Spin-Trapping Analysis and Characterization of Thermal Degradation of Thermoplastic Poly(ether–ester) Elastomer

We investigated the thermal degradation of poly­(butylene terephthalate)-<i>co</i>-poly­(ethylene oxide) (PBT-<i>co</i>-PEO), a thermoplastic poly­(ether–ester) elastomer (TPEE), through proton nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), gel permeation chromatography (GPC), and spin-trapping electron spin resonance (ESR) analysis to detect radical intermediates present during degradation. Three kinds of PBT-<i>co</i>-PEO with different component ratios of PBT/PEO were synthesized. The thermal degradation process of PBT-<i>co</i>-PEO was divided into four weight-loss stages. In the first stage from room temperature to 120 °C, we confirmed the production of two radical intermediates, O–<sup>•</sup>CH–CH<sub>2</sub> and <sup>•</sup>CH<sub>2</sub>–, by the spin-trapping method. This suggested that the initial decomposition occurred at the OCH<sub>2</sub>–CH<sub>2</sub>O bond in the PEO units. Upon annealing at 120 °C, PBT-<i>co</i>-PEO showed a small degree of random degradation, while higher PBT contents induced gelation and the production of the characteristic oligomer PBT–PEO–PBT. The gelation was attributed to cross-linking between two O–<sup>•</sup>CH–CH<sub>2</sub> moieties of PBT. In the second stage from 120 to 340 °C, a large thermo-oxidative degradation of the PEO segment occurred, accompanied by an increase in the radical amount of spin adducts. In the third stage, the thermo-oxidative degradation of PBT units was observed. The radical intermediates were thus shown to be a primary factor of the thermal degradation characteristics of TPEE.