Improved oxidative biostability of porous shape memory polymers by substituting triethanolamine for glycerol

While many aromatic polyurethane systems suffer from poor hydrolytic stability, more recently proposed aliphatic systems are oxidatively labile. The use of the renewable monomer glycerol as a more oxidatively resistant moiety for inclusion in shape memory polymers (SMPs) is demonstrated here. Glycerol-containing SMPs and the amino alcohol control compositions are compared, with accelerated degradation testing displaying increased stability (time to complete mass loss) as a result of the inclusion of glycerol without sacrificing the shape memory, thermal transitions, or the ultralow density achieved with the control compositions. Gravimetric analysis in accelerated oxidative solution indicates that the control will undergo complete mass loss by approximately 18 days, while lower concentrations of glycerol will degrade fully by 30 days and higher concentrations will possess approximately 40% mass at the same time. In real-time degradation analysis, high concentrations of glycerol SMPs have 96% mass remaining at 8 months with 88% gel fraction remaining that that time, compared to less than 50% mass for the control samples with 5% gelation. Mechanically, low glycerol-containing SMPs were not robust enough for testing at three months, while high glycerol concentrations displayed increased elastic moduli (133% of virgin materials) and 18% decreased strain to failure. The role of the secondary alcohol, as well as isocyanates, is presented as being a crucial component in controlling degradation; a free secondary alcohol can more rapidly undergo oxidation or dehydration to ultimately yield carboxylic acids, aldehydes, carbon dioxide, and alkenes. Understanding these pathways will improve the utility of medical devices through more precise control of property loss and patient risk management through reduced degradation. (c) 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47857.