Abstract
Supramolecular polymers (SMPs) have quite different crystallization behavior from the conventional polymers, because of the confinement effects of supramolecular units. Crystallization of SMPs undergoes in a “confined” and “dynamic” manner. Herein, we selected the 2-ureido-4[1H]-pyrimidione (UPy)-bonded poly(l-lactic acid) (PLLA) as a model SMP and investigated the crystallization kinetics, polymorphic crystalline structure and phase transition of supramolecular PLLAs (SM-PLLAs). SM-PLLAs were synthesized by the end functionalization of hydroxyl-terminated 2- and 3-arm PLLA precursors with different molecular weights. Crystallization rate and crystallinity of SM-PLLAs are strongly depressed in both nonisothermal and isothermal crystallizations, as compared to the nonfunctionalized PLLA precursors. Crystalline structure of SM-PLLAs is sensitive to the crystallization temperature (Tc). A low Tc (75–95 °C) facilitates the formation of metastable β crystals of PLLA in SM-PLLAs; while a high Tc (100–130 °C) fa...
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