Experimental evidence for immiscibility of enantiomeric polymers: Phase separation of high-molecular-weight poly(ʟ-lactide)/poly(ᴅ-lactide) blends and its impact on hindering stereocomplex crystallization

Although polymers tend not to mix, it remains challenging to characterize the immiscibility of enantiomeric poly(ʟ-lactide) (PLLA) and poly(ᴅ-lactide) (PDLA), particularly with equivalent and high molecular weight (high MW), which frustratingly disfavors the exclusive stereocomplexation. By introducing a random copolymer (PLC) of ʟ-lactide and caprolactone to form binary blends with PLLA and PDLA, the phase behavior of high-MW PLLA/PDLA blends was investigated mainly by using differential scanning calorimetry (DSC) and atomic force microscopy (AFM). DSC results showed that PLLA/PLC blends exhibited a single glass transition temperature (Tg), which depended on the blending ratio and precisely corresponded with the theoretical values calculated from the Fox equation. In comparison, PDLA/PLC blends showed composition-dependent heat-capacity increment at two unchanged Tg values of pure PLC and PDLA. AFM observation revealed that PLC is completely miscible with PLLA at high MW but is immiscible with PDLA, logically suggesting immiscibility of high-MW PLLA and PDLA. Moreover, AFM results demonstrated that high-MW PLLA/PDLA blends exhibited spherical droplets in asymmetric blends and bicontinuous interpenetrating worm-like patterns in symmetric counterparts, showing distinct and well-defined interfaces, confirming the microphase separation. Additionally, different MWs fundamentally led to significant differences in miscibility, which consequently affected the crystallization behaviors of PLLA/PDLA blends. This work provides evidence for (im)miscibility and its crucial impact on the crystallization of PLLA/PDLA blends and has important implications for understanding the stereocomplexation of polymers.