Synthesis, thermal properties, and specific interactions of high Tg increase in poly(2,6-dimethyl-1,4-phenylene oxide)-block-polystyrene copolymers

We have synthesized a series of block copolymers of poly(2,6-dimethyl-1,4-phenylene oxide) and polystyrene (PPO-b-PS copolymer) by atom transfer radical polymerization. The PS content in these copolymer systems was determined by using infrared spectroscopy, thermal gravimetric analysis, and solution and solid-state NMR spectroscopy; good correlations exist between these characterization methods. DSC analyses indicated that the PPO-b-PS copolymers have higher glass transition temperatures than do their corresponding PPO/PS blends. Our FTIR and solid-state NMR spectroscopic analyses suggest that the PPO-b-PS copolymers possess stronger specific interactions that are responsible for the observed relatively higher values of Tg. We found one single dynamic relaxation from the dynamic mechanical analysis, which implies dynamic homogeneity exists in the PPO-b-PS copolymer; this result is consistent with the one single proton spin–lattice relaxation time observed in the rotating frame [T1ρ(H)] during solid state NMR spectroscopic analysis. In addition, the 2D FTIR spectroscopy reveals evidence for the stronger interactions between segments of PPO and PS through the formation of π-cation complexes.