# US 2013/0158217 A1 · Polymerization initiating system and method to produce highly reactive olefin functional polymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0158217 A1 - Document ID: US20130158217A1 - Status: Published application - Kind: A1 - Application number: 13/328,569 - Filed: 2011-12-16 - Published: 2013-06-20 - Earliest claimed: 2011-12-16 - Assignees: Infineum International Limited; University of Massachusetts - Inventors: Rudolf Faust; Philip Dimitrov; Rajeev Kumar; Jacob Emert; Jun Hua - Web page: https://patentgrep.com/patent/US20130158217A1 ## CPC - C08F 110/10: Isobutene - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A method for producing highly reactive olefin polymers wherein at least 50 mol. % of the polymer chains have terminal double bonds, and a novel polymerization initiating system for accomplishing same. ## Claims ### Claim 1 A process for the preparation of polybutene having an exo-olefin content of at least 50 mol. %, which process comprises contacting isobutene or an isobutene-containing monomer mixture, with a Lewis acid catalyst complexed with an oxygen and/or sulfur-containing Lewis base, in a substantially or completely apolar solvent, and initiating polymerization of said isobutene or an isobutene-containing monomer mixture with an initiator, wherein said Lewis acid catalyst is a Lewis acid of the formula MR″mYn, wherein M is a metal selected from Fe, Ga, Hf, Zr and W; R″ is a hydrocarbyl group; Y is halogen; m is 0 or an integer of 1 to 5; and n is an integer of 1 to 6, with the proviso that m+n is equal to the valency of metal M; and the initiator is a compound of the formula RX, wherein X is a halide; R is a hydrocarbyl group capable of forming a stable carbocation, and wherein the carbon linking group R to group X is tertiary, benzylic or allylic. ### Claim 2 (depends on 1) The process of claim 1, wherein M is Ga or Fe, and R″ is a C1 to Cg alkyl group. ### Claim 3 (depends on 1) The process of claim 1, wherein m is 0 or 1. ### Claim 4 (depends on 1) The process of claim 1, wherein Y is Cl or Br. ### Claim 5 (depends on 1) The process of claim 1, wherein said Lewis base is selected from acyclic dihydrocarbyl ethers, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, basic cyclic ethers having a 5 to 7 membered cyclic group, dihydrocarbyl ketones, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, C1 to C12 aliphatic alcohols, C1 to C12 aliphatic aldehydes, acyclic aliphatic esters wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, cyclic aliphatic esters having a 5 to 7 membered cyclic group, dialkyl sulfides, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, and basic dihydrocarbyl thiocarbonyl compounds, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, and mixtures thereof ### Claim 6 (depends on 5) The process of claim 5, wherein said Lewis base is selected from acyclic dialkyl ethers, wherein each alkyl group is independently selected from C1 to C4 alkyl, cyclic ethers having a 5 to 7 membered cyclic group, basic dialkyl ketones, wherein each alkyl group is independently selected from C1 to C4 alkyl, C1 to C4 aliphatic alcohols, C1 to C4 aliphatic aldehydes, acyclic aliphatic esters wherein each hydrocarbyl group is independently selected from C1 to C4 alkyl, cyclic aliphatic esters having a 5 to 7 membered cyclic group, dialkyl sulfides, wherein each alkyl group is independently selected from C1 to C4 alkyl, and dialkyl thiocarbonyl compounds, wherein each alkyl group is independently selected from C1 to C4 alkyl, and mixtures thereof ### Claim 7 (depends on 1) The process of claim 1, wherein said apolar medium is selected from saturated C4 hydrocarbons, unsaturated C4 hydrocarbons, and mixtures thereof ### Claim 8 (depends on 1) The process of claim 1, wherein said isobutene or an isobutene-containing monomer mixture is selected from pure isobutene; a C4 refinery cut containing between about 5% and about 50% butene-1, between about 2% and about 40% butene-2, between about 2% and about 60% iso-butane, between about 2% and about 20% n-butane, and up to about 0.5% butadiene, wherein all percentages are by mass, based on the total mass of the C4 refinery cut; and mixtures of pure isobutene and said C4 refinery cut. ### Claim 9 (depends on 1) The process of claim 1, wherein said complex is contacted with said isobutene or an isobutene-containing monomer at a concentration of millimoles of Lewis acid-Lewis base complex per liter of medium of from about 1 mM to about 200 mM. ### Claim 10 (depends on 1) The process of claim 1, wherein said Lewis acid and said Lewis base are complexed by dissolving the Lewis acid in solvent to form a solution, and then adding said Lewis base to said solution. ### Claim 11 (depends on 1) The process of claim 1, wherein the polymerization process is conducted continuously. ### Claim 12 (depends on 1) The process of claim 1, wherein said polybutene product has an exo-olefin content of at least 70 mol. %. ### Claim 13 A catalyst-initiator system for catalyzing the polymerization of isobutene or an isobutene-containing monomer mixture in a substantially or completely apolar solvent to provide a polybutene product having an exo-olefin content of at least 50 mol. %, wherein said catalyst comprising a Lewis acid catalyst complexed with an oxygen and/or sulfur containing Lewis base, wherein said Lewis acid catalyst is a Lewis acid of the formula MR″mYn, wherein M is a metal selected from Fe, Ga, Hf, Zr and W; R″ is a hydrocarbyl group; Y is halogen; m is 0 or an integer of 1 to 5; and n is an integer of 1 to 6, with the proviso that m+n is equal to the valency of metal M; and the polymerization is initiated via an initiator of the formula RX, wherein X is a halide; R is a hydrocarbyl group capable of forming a stable carbocation, and wherein the carbon linking group R to group X is tertiary, benzylic or allylic ### Claim 14 (depends on 13) The catalyst-initiator system of claim 13, wherein M is Ga or Fe, and R″ is a C1 to C8 alkyl group. ### Claim 15 (depends on 13) The catalyst-initiator system of claim 13, wherein m is 0 or 1. ### Claim 16 (depends on 13) The catalyst-initiator system of claim 13, wherein Y is Cl or Br. ### Claim 17 (depends on 13) The catalyst-initiator system of claim 13, wherein said Lewis base is selected from acyclic dihydrocarbyl ethers, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, basic cyclic ethers having a 5 to 7 membered cyclic group, dihydrocarbyl ketones, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, C1 to C12 aliphatic alcohols, C1 to C12 aliphatic aldehydes, acyclic aliphatic esters wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, cyclic aliphatic esters having a 5 to 7 membered cyclic group, dialkyl sulfides, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, and basic dihydrocarbyl thiocarbonyl compounds, wherein each hydrocarbyl group is independently selected from C1 to C12 hydrocarbyl, and mixtures thereof ### Claim 18 (depends on 17) The catalyst-initiator system of claim 17, wherein said Lewis base is selected from acyclic dialkyl ethers, wherein each alkyl group is independently selected from C1 to C4 alkyl, cyclic ethers having a 5 to 7 membered cyclic group, basic dialkyl ketones, wherein each alkyl group is independently selected from C1 to C4 alkyl, C1 to C4 aliphatic alcohols, C1 to C4 aliphatic aldehydes, acyclic aliphatic esters wherein each hydrocarbyl group is independently selected from C1 to C4 alkyl, cyclic aliphatic esters having a 5 to 7 membered cyclic group, dialkyl sulfides, wherein each alkyl group is independently selected from C1 to C4 alkyl, and dialkyl thiocarbonyl compounds, wherein each alkyl group is independently selected from C1 to C4 alkyl, and mixtures thereof. ### Claim 19 (depends on 13) The catalyst-initiator system of claim 13, wherein said Lewis acid and said Lewis base are complexed by dissolving the Lewis acid in solvent to form a solution, and then adding said Lewis base to said solution.