Macromolecular Rapid Communications
Macromolecular Rapid Communications
5 years ago

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

Organometallic-Mediated Alternating Radical Copolymerization of tert-Butyl-2-Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof
S. M. Wahidur Rahaman, Christophe Detrembleur, Sanjib Banerjee, Rinaldo Poli, Antoine Debuigne, Vincent Ladmiral, Bruno Ameduri
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 rVAc = 0.01 ± 0.01 and rMAF-TBE = 0 at 40 °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. Organometallic-mediated radical copolymerization is successfully employed for 1:1 alternating controlled copolymerization (independent of the monomer feed) of VAc (electron-donating) and MAF-TBE (electron-accepting). By simply tuning the comonomer feed ratio, well-defined poly(VAc-alt-MAF-TBE) alternating copolymers or novel poly(VAc-alt-MAF-TBE)-b-PVAc diblock copolymers (comprising of one alternating block and one homopolymer block) can be prepared.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/marc.201700203

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