Poly(methylphenylphosphazene)–Graft–Poly(methyl Methacrylate) Copolymers Via Atom Transfer Radical Polymerization

Atom transfer radical polymerization (ATRP) was used to graft poly(methyl methacrylate), PMMA, onto poly(methylphenylphosphazene), [(Me)(Ph)PN]n, PMPP. A two-step process was used to convert a portion of the methyl substituents on [(Me)(Ph)PN]n to –CH2C(CH3)2OH groups and then to bromoalkyl groups, –CH2C(CH3)2OC(=O)C(CH3)2Br, the latter of which served as initiation sites for ATRP of methyl methacrylate (MMA) in the presence of CuCl/bipyridine. Variations in the length of the grafted chains were investigated and the graft copolymers were compared to the parent polymer and blends of similar composition. The new bromoalkyl derivatives of [(Me)(Ph)PN]n and the PMPP–graft–PMMA copolymers were characterized by elemental analysis, 1H and 31P NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC).