Catalytic Halogen Exchange in Miniemulsion ARGET ATRP: A Pathway to Well-Controlled Block Copolymers.

Macromolecular Rapid Communications
Yi Wang, Krzysztof Matyjaszewski

Abstract

Halogen exchange in atom transfer radical polymerization (ATRP) is an efficient way to chain-extend from a less active macroinitiator (MI) to a more active monomer. This has been previously achieved by using CuCl/L in the equimolar amount to Pn -Br MI in the chain extension step. However, this approach cannot be effectively applied in systems based on regeneration of activators (ARGET ATRP), since they operate with ppm amounts of catalysts. Herein, a catalytic halogen exchange procedure is reported using a catalytic amount of Cu in miniemulsion ARGET ATRP to chain-extend from a less active poly(n-butyl acrylate) (PBA) MI to a more active methyl methacrylate (MMA) monomer. Influence of different reagents on the initiation efficiency and dispersity is studied. Addition of 0.1 m NaCl or tetraethylammonium chloride to ATRP of MMA initiated by methyl 2-bromopropionate leads to high initiation efficiency and polymers with low dispersity. The optimized conditions are then employed in chain extension of PBA MI with MMA to prepare diblock and triblock copolymers.

References

Dec 26, 2001·Chemical Reviews·K Matyjaszewski, J Xia
Oct 13, 2006·Proceedings of the National Academy of Sciences of the United States of America·Krzysztof MatyjaszewskiNicolay V Tsarevsky
Jul 23, 2008·Journal of the American Chemical Society·Wei TangKrzysztof Matyjaszewski
Aug 30, 2008·Chemical Reviews·Per B ZetterlundMasayoshi Okubo
Apr 2, 2011·Science·Andrew J D MagenauKrzysztof Matyjaszewski
Aug 28, 2015·Chemical Reviews·Per B ZetterlundMuriel Lansalot
Mar 28, 2018·Advanced Materials·Krzysztof Matyjaszewski
May 31, 2018·Angewandte Chemie·Francesca LorandiKrzysztof Matyjaszewski

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