Control of Stereospecificity in the Radical Polymerization of N-Methyl-N-(2-pyridyl)acrylamide by Conformational Switching of the Monomer with Protonation

Radical polymerization of N-methyl-N-(2-pyridyl)acrylamide (MPyAAm) was carried out in dichloromethane at low temperatures in the presence of trifluoroacetic acid (TFA). The m dyad contents of the polymers obtained at 0°C increased linearly from 37% to 60% with increase in the [TFA]0/[MPyAAm]0 ratio from unity to 5. NMR analysis of MPyAAm-TFA mixtures in dichloromethane-d2 revealed that the favorable conformation in terms of the pyridyl group to the carbonyl group in MPyAAm switched from s-trans to s-cis by protonation. The results suggest that controlling the conformation of MPyAAm resulted in control of the stereospecificity in radical polymerization of the monomer.

This is the peer reviewed version of the following article: Hirano, T., Morikami, A. and Ute, K. (2011), Control of stereospecificity in the radical polymerization of N‐methyl‐N‐(2‐pyridyl)acrylamide by conformational switching of the monomer with protonation. J. Polym. Sci. A Polym. Chem., 49: 4164-4171., which has been published in final form at https://doi.org/10.1002/pola.24858. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.