Abstract: Reversible addition fragmentation chain transfer(RAFT) mediated miniemulsion copolymerizations of butyl methacrylate with fluoroacrylate were carried out at 70 ℃ with potassium persulphate as initiator, and the kinetics of copolymerizations were investigated. Copolymer compositions at low conversion levels were determined by ¹H NMR spectra techniques. In the presence of RAFT agent 2-cyanoprop-2-yl dithiobenzoate(CPDB), the copolymerization of BMA with FMA in miniemulsion exhibited typical features of a controlled mole-cular weights and narrow polydispersities. The reactivity ratios were evaluated by Kellen-Tudos(K-T) method, which yields the apparent reactivity ratios, r_BMA=0.63 and r_FMA=0.79. The results show that the monomer FMA with a fluorinated side chain is more reactive than BMA, and the copolymerizations have a tendency to alternate and to produce a higher FMA content in the copolymers. The spontaneous statistical copolymers with soft gradient shapes were obtained using variable initial ratios of BMA and FMA.

Key words: Reversible addition fragmentation chain transfer(RAFT), Statistical copolymer, Fluorinated acrylate