Crystallization, and morphology of poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) segmented block copolymers

A new type of poly(ether-ester) based on poly(trimethylene terephthalate) as rigid segments and poly(ethylene oxide terephthalate) as soft segments was synthesized and its crystallization behavior and morphology were investigated. Differential Scanning Calorimetry revealed that the copolymer containing 57 wt% soft segments presented a low glass transition temperature (−46.4 °C) and a high melting temperature (201.8 °C), suggesting that it had the typical characteristic of thermoplastic elastomer. With increasing soft segment content from 35 to 57 wt%, the crystallization morphology transformed from banded spherulites to compact seaweed morphology at a certain film thickness, which was due to the change of surface tension and diffusivity caused by increasing the soft segment content. Moreover, with the decrease of film thickness from 15 to 2 μm, the crystallization morphology of the copolymer (57 wt% soft segment) changed from wheatear-like, compact seaweed to dendritic. Scanning Electron Microscopy revealed that some flower-like crystals presenting in the bulk, which had been surprisingly found in the poly(ether-ester) segmented block copolymers for the first time. Possible mechanism was discussed in the text.