 or an integer from 1 to 3; and the sum of p and q is 4. ### Claim 2 (depends on 1) The catalyst component of claim 1 wherein the ROMgX compound is 2-methylpentyloxymagnesium chloride. ### Claim 3 (depends on 1) The catalyst component of claim 1 wherein the compound having the structural formula TiX.sup.1.sub.p (OR.sup.1).sub.q is selected from the group consisting of tetrahalotitaniums, alkoxytitanium trihalides, dialkoxytitanium dihalides, and mixtures thereof. ### Claim 4 (depends on 4) The catalyst component of claim 4 wherein p is 4, g is 0, and X is chloride. ### Claim 5 (depends on 4) The catalyst component of claim 4 wherein the titanium compound is titanium tetrachloride. ### Claim 6 (depends on 1) The catalyst component of claim 1 wherein said vanadium compound is selected from the group consisting of vanadium oxyhalides, vanadium alkoxides, vanadium carboxylates vanadium halides and mixtures thereof. ### Claim 7 An improved catalyst system for polymerizing .alpha.-olefins consisting essentially of a silica supported titanium/vanadium solid catalyst component prepared by the steps of: (a) pretrating a silica support to remove surface hydroxyl groups; (b) contacting said pretreated silica support with a magnesium-containing compound selected from the group consisting of hydrocarbyloxy magnesium halides having the formula ROMgX, where R is a C.sub.1 to C.sub.12 hydrocarbyl and X is a halogen; dihydrocarbyloxy magnesium; alkylmagnesium halides; magnesium aluminum-complexes having the formula (MgRR').sub.m (AlR.sub.3 ").sub.n wherein R, R' and R" are the same or different and are alkyl groups and the ratio of m/n is from about 0.05 to about 10; and mixtures thereof; (c) drying the reaction mixture obtained in step (b) to form a solid product; (d) contacting said dried solid product of step (c) with at least one modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides, and mixtures thereof; (e) washing said product of step (d) with a hydrocarbon solvent; (f) reacting the product of step (e) interchangeably or simultaneously with a vanadium-containing compound having the formula V(OR).sub.x (O).sub.y (X.sup.2).sub.z wherein R is a hydrocarbyl having from 1 to 18 carbon atoms; X.sup.2 is halogen; x is 0 or an integer from 1 to 5; y is 0 or 1; and z=(2-x-2y) or 4 or 3 when x=0, y=0; and a titanium-containing compound having the structural formula TiX.sup.1.sub.p (OR.sup.1).sub.q where X is halogen; R.sup.1 is aryl, alkyl, aralkyl, cycloalkyl or alkysilyl; p is an integer from 1 to 4; q is 0 or an integer from 1 to 3; and the sum of p and q is 4; and (g) adding an alkylaluminum first cocatalyst component, and at least one halosilane second cocatalyst component having the formula R.sup.3.sub.a SiX.sup.3.sub.b where X.sup.3 is halogen; R.sup.3 is hydrogen, alkoxy, alkyl, aryl, silyloxy or cycloalkyl; a is 0 or an integer from 1 to 3; and b is an integer from 1 to 4, with the proviso that the sum of a and b is 4 to the silica supported titanium/vanadium solid catalyst component during polymerization of said .alpha.-olefin. ### Claim 8 (depends on 7) The catalyst system of claim 7 wherein the halosilane compound is selected from the group of halosilanes consisting of trimethylchlorsilane, silicon tetrachloride, and trichlorosilane. ### Claim 9 (depends on 7) The catalyst system of claim 7 wherein the alkylaluminum compound is selected from the group consisting of trialkylaluminum, alkylaluminum halide, alkylaluminum hydride, aluminoxane and mixtures thereof. ### Claim 10 (depends on 9) The catalyst system of claim 9 wherein the alkylaluminum compound is triethylaluminum. ### Claim 11 (depends on 7) The catalyst system of claim 7 wherein the alkylaluminum component and the halosilane component are added to the solid catalyst component in a molar ratio from about 1:1:1 to about 1000:1000:1 based on aluminum:halosilane:solid catalyst. ### Claim 12 (depends on 7) The catalyst system of claim 7 wherein said ROMgX compound is 2-methylpentyloxymagnesium chloride. ### Claim 13 (depends on 7) The catalyst system of claim 7 wherein said compound having the structural formula TiX.sup.1.sub.p (OR.sup.1).sub.q is selected from the group consisting of tetrahalotitaniums, alkoxytitanium trihalides, dialkoxytitanium dihalides, and mixtures thereof. ### Claim 14 (depends on 13) The catalyst system according to claim 13 wherein p is 4, q is 0, and X is chloride. ### Claim 15 (depends on 14) The catalyst system of claim 14 wherein the titanium compound is titanium tetrachloride. ### Claim 16 (depends on 7) The catalyst system according to claim 7 wherein said vanadium compound having the structural formula V(OR).sub.x (O).sub.y (X.sup.2).sub.z is selected from the group consisting of vanadium oxyhalides, vanadium alkoxides, vanadium carboxylates, vanadium halides and mixtures thereof.