Homo- and Stereocomplex Crystallization of Star-Shaped Four-Armed Stereo Diblock Copolymers of Crystalline and Amorphous Poly(lactide)s: Effects of Incorporation and Position of Amorphous Blocks.

Star-shaped four-armed stereo diblock copolymers with an amorphous poly(dl-lactide) (PDLLA) core and a crystalline poly(l-lactide) (PLLA) or poly(d-lactide) (PDLA) shell (4-DL-L and 4-DL-D) and with a crystalline PLLA or PDLA core and amorphous PDLLA shell (4-L-DL and 4-D-DL) copolymers were synthesized. The effects of incorporation and position of amorphous PDLLA blocks on homo- and stereocomplex (SC) crystallization behavior of unblended copolymers and their blends (4-DL-L/4-DL-D and 4-L-DL/4-D-DL) were investigated during isothermal crystallization from the melt and DSC heating. The incorporated amorphous PDLLA blocks disturbed the SC crystallization and orientation of SC lamellae in the copolymer blends as well as homocrystallization and orientation of homocrystalline lamellae in the unblended copolymers compared to those reported for four-armed PLLA/four-armed PDLA homopolymer blends or four-armed PLLA homopolymers, irrespective of the position of amorphous PDLLA blocks. The disturbance effect was stronger for the amorphous PDLLA shell than for the amorphous PDLLA core. The crystallizability was higher for SC crystallites in the copolymer blends than for homocrystallites in the unblended copolymers, irrespective of the position of amorphous PDLLA blocks. SC crystallization in the copolymer blends disclaimed the positional effects of crystalline PLLA and PDLA blocks and amorphous PDLLA blocks on spherulite growth rate and crystallinity.