Organometallic-Mediated Alternating Radical Copolymerization of tert-Butyl-2-Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly-(VAc-alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (<= 1.24) and molar masses up to 57 000 g mol(-1). These copolymers have a precise 1: 1 alternating structure over a wide range of comonomer feed compositions. The reactivity ratios are determined as r(VAc) = 0.01 +/- 0.01 and r(MAF-TBE) = 0 at 40 degrees C. Remarkably, from a feed containing >50% molar VAc content, poly(VAc-alt-MAF-TBE)-b-PVAc block copolymers are produced via a one-pot synthesis. Such diblock copolymers exhibit two glass transition temperatures attributed to the alternating and homopolymer sequences. The OMRP of this fluorine-containing alternating monomer system may provide access to a wide range of new polymer materials.