Precise insertion of clickable monomer along polymer backbone by dynamic temperature controlled radical polymerization

Styrenic copolymers have been prepared that contain localized areas of high azide functionality by exploiting the unexpected copolymerization behavior of azidomethyl styrene with styrene. Kinetic studies have shown that during the nitroxide-mediated polymerization of styrene and azidomethyl styrene, small equivalents of azidomethyl styrene are consumed at a relatively higher rate. This property was further enhanced by lowering the reaction temperature, leading to a more precisely defined area of azide functionality. Furthermore, by actively controlling the reaction temperature azidomethyl styrene can be inserted into different points along the polymer backbone. This approach was used in combination with previous sequence control techniques, strong donor/acceptor comonomer pairs, to synthesize well-defined copolymers with controlled areas of functional monomers allowing for a wide scope of post-polymerization modification methods. (C) 2014 Elsevier Ltd. All rights reserved.