Microstructure analysis and thermal property of copolymers made of glycolide and ϵ‐caprolactone by stannous octoate

Abstract

AbstractGlycolide (GL) and ϵ‐caprolactone (CL) were copolymerized in bulk at relatively high temperatures using stannous octoate as a catalyst. To investigate the relationship among microstructure, thermal properties, and crystallinity, three series of copolymers prepared at various reaction temperatures, times, and comonomer feed ratios were prepared and characterized by 1H and 13C NMR, DSC, and wide‐angle X‐ray diffraction (WAXD). The 600‐MHz 1H NMR spectra provided information about not only the copolymer compositions but also about the chain microstructure. The reactivity ratios (rG and rC) were calculated from the monomer sequences and were 6.84 and 0.13, respectively. In terms of overall feed compositions, the sequence lengths of the glycolyl units calculated from the reactivity ratios exceeded those measured from the polymeric products. Mechanistic considerations based on reactivity ratios, monomer consumption data, and average sequence lengths are discussed. The unusual phase diagram of GL/CL copolymers implies that the copolymer melting temperature does not depend on its composition alone but rather on the nature of the sequence distribution. The DSC and WAXD measurements show a close relationship between polymer crystallinity and the nature of the polymer sequence. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 544–554, 2002; DOI 10.1002/pola.10123