# US 5,349,033 A · Process for the preparation of polyolefin > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,033 A - Document ID: US5349033A - Status: Granted - Kind: A - Application number: 08/117,634 - Filed: 1993-09-07 - Granted: 1994-09-20 - Earliest claimed: 1986-06-14 - Assignees: Hoechst Aktiengesellschaft - Inventors: Gerhard Thum - Web page: https://patentgrep.com/patent/US5349033A ## CPC - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F 2410/06: Catalyst characterized by its size - Y10S 526/908: Containing catalyst of specified particle size - Y10S 526/909: Polymerization characterized by particle size of product - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract It is possible to obtain globular polymers in the polymerization of alpha-olefins by means of a highly active, spherical Ziegler catalyst. The polymers have a high bulk density and can be processed very easily. ## Claims ### Claim 1 A process for the preparation of polyolefin by polymerization of alpha-olefins at a temperature from 50.degree. to 100.degree. C. and under a pressure of 3 to 12 bar in the presence of a catalyst composed of a spherical transition metal component (component A) and an organometallic compound (component B) in which the component A has been formed by reacting an organomagnesium compound with an organoaluminum compound, an electron donor, an organic chlorine compound and a transition metal compound, which comprises carrying out the polymerization in the presence of a catalyst in which the component A has been prepared by a) forming a solid composed of spherical particles having an average diameter of 20 to 110 .mu.m, a ratio of the mass average diameter D.sub.m, to the number average diameter D.sub.n is from 1.01 to 1.15 and a ratio of largest to smallest diameters ranging from 1.05 to 1.15 by reacting an organomagnesium compound of the formula R.sup.1 MgR.sup.2 in which R.sup.1 an R.sup.2 are identical or different alkyl radicals having 2 to 12 carbon atoms with an organoaluminum compound of the formula AlR.sup.3.sub.n (OR.sup.4).sub.3-n in which R.sup.3 and R.sup.4 are identical or different alkyl radicals having 1 to 8 carbon atoms and n denotes 0, 1, 2 or 3, or with the product from the reaction of aluminum trialkyls or aluminum dialkyl hydrides with diolefins containing 4 to 20 carbon atoms, and a primary, aliphatic chlorinated hydrocarbon, in an amount of 0.01 to 0.1 mol of the organoaluminum compound an 0.5 to 2.5 mol of the chlorinated hydrocarbon, relative to 1 mol of the organomagnesium compound, at a temperature from 30.degree. to 110.degree. C., b) treating the resulting solid with an electron donor consisting essentially of i) oxygen-containing compounds of aluminum, silicon, phosphorus or sulfur, or ii) nitrogen or silicon compounds having alkyl or aryl radicals containing 1 to 8 carbon atoms, or iii) aliphatic ethers, in an amount of 0.1 to 1 mol per gram atom of the magnesium present in the solid, at a temperature from 0.degree. to 100.degree. C., and c) reacting the supporting material thus obtained with a compound of the formula MeXm (OR.sup.5) 4-m in which Me is Ti or Zr, R.sup.5 is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom and m is an integer from 0 to 4, added dropwise to said supporting material in an amount of 0.1 to 2 mol per gram atom of the magnesium present in the supporting material, and at a temperature from 30.degree. to 120.degree. C. ### Claim 2 (depends on 1) The process as claimed in claim 1, wherein the electron donor is selected from the group consisting of alkoxy aluminum compounds, dialkyl sulfites, aliphatic ethers and alkyl silicates. ### Claim 3 (depends on 2) The process as claimed in claim 2, wherein the catalyst component A is in the form of spherical particles having an average diameter of 60 to 90 .mu.m. ### Claim 4 (depends on 3) The process as claimed in claim 3, wherein the catalyst component A has a ratio of mass average diameter, D.sub.m, to number average diameter D.sub.n, is from 1.01 to 1.2. ### Claim 5 (depends on 4) The process as claimed in claim 4, wherein the electron donor is added to the spherical-shaped solid in a molar ratio of 0.1 to 0.6 relative to 1 gram atom of Mg. ### Claim 6 (depends on 5) The process as claimed in claim 5, wherein the electron donor is dialkyl sulfite. ### Claim 7 (depends on 1) The process as claimed in claim 1, wherein the electron donor is selected from the group consisting of dialkyl sulfites, aliphatic ethers and alkyl silicates. ### Claim 8 (depends on 6) The process as claimed in claim 6, wherein polyethylene is prepared. ### Claim 9 (depends on 8) The process as claimed in claim 8, wherein said diameter of the polyethylene is from 600 to 1500 .mu.m. ### Claim 10 (depends on 1) The process as claimed in claim 1, wherein the electron donor is added to the spherical-shaped solid in a molar ratio of 0.1 to 0.6. ### Claim 11 (depends on 1) The process as claimed in claim 1, wherein the electron donor is dialkyl sulfite. ### Claim 12 (depends on 1) The process as claimed in claim 1, wherein polyethylene is prepared. ### Claim 13 (depends on 12) The process as claimed in claim 12, wherein said diameter of the polyethylene is from 600 to 1500 .mu.m. ### Claim 14 (depends on 10) The process as claimed in claim 10, wherein polyethylene is prepared. ### Claim 15 (depends on 12) The process as claimed in claim 12, wherein said diameter of the polyethylene is from 600 to 1500 .mu.m. ### Claim 16 A process for the preparation of a polyolefin by polymerization of alpha-olefins at a temperature from 50.degree. to 100.degree. C. and under a pressure of 3 to 12 bar in the presence of a catalyst composed of a spherical transition metal component (component A) and an organometallic compound (component B) in which the component A has been formed by reacting an organomagnesium compound with an organoaluminum compound, an electron donor, an organic chlorine compound and a transition metal compound, which comprises carrying out the polymerization in the presence of a catalyst in which the component A has been prepared by a) forming a solid composed of spherical particles having an average diameter of 20 to 110 .mu.m, a ratio of the mass average diameter D.sub.m, to the number average diameter Dn less than 1.5 and a ratio of largest to smallest diameters ranging from 1.05 to 1.15 by reacting an organomagnesium compound of the formula R.sup.1 MgR.sup.2 in which R.sup.1 an R.sup.2 are identical or different alkyl radicals having 2 to 12 carbon atoms with an organoaluminum compound of the formula AIR.sup.3 n (OR.sup.4) 3-n in which R.sup.3 and R.sup.4 are identical or different alkyl radicals having 1 to 8 carbon atoms and n denotes 0, 1, 2 or 3, or with the product from the reaction of aluminum trialkyls or aluminum dialkyl hydrides with diolefins containing 4 to 20 carbon atoms, and a primary, aliphatic chlorinated hydrocarbon, in an amount of 0.01 to 0.1 mol of the organoaluminum compound an 0.5 to 2.5 mol of the chlorinated hydrocarbon, relative to 1 mol of the organomagnesium compound, at a temperature from 30.degree. to 110.degree. C., b) treating the resulting solid with an electron donor wherein said electron donor is dialkyl sulfite and is present in an amount of 0.1. to 1 mol per gram atom of the magnesium present in the solid, at a temperature from 0.degree. to 100.degree. C., and c) reacting the supporting material thus obtained with a compound of the formula MeXm (OR.sup.5) 4-m in which Me is Ti or Zr, R.sup.5 is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom and m is an integer from 0 to 4, added dropwise to said supporting material in an amount of 0.1 to 2 mol per gram atom of the magnesium present in the supporting material, and at a temperature from 30.degree. to 120.degree. C. ### Claim 17 (depends on 16) The process as claimed in claim 16, wherein polyethylene is prepared. ### Claim 18 (depends on 16) The process as claimed in claim 16, wherein the electron donor is added to the spherical-shaped solid in a molar ratio of 0.1 to 0.6.