New copolymers based on vinylidene fluoride (VDF) and 2,3,3,3-tetrafluoroprop-1-ene (1234yf) were synthesized by organometallic-mediated radical copolymerization (OMRcP) using the combination of bis(tert-butylcyclohexyl) peroxydicarbonate initiator and bis(acetylacetonato)cobalt(II), (Co(acac)2) as a controlling agent. Kinetics studies of the copolymerization of the fluoroalkenes copolymers were monitored by GPC and 19F NMR with molar masses up to 12,200 g/mol and dispersities (Đ) ranging from 1.33 to 1.47. Such an OMRcP behaves as a controlled copolymerization, evidenced by the molar mass of the resulting copolymer-monomer conversion linear relationship. The reactivity ratios, ri, of both comonomers were determined by using the Fineman-Ross and Kelen-Tüdos fitting model leading to rVDF = 0.384 ± 0.013 and r1234yf = 2.147 ± 0.129 at 60 °C, showing that a lower reactivity of VDF integrated in the copolymer to a greater extent leads to the production of gradient or pseudo-diblock copolymers. In addition, the Q (0.03) and e (0.06 and 0.94) parameters were assessed, as well as the dyad statistic distributions and mean square sequence lengths of PVDF and P1234yf.
Keywords: 3,3,3-tetrafluoroprop-1-ene; RDRP; cobalt acetylacetonate; controlled radical polymerization; kinetics of copolymerization; organometallic radical copolymerization; reactivity ratios; vinylidene fluoride.