Crystallization and morphological transition of poly(l-lactide)–poly(ε-caprolactone) diblock copolymers with different block length ratios

Abstract

The crystallization behavior, banded spherulite and morphological transition of poly(L-lactide) (PLLA) phases within the block copolymers were investigated. All experimental results showed that the structure and thermal properties of PLLA–PCL copolymers could be adjusted by varying the ratios of the chain length of the two blocks. Morphological results indicated that the banded spherulites of PLLA formed when PLLA-rich copolymers crystallized. PCL segments introduced unbalanced stresses around PLLA lamellar crystals, which resulted in a bending moment responsible for twisting of PLLA lamellar crystals. As the block length ratio of PCL to PLLA increased, an over accumulation of PCL segments influenced the twisting of PLLA lamellae. In addition, it was interesting to find that the banded spherulite morphology changed with increasing the crystallization temperature. The crystallization temperature has an effect on the relationship between the sense of lamellar twisting and the morphological transition of PLLA, which is reflected in the fact that the band spacing of banded spherulites showed strong temperature dependence when the crystallization temperature exceeds 115 °C, while it exhibited weak temperature dependence below 115 °C. In particular, above 125 °C the band spacing disappeared and nonbanded spherulites formed.