We recently and unexpectedly discovered that the cationic polymerization of o-phthalaldehyde generates cyclic poly(phthalaldehyde) in high yield, high molecular weight, and high cyclic purity. Given this surprising result, we pursued the cationic polymerization of ethyl glyoxylate to determine if the macrocyclization phenomenon is, in fact, a general trend in low ceiling temperature polyacetals. Using NMR spectroscopy, MALDI-TOF mass spectrometry, and triple detection GPC, we have uncovered divergent macrocyclization mechanisms in the cationic polymerization of ethyl glyoxylate. Back-biting is observed either via the main-chain acetal backbone or via the pendant ester to give disparate polymer products with differing physical properties. Our recent findings in primary structural characterization of the polymers and elucidation of the polymerization mechanism will be discussed. Understanding the underlying mechanisms of polymerization and the ability to rigorously control polymer structure has profound implications towards the design of new materials. 

Divergent macrocyclization mechanisms in the cationic polymerization of ethyl glyoxylate

248th National Meeting (2014)

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