Spin-Trapping Analysis of Thermal Degradation Reaction of Poly(butylene terephthalate)

Abstract

Poly(butylene terephthalate) (PBT), and its oligomer, were doped with the spin-trapping reagent, 2-methyl-2-nitrosopropane (MNP), by a solution-casting method in order to detect the short-lived radical intermediates during thermal degradation. In the case of PBT, two types of spin adduct were observed by electron spin resonance (ESR) spectroscopy upon stepwise heating from room temperature to 200 °C and during annealing at 130 °C; the ESR spectrum exhibited an isotropic three-line signal, with a hyperfine coupling constant (hfcc) aN ≈ 0.8 mT, as well as an anisotropic component. These adducts were present on the order of 10–5 mol/L. The isotropic component was assigned to arise uniquely from the benzoyl radical, •CO-ϕ. The anisotropic component was carefully investigated by ESR spectroscopy and high-performance liquid chromatography–electrospray ionization–mass spectrometry (HPLC-ESI-MS), using low-molecular-weight model compounds such as n-butyl benzoate (BB), di-n-butyl terephthalate (DBT), and deuterat...