A series of gradient fluorinated copolymers with a broad variation of the monomer units in the polymer chain were synthesized via semibatch CPDB-mediated RAFT miniemulsion polymerization technique. In the presence of RAFT agent 2-cyanoprop-2-yl dithiobenzoate (CPDB), the copolymerization of BMA and FMA in miniemulsion exhibited typical features of a controlled molecular weights and narrow polydispersities. The macromolecular structure and thermal behavior of the synthesized fluorinated copolymers were investigated in detail. The DSC analyses show that the gradient copolymers showed a unique thermal behavior with broad range of transition temperature. It was also confirmed that the fluorinated gradient copolymer exhibited obvious surface segregation structure and ultra-low surface energy between 16.8 and 20.3 mN/m. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42936.
