Medical grade polylactide, copolyesters and polydioxanone: Rheological properties and melt stability

Rheological measurements have shown that lactide-based copolymers with L-lactide content between 50 and 100 mol% with varying comonomers, as well as polydioxanone (PDX), can be used in additive manufacturing analogously to poly(L-lactide) (PLLA) if their melt behaviour are balanced. The results indicate that copolymers can be melt processed if the temperature is adjusted according to the melting point, and parameters such as the speed are tuned to conteract the elastic response. Small amplitude oscillatory shear (SAOS) rheology, thermal and chemical characterisation allowed us to map the combined effect of temperature and frequency on the behaviour of six degradable polymers and their melt stability. Values of complex viscosity and Tan delta obtained through nine time sweeps by varying temperature and frequency showed that the molecular structure and the number of methylene units influenced the results, copolymers of L-lactide with D-Lactide (PDLLA) or glycolide (PLGA) had an increased elastic response, while copolymers with trimethylene carbonate (PLATMC) or epsilon-caprolactone (PCLA) had a more viscous behaviour than PLLA, with respect to their relative melting points. PDLLA and PLGA require an increased temperature or lower speed when processed, while PLATMC and PCLA can be used at a lower temperature and/or higher speed than PLLA. PDX showed an increased viscosity compared to PLLA but a similar melt behaviour. Negligible chain degradation were observed, apart from PLGA.