Highly oxidized polymers as an extreme of (bio)degradable polymers

A series of real and hypothetical polymers with a high content of -C(O)O- groups in the main chain was studied by ab-initio calculations. Carbon polymers with increasing levels of oxidation are normally correlated with higher tendencies toward environmental- and biodegradability. The ultimate oxidized polymer in this group is the hypothetical polymeric carbon dioxide. Results of the relatively inexpensive computational approach were consistent with experimental results and previous observations. The evaluation of free energies indicates trends in the effect of structural changes on stability as well as possible limitations. Several approaches to increasing the stability of highly oxidized carbon polymers are proposed.