Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Ring‐opening polymerization (ROP) of glycolide was studied in melt conditions and in the presence of two different initiators: 1‐dodecanol and 1,4‐butanediol and tin(II) 2‐ethylhexanoate as catalyst. Its subsequent polymerization provided poly(glycolic acid) with controlled molar masses ranging from 2000 to 42,000 g/mol with well‐defined structures characterized by NMR. Their thermal properties were evaluated by DSC analysis, and a glass transition temperature at infinite molar mass (T_g∞) of 44.8 °C was thus calculated. From rheological data, the critical molar mass for entanglement, M_c, was estimated to be near 11,000 g/mol. Furthermore, in situ polymerizations were also performed between the plates of the rheometer within a same temperature range from 210 to 235 °C. The variation of the storage and loss moduli during the polymerization step have been monitored by time sweep oscillatory experiments under an angular frequency ω = 10 rad/s. Finally, the development of an inverse rheological method allowed to calculate the bulk polymerization kinetics in the temperature range 200–230 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1440–1449, 2009