Direct Pyrolysis - Mass Spectrometry Analysis of Thermal Degradation of Thio-Click-Modified Poly(2-oxazoline)

Poly(2-(3-butenyl)-2-oxazoline)s (PBOX) with glucose-S-butyl (Glc) and perfluoroalkyl-S-butyl (F) side chains (three samples: Glc/F = 100/0, 0/100, and 88/12) are synthesized by ring-opening polymerization of 2-butenyl-2-oxazoline and thiol-ene click photochemistry, and their thermal properties are analyzed by direct-pyrolysis mass spectrometry. Significant changes in the thermal stability and thermal-degradation products are observed depending on the structure of the side chain. The thermal degradation of PBOX-Glc and PBOX-F homopolymers starts with loss of side chains at relatively low temperatures and successive cleavage along the side and main chains follows. The stability of the glucose units of the PBOX-Glc/F copolymer is significantly increased by the presence of perfluoroalkyl groups, attributable to OH···F hydrogen bonding interactions during pyrolysis. Comprehensive DP-MS analysis of the thermal degradation characteristics of thio-click-modified poly[2-(3-butenyl)-2-oxazoline] (PBOX), carrying glucose and/or perfluoroalkyl groups is carried out. Significant changes in the thermal stability and thermal degradation products are observed depending on the structure of the side chain. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.