Delaying the onset of macrogelation for the synthesis of branched and star-like polymers via conventional free-radical polymerisation: Binary solvent effects and incorporation of surfmers

It is known that the preferential solvation and conformation of a polymer in a solvent mixture are functions of the polymer's molecular weight and the solvent qualities. This paper demonstrates that these relationships can be exploited to delay the onset of macrogelation for branched poly(methyl methacrylate/ethylene glycol dimethacrylate) (p(MMA/EGDMA)) polymers and star-like poly(methyl acrylate/ethylene glycol dimethacrylate) (p(MA/EGDMA)) polymers synthesised via conventional free-radical polymerisation (CFRP) in a binary solvent mixture (consisting of a good solvent and a precipitant for the polymer). The gelation limits of the MMA/EGDMA and MA/EGDMA polymerisations in a methyl ethyl ketone (MEK)/heptane binary solvent mixture can be extended to regions of higher monomer concentration with increases in polymer yield between 13 and 50 ± 5 w/w% for the p(MMA/EGDMA) system and between 8 and 19 ± 6 w/w% for the p(MA/EGDMA) system across the gelation boundary. Thus, a facile method of increasing the concentration of batch reaction mixtures by the simple addition of small amounts of precipitant into the reaction solutions is presented. Furthermore, the gelation limits of both polymerisation systems in the binary solvent mixtures were further extended with increases in polymer yield between 11 and 17 ± 4%w/w for the p(MMA/ODA/EGDMA) system and between 8 and 20 ± 5%w/w for the p(MA/VS/EGDMA) system by the respective incorporation of octadecyl acrylate (ODA) and vinyl stearate (VS) surfmers into the polymers, demonstrating the application of steric hinderance to shield the propagating polymers from excessive cross-linking reactions.