Synthesis of Chlorotrifluoroethylene-Based Block Copolymers by Iodine Transfer Polymerization.

Various fluorinated macro-chain transfer agents (CTAs) based on vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE), or CTFE and vinylidene chloride (VDC), were synthesized by iodine transfer polymerization (ITP). These macro-CTAs were involved in a further ITP reaction that led to the synthesis of original CTFE-based block copolymers exhibiting molecular weight ranging from 2500 to 40000 g/mol and endowed with high thermal stabilities (decomposition temperature at 10% weight loss of ca. 380 °C, under air). ITP of CTFE and VDC as well as ITP of VDF thermally initiated at 100 °C by a catalytic amount of dimanganese decacarbonyl (Mn(CO)) are reported for the first time.