This research will contribute to a detailed understanding of the molecular microstructures and polymerization mechanisms of two synthetic polymers having great technological significance. These polymers are poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAC). The information to be obtained should facilitate the construction of correlations between the structures of these substances and their useful properties. Also, it should suggest synthetic procedures for tailoring the structures so as to achieve desired results. The work will involve the reductive conversion of the polymers into hydrocarbons whose molecular structures will be established by state-of-the-art 113C NMR. Knowledge of the reduction chemistries will then allow the structures of the starting polymers to be determined from those of the reduced materials. This approach, coupled with parallel studies involving deuterated reducing agents and/or deuterated polymers, will establish the formation mechanisms of various structural defects (branches, chain ends, etc.) in the polymers of interest. The research with PVC should provide conclusive answers to most of the remaining questions about the effects of structure on the thermal and oxidative stability of this polymer. Moreover, in the case of PVAC, the work should yield much information about the structure of another useful polymer, poly(vinyl alcohol), which is made from PVAC.
