Investigation of thermal characteristics of a series polyoxazolines by direct pyrolysis mass spectrometry

Atılkan, Nurcan
In the latest years, many studies especially on characterization and synthesis of polyoxazolines have been made. During these studies, new polyoxazolines such as poly(2-isopropyl-2-oxazoline) (PIPOX), poly(2-(3-butenyl)-2-oxazoline) (PBOX) and modified PBOX were synthesized. However, there has been no investigation on their thermal characteristics such as thermal stability and thermal degradation products. In this study, thermal degradation characteristics, thermal degradation products and thermal stability of PIPOX, PBOX and modified PBOX polymers PBOX-Perf, PBOX-Thiop, PBOX-Sug, PBOX-SP and PBOX-TP were investigated. In this study mercaptans 1H,1H,2H,2H-perfluoro-octanethiol, 3-mercapto-1,2 propanediol, thio-β-D-glucose derivative and their mixture were used in PBOX modifications. The effect of modification of PBOX with different mercaptans on thermal characteristics was also analyzed. For the PIPOX, formations of protonated monomer and oligomers from dimer to heptamer were observed. However, when the isopropyl group changes with 3-butenyl group, protonated oligomers up to trimer were observed because the crosslinking formed during the polymerization of unsaturated butenyl inhibited the production of oligomers. In addition to this, thermal degradation at lower temperatures was observed. The change in thermal stability and thermal degradation products were observed as a result of modification of PBOX with different mercaptans. Unlike PBOX-Sug thermal degradation started at very low temperatures for PBOX-Thiop and PBOX-Perf. This degradation observed at lower temperatures disappeared for PBOX-SP and PBOX-TP. For PBOX-Perf, PBOX-Sug and PBOX- Thiop, decomposition of side chains at low temperatures and decomposition of the main chain at high temperatures were observed. Although the same thermal degradation behavior for PBOX-TP and PBOX-Thiop was expected, since PBOX-TP was obtained as a result of modification of PBOX with high amounts of mercaptan used in PBOX-Thiop and small amounts of mercaptan used in the PBOX-Perf, the results show that neither PBOX-Thiop nor PBOX-Perf thermal degradation behavior are dominant. This is also valid for PBOX-SP. PBOX-SP has higher thermal stability when compared to PBOX-Sug.