Thermal and morphological properties of poly(l-lactic acid)/poly(d-lactic acid)-b-polycaprolactone diblock copolymer blends

Due to the brittle nature of poly(lactic acid) many attempts have been made to flexibilize this polyester for applications such as thin films and foils. However, due to complex phase behavior, many drawbacks for plasticizer and blend components are described. To overcome miscibility, post crystallization and migration issues a principle of click-chemistry was employed to change the molecular characteristics from external to internal plasticization by fixation of a plastisizing unit with help of a stereocomplex crystallization. Hydroxyl terminated polycaprolactone oligomers were used as a macroinitiator for the ring opening polymerization of d-lactide, resulting in blockcopolymers with plasticizing unit polycaprolactone and compatibilizing poly(d-lactic acid)-blocks. The generated block copolymers were blended with a poly(l-lactic acid)-matrix and formed so called stereocomplex crystals. In comparison to unbound polycaprolactone the polycaprolactone blocks show a lower migration tendency regarding a solution test in toluene. Besides that, trapping the plasticizing units via stereocomplex also improves the efficiency of the plasticizer. In comparison to polymer blends with the same amount of non-bonded polycaprolactone oligomers of the same molecular weight, block copolymers with poly(d-lactic acid) and polycaprolactone can shift the glass transition temperature to lower values. This effect can be explained by the modulated crystallization of the polycaprolactone-blocks trapped into the matrix, so that a higher effective amount can interact with the poly(l-lactic acid)-matrix.