Pulsed nuclear magnetic resonance for studying phase separation in block and segmented copolymers

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Abstract
Pulsed nuclear magnetic resonance measurements have shown that segmented polyurethanes as well as block copolymers segregate into domains with distinct mobilities. The usefulness of this technique for investigating the importance of the domain interface and for studying the mixing/ demixing of domains has been demonstrated. By examining the percent rigid material as a function of temperature, a polystyrene/butadiene block copolymer showed little evidence of domain interface effects, while in a series of segmented polyurethanes, the interface was seen to be important. The domains of a polyester soft segment and diphenylmethane diisocyanate hard segment polyurethane were mixed by annealing at 170°C. Examination of the demixing process as a function of storage temperature enabled an activation energy for domain formation of 36 ± 5 kcal/mole to be calculated. In a series of polyurethanes with varying amounts of hard segments, the material with the least amount of hard segments showed evidence of soft segment crystallinity. The mixing proces in this series was interpreted in terms of shifting correlation frequency distributions.