# US 10,370,521 B2 · Methods for synthesis of polyolefin-containing block copolymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,521 B2 - Document ID: US10370521B2 - Status: Granted - Kind: B2 - Application number: 15/809,847 - Filed: 2017-11-10 - Published: 2018-05-17 - Granted: 2019-08-06 - Earliest claimed: 2016-11-11 - Assignees: The Board of Trustees of the University of Illinois - Applicants: The Board of Trustees of the University of Illinois - Inventors: Damien S. Guironnet; Dylan J. Walsh - Web page: https://patentgrep.com/patent/US10370521B2 ## CPC - C08K 5/541: containing oxygen - C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} - C08F 4/80: selected from iron group metals or platinum group metals - C08F 10/02: Ethene - C08F 20/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - C08F 110/02: Ethene - C08F 110/06: Propene - C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate} - C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent} - C08G 81/027: {containing polyester or polycarbonate sequences} - C08G 83/003: {Dendrimers} - C08G 83/005: {Hyperbranched macromolecules} - C08K 5/5403: {containing no other elements than carbon or hydrogen} - C08L 101/00: Compositions of unspecified macromolecular compounds - C08F 2438/00: Living radical polymerisation - C08F 2438/01: Atom Transfer Radical Polymerization [ATRP] or reverse ATRP - C08F 2810/40: taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A methodology is described for the synthesis of polyolefin containing block-copolymers using a catalytic postpolymerization modification strategy. Common polyolefin grades may be converted into macroinitiators using a cross-metathesis reaction. The functionalized polyolefins may then be used to initiate living: coordinative ring opening polymerization of cyclic ester monomer, anionic ring opening polymerization of epoxide monomer, and radical polymerization of vinylic monomer, to yield the corresponding block copolymers. ## Claims ### Claim 1 A method for preparing a polyolefin-containing block copolymer via three consecutive reactions comprising: (a) preparing an alkenyl terminated polyolefin via an insertion polymerization reaction of an olefin monomer; (b) preparing a polyolefin macroinitiator by functionalizing the alkenyl end group of the polyolefin of step (a) via a catalytic cross metathesis reaction; and (c) carrying out a living polymerization reaction initiated by the polyolefin macroinitiator of step (b); to provide the polyolefin-containing block copolymer. ### Claim 2 (depends on 1) The method of claim 1 where the polyolefin-containing block copolymer comprises polyethylene, polypropylene, poly(1-olefin) or a combination thereof. ### Claim 3 (depends on 1) The method of claim 1 where the polyolefin-containing block copolymer comprises a star-shaped polymer. ### Claim 4 (depends on 1) The method of claim 1 where the olefin monomer of step (a) has the structure of Formula (I): where R is linear or branched C1-18 alkyl. ### Claim 5 (depends on 4) The method of claim 4 where the alkenyl terminated polyolefin of step (a) has the structure of Formula (II): where X is H or linear or branched C1-18 alkyl. ### Claim 6 (depends on 5) The method of claim 5 where the alkenyl terminated polyolefin of step (a) has the structure of one of the following formulas: where X is H or linear or branched C1-18 alkyl. ### Claim 7 (depends on 1) The method of claim 1 where the insertion polymerization reaction of step (a) utilizes a catalyst comprising nickel, titanium, palladium, zirconium, iron, hafnium, cobalt, vanadium or chromium. ### Claim 8 (depends on 1) The method of claim 1 where the catalytic cross metathesis reaction of step (b) comprises adding a ruthenium based methathesis catalyst and a cross-coupling compound to the olefin terminated polyolefin of step (a). ### Claim 9 (depends on 8) The method of claim 8 where the cross-coupling compound comprises an acrylate. ### Claim 10 (depends on 1) The method of claim 1 where the living polymerization reaction of step (c) comprises: (i) a coordinative Ring Opening Polymerization (cROP) reaction of a cyclic ester monomer; (ii) an anionic Ring Opening Polymerization (aROP) reaction of an epoxide monomer; or (iii) an Atom Transfer Radical Polymerization (ATRP) reaction of a vinylic monomer. ### Claim 11 (depends on 10) The method of claim 10 where the cyclic ester monomer comprises a lactide. ### Claim 12 (depends on 10) The method of claim 10 where the epoxide monomer comprises tert-butyl glycidyl ether (tBuGE). ### Claim 13 (depends on 10) The method of claim 10 where the vinylic monomer comprises styrene. ### Claim 14 A method for preparing a polyolefin-containing block copolymer via three consecutive reactions comprising: (a) preparing an alkenyl terminated polyolefin via an insertion polymerization reaction of an olefin monomer; (b) preparing a polyolefin macroinitiator by functionalizing the alkenyl end group of the polyolefin of step (a) via a catalytic cross metathesis reaction comprising adding a ruthenium based methathesis catalyst and a cross-coupling compound comprising an acrylate to the alkenyl terminated polyolefin of step (a); and (c) carrying out a living polymerization reaction initiated by the polyolefin macroinitiator of step (b) via: (i) running a coordinative Ring Opening Polymerization (cROP) reaction of a cyclic ester monomer; or (ii) hydrogenating the polyolefin macroinitiator of step (b), then running an anionic Ring Opening Polymerization (aROP) reaction of an epoxide monomer; to provide the polyolefin-containing block copolymer. ### Claim 15 (depends on 14) The method of claim 14 where the cROP reaction of a cyclic ester monomer is catalyzed with tin, aluminum, zirconium, zinc, cobalt or indium. ### Claim 16 (depends on 14) The method of claim 14 where the acrylate comprises 2-hydroxyethyl acrylate (HEA), 2-(2-bromoisobutyryloxy) ethyl acrylate (BIEA) or 1-((2-bromo-2-methylpropanoyl)-3-hydroxypropan-2-yl acrylate. ### Claim 17 (depends on 14) The method of claim 14 where the cyclic ester monomer comprises polylactic acid (PLA) or caprolactone. ### Claim 18 (depends on 17) The method of claim 17 where the polyolefin-containing block copolymer comprises l-HDPE-PLA, h-HDPE-PLA, synPP-PLA, LLDPE-PLA, HBPE-PLA or iso-PP-PLA. ### Claim 19 (depends on 14) The method of claim 14 where the hydrogenated polyolefin macroinitiator of step (c) (ii) is reduced to a primary alcohol with a reducing agent and the aROP reaction of an epoxide monomer is catalyzed with KN(TMS)2. ### Claim 20 A method for preparing a polyolefin-containing block copolymer via three consecutive reactions comprising: (a) preparing an alkenyl terminated polyolefin via an insertion polymerization reaction of an olefin monomer; (b) preparing a polyolefin macroinitiator by functionalizing the alkenyl end group of the polyolefin of step (a) via a catalytic cross metathesis reaction comprising adding a ruthenium based methathesis catalyst and a cross-coupling compound comprising an acrylate to the olefin terminated polyolefin of step (a); and (c) carrying out a living polymerization reaction initiated by the polyolefin macroinitiator of step (b) via an Atom Transfer Radical Polymerization (ATRP) reaction of a vinylic monomer; to provide the polyolefin-containing block copolymer.