Abstract
Three polystyrene-block-poly(2-vinylpyridine) (S2VP diblock) and three polystyrene-block-poly(4-vinylpyridine) (S4VP diblock) copolymers with varying molecular weights and block compositions were synthesized via anionic polymerization, and their order−disorder transition temperatures (TODTs) were determined using oscillatory shear rheometry and small-angle X-ray scattering (SAXS). It has been found that for comparable molecular weight and block composition the TODT of S4VP diblock copolymer is exceedingly high compared with that of S2VP diblock copolymer. The experimental observation has been confirmed by theoretical predictions from currently held mean-field theory. For the theoretical predictions, temperature-dependent interaction parameters for the polystyrene (PS)/poly(2-vinylpyridine) (P2VP) pair and the PS/poly(4-vinylpyridine) (P4VP) pair were determined from SAXS profiles obtained at varying temperatures ranging from 125 to 185 °C for a low-molecular-weight (LMW) S2VP diblock copolymer and ranging...
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