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Title: In pursuit of RAFT-functional polyethylene : exploration of a novel class of Sn-RAFT agents and the preparation and application of RAFT-functional polyethylene-like poly(ω-pentadecalactone)
Author: Pflughaupt, Robin L.
ISNI:       0000 0004 5363 8323
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2014
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This work explores the preparation of Reversible Addition-Fragmentation chain-Transfer (RAFT)-functional polyethylene (PE). Challenges in developing methods to control the polymerization of primary radicals and prepare functional polyethylene are significant. Modest control over ethylene polymerization demonstrated via F-RAFT polymerization inspired our interest in RAFT agent design and we envisaged that metallo-RAFT agents could present different reactivities towards primary radicals. Considering the challenge of attempting to develop chemistry for the controlled radical polymerization of primary radicals, preparation of RAFT-functional polyethylene-like poly(ω-pentadecalactone) (PPDL) was also investigated. We envisaged the preparation of RAFT-functional PPDL to be more convenient than reported strategies to prepare functional polyethylene all whilst being a “green” alternative to PE that may be suitable for some applications. Chapter 1 discusses challenges in preparing functional polyethylene via controlled radical polymerization techniques. Furthermore, metallo-RAFT chemistry and the ring-opening polymerization of macrocyclic esters are reviewed. Chapter 2 describes the synthesis of PPDL via enzymatic ring-opening polymerization (eROP). Using a bifunctional initiator appropriate for the RAFT polymerization of acrylic and styrenic monomers, RAFT-functional poly(ω-pentadecalactone) was prepared. Furthermore, chain extension of the macro-chain-transfer agent was utilized to prepare acrylic and styrenic block copolymers of PPDL. To our knowledge, this is the first preparation of block copolymers of poly(ω-pentadecalactone) via a combination of eROP and RAFT polymerization techniques. Chapter 3 describes the large scale synthesis and characterization of a selection of acrylic block copolymers of PPDL suitable for fuels applications. Furthermore, the fuels testing of these copolymers for cold flow applications is described. In general, all block copolymers of PPDL, in particular poly(ω-pentadecalactone)-b-poly(isodecyl acrylate) improved the cold flow performance of various diesel fuels. Chapter 4 reports the synthesis of Sn-RAFT agents and their subsequent use in the controlled radical polymerization of several vinylic monomers. Chapter 5 summarizes the findings in chapters 2 – 4 and Chapter 6 communicates the associated experimental data.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry