Heterogeneous Nucleation Effect of N, N'-Adipic Bis(4-phenylbutyric Acid) Dihydrazide on Crystallization Process of Poly(L-lactic Acid)

Abstract

Enhancing crystallization ability is a fundamental challenges in Poly(L-lactic acid) (PLLA) industry, therefore, the goal of this work was to synthesis a new organic nucleating agent N, N'-adipic bis(4-phenylbutyric acid) dihydrazide (APAD), and investigate its effect on non-isothermal crystallization, isothermal crystallization, melting behavior, thermal stability, and optical property of PLLA. Non-isothermal melt crystallization results showed that APAD acted as more effective nucleating and accelerating agent for the crystallization of PLLA, as a result, upon cooling at 1 °C/min, PLLA/0.5 %APAD had the highest onset crystallization temperature 136.4 °C and the crystallization peak temperature 132.0 °C, as well as the largest non-isothermal crystallization enthalpy 48.1 J/g. However, with increasing of APAD concentration from 0.5 wt.% to 3 wt.%, the crystallization peak shifted to the lower temperature. In contrast, for the non-isothermal cold crystallization process, the effect of APAD concentration on the crystallization behavior of PLLA was negligible. Additionally, the non-isothermal crystallization process was also depended on the cooling rates and the final melting temperature. In isothermal crystallization section, to compare with the primary PLLA, the crystallization half-time of PLLA/APAD could decrease from 254.3 s to the minimum value 29.4 s, with 0.5 wt.% APAD contents at 125 °C. Melting behavior of PLLA/APAD samples under different conditions further confirmed the heterogeneous nucleation effect of APAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Finally, the addition of APAD decreased the thermal stability to some extent, although APAD could not change the thermal decomposition profile of PLLA. And a drop of PLLA/APAD samples in light transmittance resulted from the double influence of the enhancement of crystallization and the opaqueness of APAD.