Controlled Organocatalytic Ring-Opening Polymerization of ε-Thionocaprolactone

Authors

Partha P. Datta, University of Rhode Island
Matthew K. Kiesewetter, University of Rhode IslandFollow

Document Type

Article

Date of Original Version

2016

Department

Chemistry

Abstract

For the first time, the controlled ring-opening polymerization (ROP) of ε-thionocaprolactone (tnCL) is conducted. The organocatalytic ROP of tnCL occurs without carbonyl scrambling, leading to homopoly(ε-thionocaprolactone) (PtnCL). The ROP by base catalysts alone is proposed to proceed via a nucleophilic mechanism, while the addition of an H-bond donating thiourea (TU) is shown to provide excellent reaction control. The increased reaction control provided by the TU occurs in the virtual absence of binding between tnCL and TU, and a mechanistic account for this observation is discussed. The monomer ring strain is measured and found to be similar to δ-valerolactone (VL). Copolymers with VL are synthesized, and the resulting analysis of the copolymer materials properties provides the only known physical characterizations of poly(thio(no)ester-co-ester)s.

Citation/Publisher Attribution

Datta, P. P., & Kiesewetter, M. K. (2016). Controlled Organocatalytic Ring-Opening Polymerization of ε-Thionocaprolactone. Macromolecules, 49(3), 774-780. doi: 10.1021/acs.macromol.6b00136

Available at: http://dx.doi.org/10.1021/acs.macromol.6b00136