One‐Pot Synthesis of PTFEMA‐<i>b</i>‐PMMA‐<i>b</i>‐PTFEMA by Controlled Radical Polymerization with a Difunctional Initiator in Conjugation with Photoredox Catalyst of Ir(ppy)₃ Under Visible Light

Abstract

Visible‐light‐induced free radical polymerization of methyl methacrylate (MMA) and 1,1,1‐trifluoroethyl methacrylate (TFEMA) with a difunctional initiator, dimethyl 2,6‐dibromoheptanedioate (DMDBHD), conjugated with a photoredox catalyst, tris(2‐phenylpyridinato)iridium(III) ( fac ‐[Ir(ppy) 3 ]), is investigated. Kinetic studies demonstrate that homopolymerizations of both MMA and TFEMA are controlled radical polymerizations. The linear increase of molecular weights with monomer conversion and the narrow PDIs (1.2–1.4) reveal a good living character. In addition, PTFEMA‐ b ‐PMMA‐ b ‐PTFEMA triblock copolymer is prepared by a one‐pot process with sequential monomer addition. The of the triblock copolymers increases linearly with monomer conversion and the PDI of block copolymers is still maintained around 1.2–1.4. Experimental data confirm that the products are pure block polymers. Furthermore, the molar fraction of the TFEMA monomeric unit in the block copolymer is about 21.96%, close to the theoretical value 21.00% calculated from the monomer conversion. image