Hetero-stereocomplex formation of stereoblock copolymer of substituted and non-substituted poly(lactide)s

Abstract

The crystallization behavior of the stereoblock copolymer of substituted and non-substituted poly(lactide)s, i.e., poly( d-2-hydroxybutyrate) and poly( l-lactide) chains having the opposite configurations [P(D-2HB)- b-PLLA] and the reference block copolymer of poly( d-2-hydroxybutyrate) and poly( d-lactide) chains with the identical configurations [P(D-2HB)- b-PDLA] was investigated. At the crystallizable temperature range of 60–160 °C, the crystallized P(D-2HB)- b-PLLA contained solely the hetero-stereocomplex crystallites as a crystalline species, without formation of poly( d-2-hydroxybutyrate) or poly( l-lactide) homo-crystallites, in contrast with their polymer blends. On the other hand, at the crystallizable temperature range of 60–140 °C, the crystallized P(D-2HB)- b-PDLA had only PDLA homo-crystallites as crystalline species, reflecting no co-crystallites formation between poly( d-2-hydroxybutyrate) and poly( d-lactide) chains having the same configurations. The equilibrium melting temperature of hetero-stereocomplex crystallites in P(D-2HB)- b-PLLA was 189.0 °C, which was higher than 171.3 °C of PDLA homo-crystallites in P(D-2HB)- b-PDLA. Although the final crystallinity of P(D-2HB)- b-PLLA was higher than those of P(D-2HB)- b-PDLA, the spherulite growth rate of P(D-2HB)- b-PLLA was lower.The regime analysis indicated unusual nucleation mechanism of P(D-2HB)- b-PLLA.