Nitroxide mediated radical polymerization for the preparation of poly(vinyl chloride) grafted poly(acrylate) copolymers

Abstract

In view to control the thermal properties of PVC without the use of toxic phthalate derivatives, alkoxyamines were grafted onto an azide modified PVC, through copper catalyzed azide–alkyne cycloaddition (CuAAC), to initiate a radical polymerization of acrylate monomers including butyl acrylate (BA) and polyethylglycol acrylate (PEGA) monomers. A series of PVC-g-PBA copolymers having various glass transition temperatures (T_g) between 63.5 to −10.5 °C were obtained. The PVC-g-PEGA copolymers presented a semi-crystalline behavior with a T_g of −4 °C and a T_m of 43 °C. This method, combining CuAAC click reaction and radical polymerization, was efficient to covalently link a plasticizing group on PVC. This “grafting from” strategy using alkoxyamine functionalized PVC can be expanded to produce new materials via nitroxide mediated polymerization of various monomers.