Synthesis of heat-resistant living polymer particles by one-step reversible addition-fragmentation chain transfer precipitation polymerization of styrene and N-phenylmaleimide

For the first time, the synthesis of heat-resistant, "living" polymer particles via one-step reversible addition-fragmentation chain transfer precipitation polymerization (RAFTPP) of styrene (St) and N-phenylmaleimide (PhMI) is reported. Gel permeation chromatography and nuclear magnetic resonance spectroscopy confirmed that the polymerization proceeded in a living manner. The scanning electron microscopy results showed that the monodisperse P(St-PhMI)_RAFTPP particles with a diameter of 1.88 μm were successfully synthesized. The P(St-PhMI)_RAFTPP showed excellent thermal stability with a high glass transition temperature and a 5% weight loss temperature. The surface concentration of the RAFT groups was determined to be 0.181 groups/nm2 due to fragmentation of the RAFT groups exposed on the particles. The small-angle neutron scattering measurements showed the particle formation mechanism, in which the swollen, growing polymer chains were consumed for particle formation. The introduction of grafted chains by surface-initiated RAFT polymerization demonstrated the possibility of further functionalization of P(St-PhMI)_RAFTPP particles by exploiting their living nature.