Synthesis and Characterization of Polystyrene-b-Poly(4-vinyl pyridine) Block Copolymers by Atom Transfer Radical Polymerization

We aimed at the synthesis of well-define PS-b-P4VP by using atom transfer radical polymerization in two-step process. First, polystyrenes with benzyl bromide end group (PS-Br; by ATRP) were prepared as macroinitiator for the next ATRP of 4-vinyl pyridine and characterized these polymers from 1H-NMR and MALDI-TOF. Comparing with MALDI-TOF-MS, 1H-NMR and GPC analyses, this indicates that the formation of the block copolymer can be observed. During the polymerizations, molecular weight distribution and kinetics have been evaluated from GPC traces and 1H-NMR analyses. We further characterized the thermal properties of these block polymers by DSC and TGA. DSC measurement on the PS-b-P4VP block copolymers exhibited two glass transitions, indicating that the resulting block copolymers are phase separated. Two maxima differential peaks were observed on the TGA trace for the PS-b-P4VP block copolymers might be assigned to the decomposition of the P4VP blocks at 380 ○C and the PS blocks at higher temperature.