Reaction Control in Radical Polymerization of Di-n-butyl Itaconate Utilizing a Hydrogen-Bonding Interaction

We have reported that intramolecular chain-transfer reaction takes place in radical polymerization of itaconates at high temperatures and/or at low monomer concentrations. In this paper, radical polymerizations of di-n-butyl itaconate (DBI) were carried out in toluene at 60°C in the presence of amide compounds. The 13C NMR spectra of the obtained poly(DBI)s indicated that the intramolecular chain-transfer reaction was suppressed as compared with in the absence of amide compounds. The NMR analysis of DBI and N-ethylacetamide demonstrated both 1:1 complex and 1:2 complex were formed at 60°C through a hydrogen-bonding interaction. The ESR analysis of radical polymerization of diisopropyl itconate (DiPI) was conducted in addition to the NMR analysis of the obtained poly(DiPI). It was suggested that the suppression of the intramolecular chain-transfer reaction with the hydrogen-bonding interaction was achieved by controlling the conformation of the side chain at the penultimate monomeric unit of the propagating radical with an isotactic stereosequence.

This is the peer reviewed version of the following article: Hirano, T., Higashi, K., Seno, M. and Sato, T. (2004), Reaction control in radical polymerization of di‐n‐butyl itaconate utilizing a hydrogen‐bonding interaction. J. Polym. Sci. A Polym. Chem., 42: 4895-4905., which has been published in final form at https://doi.org/10.1002/pola.20293. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.