Crystallization and properties of nucleated poly(l-lactic acid): Effect of cyclopentanecarboxylic acid derivative as a new nucleating agent

In this study, the potential effects of N, N'-dodecanedioic bis(cyclopentanecarboxylic acid) dihydrazide (BCADD) as a new additive in poly(L-lactic acid) (PLLA) was estimated. The comparative study on the melt-crystallization showed that the BCADD as heterogeneous nuclei facilitated crystallization of PLLA in cooling, which indicated by the obvious crystallization exotherms and sharp melt-crystallization peak. Unfortunately, with increasing of BCADD from 0.5 wt% to 3 wt%, it is unexpected that the melt-crystallization peak of the BCADD-nucleated PLLA shifted toward the lower temperature and became flatter, evidencing the importance of BCADD loading for PLLA's crystallization. Additionally, the cooling rate and the final melting temperature were also proved to be important influence factors during PLLA's melt-crystallization process, but in contrast with the effect of the final melting temperature on the melt-crystallization, a higher cooling rate could more seriously weaken crystallization ability of the BCADD-nucleated PLLA. The chemical nucleation mechanism was proposed to explain the promoting effect of BCADD on the crystallization of PLLA via the analysis of frontier orbital energy. The melting behaviors after crystallization further confirmed the crystallization accelerating role of BCADD, and the melting behaviors were affected by the heating rate, crystallization temperature and BCADD loading. Although the onset thermal decomposition of the BCADD-nucleated PLLA occurred at lower temperature comparing with the pure PLLA, the intermolecular interaction of PLLA with BCADD attempted to prevent the decrease of thermal stability. Overall, the addition of BCADD resulted in the complicated effect on the tensile modulus and tensile strength of PLLA, but the elongation at break continuously decreased when increasing BCADD loading.

Automated summary

This study evaluated the potential effects of BCADD as an additive in PLLA, and found that BCADD acted as a heterogeneous nucleus to facilitate PLLA crystallization. However, excessive loading of BCADD weakened the crystallization ability of PLLA. Cooling rate and final melting temperature were important factors in the melt-crystallization process, and a higher cooling rate had a negative impact on the crystallization ability of BCADD-nucleated PLLA. The chemical nucleation mechanism and melting behaviors further confirmed the crystallization accelerating role of BCADD and its influence on PLLA properties.