Access to cyclic polystyrenes via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry

The coupling of the reversible addition fragmentation chain transfer (RAFT) polymerization technique with the copper-catalyzed Huisgen 1,3-dipolar cycloaddition ("click chemistry") as a simple and effective way to generate polystyrene (PS) macrocycles is presented. The novel strategy entails the synthesis of linear PS backbones followed by endgroup modification to facilitate click chemistry for the formation of ring shaped polymers. An azido group modified 4-cyanopentanoic acid dithiobenzoate is employed as the chain transfer agent in the RAFT mediated polymerization of styrene to form PS with M-n from 2000 g mol(-1) to 6000 g mol(-1) and PDI < 1.2. To facilitate the cyclization of the polystyrene chains by click coupling, the thiocarbonylthio endgroup is removed and concomitantly replaced by an alkyne bearing function. This is carried out via the radical decomposition of excess azobis(4-cyano valeric acid) (ACVA) modified with an alkyne endgroup in the presence of the thiocarbonylthio-capped PS. The successful click endgroup modifications of several polystyrenes along with the results from the cyclization of a PS with M-n = 4300 g mol(-1) are discussed in detail. This improved method avoids the presence of thiocarbonylthio functions in the macrocycle, thus considerably increasing the chemical stability of these polymers. (C) 2008 Elsevier Ltd. All rights reserved.