Copolymerization of ε-caprolactone and morpholine-2,5-dione derivatives

Novel biodegradable poly(ester-amide)s were prepared by ring-opening copolymerization of ε-caprolactone and 3- and/or 6-alkyl-substituted morpholine-2,5-dione derivatives. The copolymerizations were carried out in the bulk using stannous octoate as an initiator. Molecular weights of the copolymers ranged from 1,0 · 10⁴ to 8,3 · 10⁴ and decreased with increasing mole fractions of morpholine-2,5-dione derivatives in the feed. ¹³C NMR sequence analysis indicated that the copolymers had a random distribution of ε-oxycaproyl and depsipeptide units, which resulted from the occurrence of transesterification reactions during copolymerization. The results of the DSC measurements and ¹³C NMR sequence analysis showed a close relationship between the crystallinity and average length of ε-oxycaproyl blocks. Copolymers with a mole fraction of depsipeptide units smaller than 0,20 were semi-crystalline, whereas incorporation of larger amounts of depsipeptide units resulted in amorphous copolymers. The melting point depression as a function of the molar composition of the semi-crystalline copolymers was in good agreement with the melting point depression predicted by the Baur equation, which indicated the rejection of depsipeptide units from crystals consisting of ε-oxycaproyl units.