Nitroxide-mediated polymerization of bio-based farnesene and glycidyl methacrylate
May 20-25, 2018
There is increasing interest in using bio-based monomers to synthesize polymers that have comparable properties to petroleum-derived polymers. Terpenes like farnesene and myrcene have multiple unsaturated carbon-carbon bonds that can be polymerized like commonly known dienes (i.e. butadiene, isoprene). Farnesene is naturally found in essential oils and released as a pheromone to repel insects, but can also be produced through microbial pathways. In this work, farnesene (Far) and glycidyl methacrylate (GMA) were randomly copolymerized via nitroxide-mediated polymerization (NMP). Traditionally, NMP of methacrylates is not well-controlled due to slow recombination between the nitroxide radical and growing radical chain.1-2 The succinamidyl ester form of the commercial BlocBuilder MA initiator, NHS-BlocBuilder, shows good control over NMP of methacrylates with the addition of 5-10 mol% of controlling monomer like styrene, without any additional free nitroxide.3 At 120°C, copolymerizations of Far and GMA at various molar compositions without controlling monomer were done using NHS-BlocBuilder in bulk. Reactivity ratios of Far/GMA copolymerization were determined to be rFar = 0.58 and rGMA = 0.25 and the Mayo-Lewis plot is shown in Figure 1. For Far-rich compositions, dispersity was ~1.4 and showed linear chain growth. GMA-rich copolymerizations were also done at 90°C and showed good control suggesting that farnesene can act as a controlling monomer for NMP of GMA. Chain extension of Far/GMA random copolymers will be done with styrene to investigate chain-fidelity. Furthermore, a newly developed initiator based on a new class of alkoxyamines4 will be used to copolymerize farnesene and GMA and its kinetics will be compared with NHS-BlocBuilder.
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Sharmaine Luk and Milan Marić, "Nitroxide-mediated polymerization of bio-based farnesene and glycidyl methacrylate" in "Polymer Reaction Engineering X (PRE 10)", John Tsavalas, University of New Hampshire, USA Fouad Teymour, Illinois Institute of Technology, USA Jeffrey Stubbs, HP Inc., USA Jose R. Leiza, University of the Basque Country, Spain Eds, ECI Symposium Series, (2018). http://dc.engconfintl.org/prex/16