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Updated: Oct 3, 2026

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Enzyme-catalyzed ring-opening copolymerization of 5-methyl-5-benzyloxycarbonyl-1,3-dioxan-2-one (MBC) with
T F al-Azemi1, J P Harmon, K S Bisht
1Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, Florida 33620, USA.
Abstract:
Enzymatic ring-opening copolymerization of 5-methyl-5-benzyloxycarbonyl-1,3-dioxan-2-one (MBC) with trimethylene carbonate (TMC) was investigated. A route to aliphatic polycarbonates decorated with pendent carboxylic acid groups is demonstrated. Lipase from Pseudomonas fluorescens (AK) was selected to perform the copolymerization at various monomers feed ratios. Copolymers with different composition were prepared by varying the monomer feed ratio from 10% to 80% MBC. 1H, 13C, and 1H-13C HETCOR NMR spectra were used to analyze the microstructure of the copolymers. The 1H NMR spectra indicated lower incorporation of TMC in the copolymer than was expected from the monomer feed ratio. Analysis of the 13C spectra did not indicate an ordered structure but instead suggested the formation of random polymers. This was further confirmed by the thermal data obtained for representative samples. The thermal properties at different feed ratios of poly[MBC-co-TMC] copolymers were investigated by differential scanning calorimetry (DSC). No melting temperature (Tm) for either homopolymers or copolymers was observed. A plot of 1/Tg(K) vs the weight composition of MBC in the copolymers was constructed and was consistent with copolymers that tend toward random distribution; this was confirmed from the NMR data.
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