Polymerization of Biobased Farnesene in Miniemulsions by Nitroxide-Mediated Polymerization

Sharmaine B Luk; Milan Maríc

doi:10.1021/acsomega.0c05992

Polymerization of Biobased Farnesene in Miniemulsions by Nitroxide-Mediated Polymerization

ACS Omega. 2021 Feb 11;6(7):4939-4949. doi: 10.1021/acsomega.0c05992. eCollection 2021 Feb 23.

Authors

Sharmaine B Luk¹, Milan Maríc¹

Affiliation

¹ Department of Chemical Engineering, McGill University, 3610 Rue University, Montréal, Québec H3A 0C5, Canada.

Abstract

Biobased farnesene (Far) was polymerized by nitroxide-mediated polymerization in miniemulsions using two different alkoxyamine initiators, the SG1-based and succinimidyl-modified BlocBuilder (NHS-BB) and Dispolreg 007 (D7). Stable emulsions were observed after 30 h of reaction at 90 °C, where NHS-BB-initiated systems resulted in smaller particles (∼300 nm) than using D7 (∼400 nm). Successful chain extension of the poly(Far) macroinitiators (24,500-39,700 g mol^-1) with styrene were achieved using 15 wt % surfactant relative to monomer concentration. Compartmentalization effects were not observed in these emulsions as the polymerization rate was still much slower compared to the bulk, even though Z-averaged particle sizes were around 300-400 nm. Finally, all biobased diblock copolymers were synthesized by chain-extending poly(Far) macroinitiators with isobornyl methacrylate (iBOMA), where the D7 initiator showed more effective chain extension (less unreacted macroinitiator) than NHS-BB.