Work

Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization

Year: 2014

Type: article

Abstract: Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active “living” organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by 1H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP. One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species. The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.

Source: Macromolecules

DOI: 10.1021/ma501847x

Authors: Oleg I. Kazakov, Partha P. Datta, Meghedi Isajani, Elizabeth T. Kiesewetter, Matthew K. Kiesewetter

Institution: University of Rhode Island

Language: English

Topic: biodegradable polymer synthesis and properties

Subfield: Biomaterials

Field: Materials Science

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: American Chemical Society Petroleum Research Fund, National Institute of General Medical Sciences