Synergistic effect of star‐shaped architecture and poly(ethylene glycol) moieties on poly(lactic acid) stereocomplex crystallization behaviors

Abstract

AbstractStereocomplex (sc) crystal formation represents an important strategy to improve the physical properties of poly(lactic acid) (PLA), including enhanced thermal resistance, anti‐hydrolysis and mechanical performance. Therefore, understanding and controlling the sc crystallization behaviors is an important and widely studied research topic. Herein, we investigate the cooperative effect of star‐shaped PLA chain topology and poly(ethylene glycol) incorporation on sc formation. We synthesize a series of poly(lactides), including poly(l‐lactic acid) (PLLA), poly(d‐lactic acid), star‐shaped PLLA and poly(d‐lactic acid)‐poly(ethylene glycol)‐poly(d‐lactic acid) (DED) triblock copolymer, via ring‐opening polymerization of lactide, followed by solution blending to form PLA stereocomplexes (scPLAs). The chemical structure of the prepared scPLAs is characterized by Fourier transform infrared and nuclear magnetic resonance, whereas the crystallization behavior and spherulite morphology are investigated by wide‐angle X‐ray diffraction, DSC and polarized optical microscopy. Linear PLLA/star‐shaped poly(d‐lactic acid) presents rapid crystallization behaviors and high crystallinity due to the excellent nucleation ability of star‐shaped chain topology. For isothermal crystallization, star‐shaped PLLA/DED exhibits the fastest crystallization kinetics, the highest crystallinity and the lowest crystallization half‐time of all samples. It is found that addition of poly(ethylene glycol) segments can increase chain mobility and backbone flexibility, further facilitating the crystallization of scPLA containing star‐shaped chain architecture. These results demonstrate an effective approach to cooperatively promote scPLA formation, with potential use for practical applications. © 2022 Society of Industrial Chemistry.