Poly(L-Lactide), 8. High-Temperature Hydrolysis of Poly(L-Lactide) Films with Different Crystallinities and Crystalline Thicknesses in Phosphate-Buffered Solution

Poly(L-lactide) (PLLA) films having different crystallinities (Xc's) and crystalline thicknesses (Lc's) were prepared by annealing at different temperatures (Ta's) from the melt and their high-temperature hydrolysis was investigated at 97°C in phosphate-buffered solution. The changes in remaining weight, molecular weight distribution, and surface morphology of the PLLA films during hydrolysis revealed that their hydrolysis at the high temperature in phosphate-buffered solution proceeds homogeneously along the film cross-section mainly via the bulk erosion mechanism and that the hydrolysis takes place predominantly and randomly at the chains in the amorphous region. The remaining weight was higher for the PLLA films having high initial Xc when compared at the same hydrolysis time above 30 h. However, the difference in the hydrolysis rate between the initially amorphous and crystallized PLLA films at 97°C was smaller than that at 37°C, due to rapid crystallization of the initially amorphous PLLA film by exposure to crystallizable high temperature in phosphate-buffered solution. The hydrolysis constant (k) values of the films at 97°C for the period of 0–8 h, 0.059–0.085 h–1 (1.4–2.0 d–1), were three orders of magnitude higher than those at 37°C for the period of 0–12 months, 2.2–3.4×10–3 d–1. The melting temperature (Tm) and Xc of the PLLA films decreased and increased, respectively, monotonously with hydrolysis time, excluding the initial increase in Tm for the PLLA films prepared at Ta = 100, 120, and 140°C in the first 8, 16, and 16 h, respectively. A specific peak that appeared at a low molecular weight around 1×104 in the GPC spectra was ascribed to the component of one fold in the crystalline region. The relationship between Tm and Lc was found to be Tm (K) = 467·[1–1.61/Lc (nm)] for the PLLA films hydrolyzed at 97°C for 40 h.