Synthesis and Characterization of a Phosphonated Graft Copolyimide

A new synthesis route of phosphonated multiblock, branched copolyimide is proposed in this research. The synthesis and characterization of the series of new phosphonated graft copolyimides were prepared by combination of one-step high temperature polymerization and phosphonation method by lithiation and reaction with excess diethylchlorophosphate. The phosphonate ester product was converted to the phosphonic acid by hydrolysis. A branched polyimide structure was achieved by coupling the two polyimides with 3, 3'-diaminobenzidine. A phosphonated branched copolyimide with 32% mol phosphonation exhibited high thermal stability, with a decomposition temperature in nitrogen of ∼475°C. Proton exchange membranes prepared from these copolyimides had proton conductivity of 0.02 - 0.03 S/cm at 100% humidity over a temperature range of 40 - 100°C

Nitroxide mediated and atom transfer radical graft polymerization of atactic polymers onto syndiotactic polystyrene

'Living' radical graft polymerization was employed to prepare graft copolymers with nitroxide-mediated arylated syndiotactic polystyrene as the backbone and polystyrene (PS), poly(p-methylstyrene) (PMS) and poly(methylmethacrylate) (PMMA) as branches. A two-stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS) was modified by the Friedel-Crafts reaction to introduce chlorine; second, the chlorine groups were converted to nitroxide mediated groups by coupling with 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-OH). The resulting macroinitiator (sPS-TEMPO) for 'living' free radical polymerization was then heated in the presence of styrene and p-methylstyrene to form graft and block copolymers. We used the obtained copolymer and N-bromosuccinimide as brominating agent to achieve polymers with bromine groups. This brominated copolymer was used as a macroinitiator for polymerizing methyl methacrylate in the presence of the CuBr/bpy catalyst system. The formation of the graft and block copolymers was confirmed by DSC, ¹H NMR and FTIR spectroscopy. This approach using macroinitiators is an effective method for the preparation of new materials