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

Yamazaki, Shun*; Kaneko, Naoya*; Kato, Atsuya*; Watanabe, Kohei*; Aoki, Daisuke*; Taniguchi, Tatsuo*; Karatsu, Takashi*; Ueda, Yuki   ; Motokawa, Ryuhei   ; Okura, Koki*; Wakiya, Takeshi*

Synthesis of heat-resistant, living polymer particles via one-step reversible addition-fragmentation chain transfer precipitation polymerization (RAFTPP) of styrene and -phenylmaleimide 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 micrometer were successfully synthesized. The P(St-PhMI) RAFTPP showed excellent thermal stability with a high glass transition temperature and a 5 percent weight loss temperature. The surface concentration of the RAFT groups was determined to be 0.181 groups/square-nanometer 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.