Reversible AdditionFragmentation Chain Transfer (RAFT) polymerization in miniemulsion based on in situ surfactant generation

Reversible additionfragmentation chain transfer (RAFT) polymerization of styrene has been implemented in aqueous miniemulsion based on the in situ surfactant generation approach using oleic acid and potassium hydroxide in the absence of high energy mixing. The best results were obtained using the RAFT agent 3-benzylsulfanyl thiocarbonyl sufanylpropionic acid (BSPAC), most likely as a result of the presence of a carboxylic acid functionality in the RAFT agent that renders it surface active and thus imparts increased colloidal stability. Stable final miniemulsions were obtained with no coagulum with particle diameters less than 200nm. The results demonstrate that the RAFT miniemulsion polymerization of styrene employing the low energy in situ surfactant method is challenging, but that a system that proceeds predominantly by a miniemulsion mechanism can be achieved under carefully selected conditions. © 2011 CSIRO