Polymerization of Biobased Farnesene in Miniemulsions by Nitroxide-Mediated Polymerization

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 degrees C, where NHS-BB-initiated systems resulted in smaller particles (similar to 300 nm) than using D7 (similar to 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.

Automated summary

This study focused on the polymerization of biobased farnesene in miniemulsions using different alkoxyamine initiators. The stable emulsions were observed with varying particle sizes depending on the initiator used, and successful chain extension was achieved. Additionally, diblock copolymers were synthesized by extending the poly(Far) macroinitiators with isobornyl methacrylate, showing differences in effectiveness between the initiators used.