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dc.contributor.authorMcLaren, Michaelen
dc.description.abstractChemistry for introducing a long-chain branch (LCB) architecture to linear, isotactic polypropylene (PP) is described, wherein degradation of the polymer matrix through β-scission of macroradicals is inhibited by an additive comprised of a nitroxyl that bears a polymerizable functional group. Trapping of alkyl macroradicals by the nitroxyl yields a macromonomer derivative that crosslinks when exposed to residual initiator-derived radicals. As such, formulations containing 4-acryloyloxy-2,2,6,6,-tetramethylpiperidine-1-oxyl (AOTEMPO) and a peroxide transform linear PP into a gel-free, long-chain branched derivative (LCB-PP) that exhibits exceptional strain hardening with minimal loss in matrix molecular weight. The chemistry is extended to produce PP bearing pendant anhydride and/or imide grafts. Formulations containing 4-vinyl ether-2,2,6,6-tetramethylpiperidine-1-oxyl (VETEMPO), maleic anhydride (MA), and peroxide produced anhydride-functionalized polypropylene (PP-g-MA). Following macroradical trapping by VETEMPO, pendant vinyl ether groups undergo a strictly alternating copolymerization with MA, thereby introducing anhydride without incurring large-scale matrix degradation. At a given melt viscosity, this technology provided PP-g-MA derivatives with higher graft content than standard peroxide-only reactions. Moreover, when combined with the difunctional monomer N,N’-1,3-phenylene-dimaleimide (PDM), VETEMPO enabled the production of highly crosslinked PP with an appreciable gel fraction.en
dc.relation.ispartofseriesCanadian thesesen
dc.rightsAttribution-NonCommercial-ShareAlike 3.0 United Statesen
dc.rightsQueen's University's Thesis/Dissertation Non-Exclusive License for Deposit to QSpace and Library and Archives Canadaen
dc.rightsProQuest PhD and Master's Theses International Dissemination Agreementen
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dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.en
dc.subjectLong-Chain Branchingen
dc.subjectRadical Modificationen
dc.subjectFunctional Nitroxylsen
dc.subjectMaleic Anhydrideen
dc.subjectPolymer Functionalizationen
dc.titleFunctional Nitroxyls for Polypropylene Modificationen
dc.contributor.supervisorParent, J. Scotten
dc.contributor.departmentChemical Engineeringen's University at Kingstonen

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Except where otherwise noted, this item's license is described as Attribution-NonCommercial-ShareAlike 3.0 United States