2025 (4) 3
https://doi.org/10.15407/polymerj.47.04.200
ASSESSMENT OF THERMODEGRADATION OF IONOMER POLYURETHANES AFTER ACCELERATED DEGRADATION USING PYROLYTIC MASS SPECTROMETRY
OLEXANDRA BRYKOVA (ORCID: 0000-0002-5112-2329), OLENA AKHRANOVYCH (ORCID: 0000-0003-1652-9323), VOLODYMYR BORTNYTSKYI (ORCID: 0000-0003-4954-6533), YURI SAVELIEV (ORCID: 0000-0003-3356-9087)
Institute of Macromolecular Chemistry of the NAS of Ukraine
48 Kharkivske Highway, Kyiv, 02155, Ukraine
e-mail: elena_akh@ukr.net
Abstract
The thermal degradation of film materials obtained from waterborne polyurethane dispersions (WPUD) based on: castor oil (WPUD -1), xanthan (WPUD -2), castor oil and xanthan (WPUD -3) initial samples and after their exposure in a climate chamber (WPUD -1 * , 2 * , 3 * ), where the processes of natural degradation under the influence of UV radiation, moisture and elevated temperature are simulated, were investigated using the pyrolytic mass spectrometry (PMS) method. According to the results of exposure of polymers in a climate chamber, it was established that insignificant processes of deterioration, the initial stage of degradation, occur in the case of a sample synthesized using exclusively petrochemical raw materials (WPUD -m), and fragmentation (degradation) in the case of samples of film materials WPUD -1 * , 2 * , 3 * . The results of studies of accelerated aging of polymer samples indicate the influence of the nature of the polymer macro chain components on this process. Namely, components of natural origin accelerate this process, while the effect of the simultaneous content of vegetable oil and exopolysaccharide has signs of synergy of the process. The results of PMS show that for WPUD -1, 1*, parallel pyrolytic processes are characteristic: dissociation into isocyanate and alcohol and cleavage into primary amine, CO 2 and alkene, which leads to the rearrangement of the isocyanate fragment (m/z 56) into the amino group fragment (m/z 30) with the release of carbon dioxide (m/z 44) and the presence of fragments of the ” alkyl ” series. During the pyrolysis of WPUD -2 and WPUD -3, both before and after exposure in the climate chamber, the process of decarboxylation (m/z 44) and dehydration (m/z 18) dominates. This is due to the presence of xanthan in the polymer structure, which is caused by the degradation of the side groups of the xanthan chain (decomposition of mannose, glucuronic and pyruvic acid units), as well as dimethylolpropionic acid as a component of the ionomer polyurethane chain. And in general, for all the studied samples after accelerated degradation, a significant decrease in the intensity of the release of volatile pyrolysis products, an increase in the number of formed ionic fragments, and for samples based on Xa and castor oil + Xa, decrease in molecular weight and maximum m/z, which indicates a change in the mechanism of thermal destruction.
Keywords: anionic aqueous dispersion, pyrolysis mass spectrometry, castor oil, xanthan.
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