Different crystallinity of poly(d,l-lactide-co-p-dioxanone) copolymers acquired by control of chain microstructure

Poly(d,l-lactide-co-p-dioxanone) (P(LA-co-PDO)) copolymers with different chain microstructures were synthesized by one-step or two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monomers using stannous octoate [Sn(Oct)2]/n-dodecanol as the initiating system. The average sequence lengths of the lactidyl (LLA) and dioxanyl (LPDO) units were calculated from the 1H NMR spectra. It was found that both LLA and LPDO values from the two-step syntheses were significantly longer than those from the corresponding one-step syntheses, indicating more blocky structure achieved for the two-step copolymers. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline, while the one-step copolymers were completely amorphous. In conclusion, the crystallinity of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the microstructure of the copolymers via different polymerization routes.