Stereospecific Radical Polymerization of N-tert-Butoxycarbonylacrylamide in the Presence of Fluorinated Alcohols

Radical polymerization of N-tert-butoxycarbonylacrylamide (NBocAAm) in toluene at low temperatures in the presence of the fluorinated alcohols, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol and nonafluoro-tert-butanol, afforded atactic, heterotactic and syndiotactic polymers, respectively. NMR analysis revealed that the fluorinated alcohols formed hydrogen bonding-assisted complexes with NBocAAm, with different structures. The difference in the structures of the complexes was responsible for the differences in the induced stereospecificities. Based on the structures of the complexes between NBocAAm and the fluorinated alcohols, mechanisms for the three kinds of stereospecific radical polymerizations are proposed.

This is the peer reviewed version of the following article: Hirano, T., Yamaoka, R., Miyazaki, T. and Ute, K. (2010), Stereospecific radical polymerization of N‐tert‐butoxycarbonylacrylamide in the presence of fluorinated alcohols. J. Polym. Sci. A Polym. Chem., 48: 5718-5726., which has been published in final form at https://doi.org/10.1002/pola.24373. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.