# US 5,710,229 A · Large-pole polyolefin, a method for its production and a procatalyst containing a transesterification product of a lower alcohol and a phthalic acid ester > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,710,229 A - Document ID: US5710229A - Status: Granted - Kind: A - Application number: 08/431,796 - Filed: 1995-05-01 - Granted: 1998-01-20 - Earliest claimed: 1991-05-09 - Assignees: Borealis Holding A/S - Inventors: Thomas Garoff; Timo Leinonen; Eero Iiskola - Web page: https://patentgrep.com/patent/US5710229A ## CPC - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F 110/06: Propene - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract The invention relates to a method for preparing polyolefins by polymerizing an olefin with a procatalyst composition prepared by bringing together MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester. The invention also relates to a polyolefin obtained by polymerizing an olefin in the presence of a procatalyst prepared by bringing together MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester, as well as to a procatalyst composition suitable for the preparation of a large-pore polyolefin, which composition has been prepared by bringing together MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester. ## Claims ### Claim 1 A process for making a procatalyst composition suitable for preparing polyolefins having a median pore diameter of at least 15 .mu.m, a) contacting and mixing together (i) a solid MgCl.sub.2 carrier selected from the group consisting of solid MgCl.sub.2 and MgCl.sub.2 impregnated on silica, (ii) a lower alcohol R.sub.1 OH wherein R.sub.1 is a C.sub.1 -C.sub.4 -alkyl group, (iii) a titanium compound, and (iv) a first alkyl ester of phthalic acid, wherein the alkyl moiety of said first alkyl ester of phthalic acid has at least 6 carbon atoms, to form a composition comprising a contacting product comprising b) heating said composition comprising said contacting product to a temperature of between 130.degree. C. and 140.degree. C. to transesterify said lower alcohol and said first alkyl ester of phthalic acid into a transesterification product comprising a second alkyl ester of phthalic acid, wherein the alkyl moiety of said second alkyl ester of phthalic acid is said C.sub.1 -C.sub.4 -alkyl group, R.sub.1 ; and c) separating and washing said transesterification product; and d) recovering said transesterification product as said procatalyst composition. ### Claim 2 (depends on 1) The process according to claim 1, wherein said washing step c) comprises: separating and washing said transesterification product; and reacting the washed transesterification product with an additional amount of titanium compound, thereby obtaining a further titanated transesterification product; and wherein said recovering step d) comprises recovering said further titanated transesterification product as said procatalyst composition. ### Claim 3 A procatalyst composition suitable for preparing polyolefins having a median pore diameter of at least 15 .mu.m, said composition being produced by a process which comprises: a) contacting and mixing together (i) a solid MgCl.sub.2 carrier selected from the group consisting of solid MgCl.sub.2 and MgCl.sub.2 impregnated on silica, (ii) a lower alcohol R.sub.1 OH wherein R.sub.1 is a C.sub.1 -C.sub.4 -alkyl group, (iii) a titanium compound, and (iv) a first alkyl ester of phthalic acid, wherein the alkyl moiety of said first alkyl ester of phthalic acid has at least 6 carbon atoms, to form a composition comprising a contacting product; b) heating said composition comprising contacting product to a temperature of between 130.degree. C. and 140.degree. C. to transesterify said lower alcohol and said first alkyl ester of phthalic acid and form a transesterification product comprising a second alkyl ester of phthalic acid, wherein the alkyl moiety of said second alkyl ester of phthalic acid is said C.sub.1 -C.sub.4 -alkyl group, R.sub.1 ; c) separating and washing said transesterification product; and d) recovering said transesterification product as said procatalyst composition. ### Claim 4 (depends on 3) The procatalyst composition according to claim 3, wherein said washing step c) comprises: separating and washing said transesterification product; and then reacting the washed transesterification product with an additional amount of titanium compound, thereby obtaining a further titanated transesterification product; and wherein said recovering step d) comprises recovering said further titanated transesterification product as said procatalyst composition. ### Claim 5 (depends on 3) The procatalyst composition according to claim 3, wherein said transesterification has been carried out in a solvent having a boiling point which exceeds the transesterification temperature. ### Claim 6 (depends on 5) The procatalyst composition according to claim 5, wherein said solvent is nonane or decane. ### Claim 7 (depends on 3) The procatalyst composition according to claim 3, wherein said lower alcohol R.sub.1 OH is ethanol. ### Claim 8 (depends on 3) The procatalyst composition according to claim 3, wherein said titanium compound is TiCl.sub.4. ### Claim 9 (depends on 3) The procatalyst composition according to claim 3, wherein said phthalic acid ester is diisohexyl phthalate, diisodecyl phthalate or ditridecyl phthalate. ### Claim 10 A method for preparing polyolefins having a median pore diameter of at least 15 .mu.m, comprising: (A) a polymerizing step, comprising contacting olefins with a procatalyst composition, wherein said procatalyst composition has been prepared by a process comprising: (a) contacting and mixing together (i) a solid MgCl.sub.2 carrier selected from the group consisting of solid MgCl.sub.2 and MgCl.sub.2 impregnated on silica, a (ii) lower alcohol R.sub.1 OH wherein R.sub.1 is a C.sub.1 -C.sub.4 -alkyl group, (iii) and a titanium compound to form a composition comprising a first reaction product, and reacting said composition comprising a first reaction product with a first alkyl ester of phthalic acid, wherein the alkyl moiety of said first alkyl ester of phthalic acid has at least 6 carbon atoms, to form a composition comprising a contacting product; (b) heating said composition comprising contacting product to a temperature of between 130.degree. C. and 140.degree. C. thereby transesterifying said lower alcohol and said first alkyl ester of phthalic acid into a transesterification product comprising a second alkyl ester of phthalic acid, wherein the alkyl moiety of said second alkyl ester of phthalic acid is said C.sub.1 -C.sub.4 -alkyl group, R.sub.1 ; (c) separating and washing said transesterification product; and (d) recovering the washed transesterification product as said procatalyst composition; and (B) recovering the polyolefin prepared with said procatalyst composition. ### Claim 11 (depends on 10) The method of preparing polyolefins according to claim 10, wherein after recovering the washed transesterification product of step (d), the washed transesterification product is reacted with an additional amount of titanium compound, thereby obtaining a further titanated transesterification product as said procatalyst composition. ### Claim 12 (depends on 10) The method according to claim 10, wherein said phthalic acid ester is diisohexyl phthalate. ### Claim 13 (depends on 10) The method according to claim 10, wherein said olefin is propylene. ### Claim 14 (depends on 10) The method according to claim 10, wherein said lower alcohol R.sub.1 OH is ethanol. ### Claim 15 (depends on 10) The method according to claim 10, wherein said titanium compound is TiCl.sub.4. ### Claim 16 (depends on 10) The method according to claim 10, wherein said phthalic acid ester is di-isodecyl phthalate or ditridecyl phthalate. ### Claim 17 (depends on 10) The method according to claim 10, wherein said polymerizing step further comprises simultaneously contacting said olefin with an organometallic cocatalyst. ### Claim 18 (depends on 17) The method according to claim 17, wherein said cocatalyst is trialkyl aluminum. ### Claim 19 (depends on 17) The method according to claim 17, wherein said polymerizing step further comprises simultaneously contacting said olefin with an external donor. ### Claim 20 (depends on 19) The method according to claim 19, wherein said external donor is cyclohexylmethyldimethoxy silane. ### Claim 21 (depends on 10) The method according to claim 10, wherein said phthalic acid ester is di-isodecyl phthalate. ### Claim 22 (depends on 21) The method according to claim 21, wherein said polyolefin has a large proportion of pores having a diameter of 10-100 .mu.m. ### Claim 23 (depends on 10) The method according to claim 10, wherein said phthalic acid ester is ditridecyl phthalate. ### Claim 24 (depends on 23) The method according to claim 23, wherein said polyolefin has a large proportion of pores having a diameter of 10-100 .mu.m. ### Claim 25 (depends on 10) A polyolefin having a median pore diameter of at least 15 .mu.m, which has been prepared by the process of claim 10. ### Claim 26 (depends on 25) The polyolefin according to claim 25, wherein said pores have a median diameter of at least 25 .mu.m. ### Claim 27 (depends on 25) The polyolefin according to claim 25, wherein said polyolefin has a pore volume of at minimum 0.30 ml/g. ### Claim 28 (depends on 27) The polyolefin according to claim 27, wherein said pore volume is at least 0.40 ml/g.