Free Radical Techniques of Deriving α, ω End Functional Polymers and Block Copolymers Via Thermal Iniferters

Abstract

The initiator, chain transfer and terminator (Iniferter) properties of the tetraalkyl thiuram disulfides during vinyl polymerization have been exploited to end-functionalise polymethyl methacrylate (PMMA) and polystyrene (PS). Typically hydroxyl and amido phosphate groups were chosen. Polymers bearing the iniferter groups in their backbone served as polymeric thermal iniferters for vinyl polymerization leading to vinyl block copolymers. The syntheses of poly(phosphonamide-b-methylmethacrylate) and poly(phosphonamide-b-styrene) by this technique have been described. The kinetics of polymerization led to the evaluation of the various kinetic paramaters pertaining to the initiating, chain transferring and radical terminating properties of the iniferter groups as a function of their chemical environment.