# US 4,398,005 A · Novel polymerization catalyst and process for using same to polymerize olefins > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,398,005 A - Document ID: US4398005A - Status: Granted - Kind: A - Application number: 06/401,628 - Filed: 1982-07-26 - Granted: 1983-08-09 - Earliest claimed: 1981-01-23 - Assignees: Gulf Research & Development Company - Inventors: Harold E. Swift; Richard W. Lunden - Web page: https://patentgrep.com/patent/US4398005A ## CPC - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract There is provided a solid, particulate, catalytic complex suitable for the stereospecific polymerization of olefins prepared by reducing TiCl.sub.4, contacting the resultant reduced solid with a complexing agent to obtain a treated solid and contacting the treated solid with TiCl.sub.4 in the presence of silica which has been treated with an aromatic ester. When such a catalyst complex is combined with a suitable activator to polymerize olefins, a high degree of stereospecificity is attained, the activity of the catalyst complex is reduced for polymerization control and the efficiency of the titanium employed is enhanced. ## Claims ### Claim 1 A process for the polymerization of olefins which comprises contacting said olefin at elevated temperatures and elevated pressures with an activator and a solid, particulate, catalyst complex prepared by a process comprising reducing TiCl.sub.4, containing the resultant reduced solid with a complexing agent to obtain a treated solid and contacting the treated solid with TiCl.sub.4 in the presence of silica which has been treated with an aromatic ester. ### Claim 2 (depends on 1) A process as defined in claim 1 wherein said aromatic ester is selected from the group consisting of those having the following formulas: ##STR2## wherein each Y is a member selected from the group consisting of alkyl radicals having from about one to about eight carbon atoms and alkenyl radicals having from about two to about eight carbon atoms, each X is a member selected from the group consisting of hydrogen, halogen radicals, alkoxy radicals having from about one to about eight carbon atoms, alkyl radicals having from about one to about eight carbon atoms and alkenyl radicals having from about two to about eight carbon atoms, and x has a value of one or two. ### Claim 3 (depends on 1) A process as defined in claim 1 wherein said aromatic ester is ethyl benzoate. ### Claim 4 (depends on 1) A process as defined in claim 1 wherein said silica has a mean particle size in the range of about 1 to about 100 microns. ### Claim 5 (depends on 1) A process as defined in claim 1 wherein said silica has a mean particle size in the range of about 1 to about 25 microns. ### Claim 6 (depends on 2) A process as defined in claim 2 wherein said silica has a mean particle size in the range of about 1 to about 100 microns. ### Claim 7 (depends on 2) A process as defined in claim 2 wherein said silica has a mean particle size in the range of about 1 to about 25 microns. ### Claim 8 (depends on 3) A process as defined in claim 3 wherein said silica has a mean particle size in the range of about 1 to about 100 microns. ### Claim 9 (depends on 3) A process as defined in claim 3 wherein said silica has a mean particle size in the range of about 1 to about 25 microns. ### Claim 10 (depends on 1) A process as defined in claim 1 wherein said silica is calcined at a temperature in the range of about 350.degree. to about 700.degree. C. for about one to about five hours prior to being treated with said aromatic ester. ### Claim 11 (depends on 1) A process as defined in claim 1 wherein said silica is calcined at a temperature in the range of about 400.degree. to about 500.degree. C. for about two to about three hours prior to being treated with said aromatic ester. ### Claim 12 (depends on 2) A process as defined in claim 2 wherein said silica is calcined at a temperature in the range of about 350.degree. to about 700.degree. C. for about one to about five hours prior to being treated with said aromatic ester. ### Claim 13 (depends on 2) A process as defined in claim 2 wherein said silica is calcined at a temperature in the range of about 400.degree. to about 500.degree. C., for about two to about three hours prior to being treated with said aromatic ester. ### Claim 14 (depends on 3) A process as defined in claim 3 wherein said silica is calcined at a temperature in the range of about 350.degree. to about 700.degree. C. for about one to about five hours prior to being treated with said aromatic ester. ### Claim 15 (depends on 3) A process as defined in claim 3 wherein said silica is calcined at a temperature in the range of about 400.degree. to about 500.degree. C. for about two to about three hours prior to being treated with said aromatic ester. ### Claim 16 (depends on 1) A process as defined in claim 1 wherein said silica is treated with said aromatic ester by introducing them into a hydrocarbon solvent, the molar ratio of aromatic ester to silica being in the range of about 1:10 to about 1:1, and heating the resultant slurry to a temperature in the range of about 70.degree. to about 300.degree. C. for about one to about ten hours. ### Claim 17 (depends on 1) A process as defined in claim 1 wherein said silica is treated with said aromatic ester by introducing them into a hydrocarbon solvent, the molar ratio of aromatic ester to silica being in the range of about 1:8 to about 1:2, and heating the resultant slurry to a temperature in the range of about 100.degree. to about 200.degree. C. for about two to about five hours. ### Claim 18 (depends on 2) A process as defined in claim 2 wherein said silica is treated with said aromatic ester by introducing them into a hydrocarbon solvent, the molar ratio of aromatic ester to silica being in the range of about 1:10 to about 1:1, and heating the resultant slurry to a temperature in the range of about 70.degree. to about 300.degree. C. for about one to about ten hours. ### Claim 19 (depends on 2) A process as defined in claim 2 wherein said silica is treated with said aromatic ester by introducing them into a hydrocarbon solvent, the molar ratio of aromatic ester to silica being in the range of about 1:8 to about 1:2, and heating the resultant slurry to a temperature in the range of about 100.degree. to about 200.degree. C. for about two to about five hours. ### Claim 20 (depends on 3) A process as defined in claim 3 wherein said silica is treated with said aromatic ester by introducing them into a hydrocarbon solvent, the molar ratio of aromatic ester to silica being in the range of about 1:10 to about 1:1, and heating the resultant slurry to a temperature in the range of about 70.degree. to about 300.degree. C. for about one to about ten hours. ### Claim 21 (depends on 3) A process as defined in claim 3 wherein said silica is treated with said aromatic ester by introducing them into a hydrocarbon solvent, the molar ratio of aromatic ester to silica being in the range of about 1:8 to about 1:2, and heating the resultant slurry to a temperature in the range of about 100.degree. to about 200.degree. C. for about two to about five hours. ### Claim 22 (depends on 1) A process as defined in claim 1 wherein said TiCl.sub.4 is reduced to a solid product based on TiCl.sub.3 by means of treatment with a reducing agent of the formula AlR.sub.n X.sub.3-n, wherein R is a hydrocarbon radical containing from about 1 to about 18 carbon atoms, X is halogen and n is an integer greater than 0 but no greater than 3, said treatment being conducted in an inert medium. ### Claim 23 (depends on 2) A process as defined in claim 2 wherein said TiCl.sub.4 is reduced to a solid product based on TiCl.sub.3 by means of treatment with a reducing agent of the formula AlR.sub.n X.sub.3-n, wherein R is a hydrocarbon radical containing from about 1 to about 18 carbon atoms, X a halogen and n is an integer greater than 0 but no greater than 3, said treatment being conducted in an inert medium. ### Claim 24 (depends on 3) A process as defined in claim 3 wherein said TiCl.sub.4 is reduced to a solid product based on TiCl.sub.3 by means of treatment with a reducing agent of the formula AlR.sub.n X.sub.3-n, wherein R is a hydrocarbon radical containing from about 1 to about 18 carbon atoms, X is halogen and n is an integer greater than 0 but no greater than 3, said treatment being conducted in an inert medium. ### Claim 25 (depends on 1) A process as defined in claim 1 wherein said complexing agent is an organic compound containing groups capable of donating one or more pairs of electrons selected from the group consisting of ethers, thioethers, thiols, phosphines, stibines, arsines, amines, amides, ketones and esters, said treatment being conducted in an inert diluent. ### Claim 26 (depends on 2) A process as defined in claim 2 wherein said complexing agent is an organic compound containing groups capable of donating one or more pairs of electrons selected from the group consisting of ethers, thioethers, thiols, phosphines, stibines, arsines, amines, amides, ketones and esters, said treatment being conducted in an inert diluent. ### Claim 27 (depends on 3) A process as defined in claim 3 wherein said complexing agent is an organic compound containing groups capable of donating one or more pairs of electrons selected from the group consisting of ethers, thioethers, thiols, phosphines, stibines, arsines, amines, amides, ketones and esters, said treatment being conducted in an inert diluent. ### Claim 28 (depends on 1) A process as defined in claim 1 wherein said complexing agent is selected from the group consisting of those having the formulas R'--O--R", R'--S--R", R'--N--R" and R'--S--H, wherein R' and R" are each a hydrocarbon radical containing from 1 to 15 carbon atoms. ### Claim 29 (depends on 2) A process as defined in claim 2 wherein said complexing agent is selected from the group consisting of those having the formulas R'--O--R", R'--S--R", R'--N--R" and R'--S--H, wherein R' and R" are each a hydrocarbon radical containing from 1 to 15 carbon atoms. ### Claim 30 (depends on 3) A process as defined in claim 3 wherein said complexing agent is selected from the group consisting of those having the formulas R'--O--R", R'--S--R", R'--N--R" and R'--S--H, wherein R' and R" are each a hydrocarbon radical containing from 1 to 15 carbon atoms. ### Claim 31 (depends on 1) A process as defined in claim 1 wherein the weight percent of the treated silica in the catalytic complex is in the range of about 90 to about 10. ### Claim 32 (depends on 1) A process as defined in claim 1 wherein the weight percent of the treated silica in the catalytic complex is in the range of about 60 to about 40. ### Claim 33 (depends on 2) A process as defined in claim 2 wherein the weight percent of the treated silica in the catalytic complex is in the range of about 90 to about 10. ### Claim 34 (depends on 2) A process as defined in claim 2 wherein the weight percent of the treated silica in the catalytic complex is in the range of about 60 to about 40. ### Claim 35 (depends on 3) A process as defined in claim 3 wherein the weight percent of the treated silica in the catalytic complex is in the range of about 90 to about 10. ### Claim 36 (depends on 3) A process as defined in claim 3 wherein the weight percent of the treated silica in the catalytic complex is in the range of about 60 to about 40. ### Claim 37 (depends on 1) A process as defined in claim 1 wherein said activator has the formula AlR"'.sub.m X'.sub.3-m wherein R"' is a hydrocarbon radical containing from 1 to 18 carbon atoms, X' is halogen and m is a number greater than 0 but no greater than 3. ### Claim 38 (depends on 2) A process as defined in claim 2 wherein said activator has the formula AlR"'.sub.m X'.sub.3-m wherein R"' is a hydrocarbon radical containing from 1 to 18 carbon atoms, X' is halogen and m is a number greater than 0 but no greater than 3. ### Claim 39 (depends on 3) A process as defined in claim 3 wherein said activator has the formula AlR"'.sub.m X'.sub.3-m wherein R"' is a hydrocarbon radical containing from 1 to 18 carbon atoms, X' is halogen and m is a number greater than 0 but no greater than 3.