Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r1 (HFIB) = 0, r2 (VPFB) = 0.373, and r1r2 = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB-co-VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average Tgs of HFIB-co-VTFA and HFIB-co-VPFB were 52 and 71 degrees C, respectively. From these results, the Tg of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 degrees C, which may be useful in the assessment of Tgs of HFIB copolymers with other vinyl monomers. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012