Toward exclusive stereocomplex crystallization of high-molecular-weight poly(L-lactic acid)/poly(D-lactic acid) blends with outstanding heat resistance via incorporating selective nucleating agents.

In high molecular weight poly(L-lactic acid)/poly(D-lactic acid) (HMW PLLA/PDLA) blends, the construction of exclusive stereocomplex crystals (SC) with high crystallinity and strong melt memory remains a great challenge. In the present study, various norbornene dicarboxylate complexes (TMXNa, Mg, Al, or Ca) were employed as the stereo-selective nucleating agents (NAs), and their effect on the crystallization characteristics, rheological behavior, and heat resistance of PLLA/PDLA blends were thoroughly studied. Strikingly, TMX-Al facilitated the construction of exclusive SC with over 50 % crystallinity and excellent melt memory. The dense SC crystals network structure boosted the heat resistance of L/D-xAl blends with a VST as high as 145 °C. The strengthened intermolecular interaction fostered the generation of pre-ordered structure in the melt and enhanced chain interdiffusion, which contributed to intermolecular nucleation and SC crystallization in L/D-xAl blend. This study opens up a new avenue for melt processing and application development of SC-PLA materials.

Multiple noncovalent interactions tailored crystallization and performance reinforcement mechanisms of Biopolyester Composites with functional Cellulose Nanocrystals.

The slow crystallization and weak mechanical features of poly (butylene adipate-co-terephthalate) (PBAT) have become a severe industrial problem in food packaging. Inspired by principle of bionic structure, functional cellulose nanocrystals (CNC) modified with hexamethylene diisocyanate (HMDI) and toluene diisocyanate (TDI) can enhance the crystallization ability and mechanical properties of PBAT nanocomposites. Significantly, CNC-T (CNC modified by TDI) showed a stronger reinforced effect on PBAT properties than unmodified CNCs and CNC-H (CNC modified by HMDI) nanofillers due to hydrogen bonds, π-π interaction between PBAT matrix and CNC-T nanofillers with benzene ring structure. Thus, compared with pure PBAT, PBAT/5CNC-T composites displayed an enhancement of 34.5 % on the tensile strength and exhibited the most robust nucleation ability on PBAT crystallization than CNC and CNC-H. Meanwhile, the possible nucleation, crystallization, and performance reinforcement mechanisms of PBAT nanocomposites have been presented, which is very beneficial for designing robust PBAT nanocomposites with functional cellulose nanocrystals for potential green packaging.