Controlled synthesis of random, block-random and gradient styrene, methyl methacrylate and acrylonitrile Terpolymers via Nitroxide-mediated free radical polymerization

Different types of the styrene - methyl methacrylate -acrylonitrile terpolymers were synthesized according to the recently proposed concept of the living nitroxide-mediated terpolymerization. Random azeotropic and gradient terpolymers were prepared using the living TEMPO-mediated polymerization. Block random terpolymer was obtained via the living terpolymerization initiated by macro-alkoxyamine polystyrene-SG1. In all systems, terpolymerization proceeds in the living manner even in the presence of TEMPO. Upon complete polymerization at high conversions of monomers, the molecular weight of terpolymers linearly increases with the monomer conversion. The resultant terpolymers were characterized by the methods of turbidimetric titration, GPC, DSC, and TGA, and their characteristics were compared with their non-living analogs synthesized by the conventional radical polymerization. The effect of the macromolecular structure on the thermal stability of the terpolymers was studied.