The Influence of Diisocyanate Structure on Thermal Stability of Thermoplastic Polyurethane Elastomers Based on Diphenylmethane-Derivative Chain Extender with Sulfur Atoms

The work is a continuation of the research on thermoplastic polyurethane (TPU) elastomers containing sulfur atoms which are incorporated into the polyurethane chain using aliphatic-aromatic chain extenders. These materials show some improved properties in relation to conventional ones, e.g., adhesion to metals, bacterial resistance and refractive index. The present study deals with the detailed characteristics of the process of thermal decomposition of TPU elastomers obtained from 2,2′-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 1,1′-methanediylbis(4-isocyanatobenzene) (MDI) or 1,6-diisocyanatohexane (HDI) and poly(oxytetramethylene) diol of M(n) = 2000 g/mol by thermogravimetric analysis coupled on-line with Fourier transform infrared spectroscopy. The analysis was performed under inert and oxidative conditions. All TPU elastomers were found to have a relatively good thermal stability, with those based on aromatic diisocyanate being at an advantage. In helium, they are stable up to 280–282 °C (from HDI) and 299–301 °C (from MDI), whereas in synthetic air up to 252–265 °C (from HDI) and 261–272 °C (from MDI), as measured by the temperature of 1% mass loss. Depending on the content of the hard segments and the tested atmosphere, the TPU elastomers decompose from one to four stages. From the analysis of the volatile decomposition products, it follows that the decomposition of both types of hard segments was accompanied by the evolution of carbonyl sulfide, carbon dioxide, water, sulfide dioxide, alcohols and aromatic compounds. For the hard segment derived from HDI, isocyanates, amines, and unsaturated compounds were also identified, while for the MDI-derived one, aldehydes were discovered. In turn, the polyether soft segment decomposed mainly into aliphatic ethers, aldehydes, and carbon monoxide.