Nitroxide-mediated polymerization of bio-based farnesene and glycidyl methacrylate

Conference Dates

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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