Study on the Differences in Crystallization Behavior of Poly(lactic acid) (PLA) Induced by Amide-based and Hydrazide-based Nucleating Agents

Jiang-Hua Lin; Wen-Hao Xiao; Jing-Bo Wu; Jia-Le Wu; Rui-Jie Xu; Cai-Hong Lei

doi:10.1007/s10118-026-3575-z

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Study on the Differences in Crystallization Behavior of Poly(lactic acid) (PLA) Induced by Amide-based and Hydrazide-based Nucleating Agents

RESEARCH ARTICLE | Updated：2026-03-26

- Study on the Differences in Crystallization Behavior of Poly(lactic acid) (PLA) Induced by Amide-based and Hydrazide-based Nucleating Agents
- Study on the Differences in Crystallization Behavior of Poly(lactic acid) (PLA) Induced by Amide-based and Hydrazide-based Nucleating Agents
- Chinese Journal of Polymer Science 2026年44卷第4期页码：1173-1185
- Affiliations：
  
  Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
- Author bio：
  
  xu565786@163.com (R.J.X.)
  lch528@gdut.edu.cn (C.H.L.)
- Funds：
  
  This work was financially supported by the Project of the National Science Foundation of China (Nos. 52173033, 51773044 and 51603047), Foshan Science and Technology Innovation Project (No. FS0AA-KJ919-4402-0145).;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3575-z.The data that support the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3575-z
  中图分类号：
- 收稿：2025-11-18，
  
  录用：2026-01-14，
  
  网络首发：2026-03-10，
  
  纸质出版：2026-04-05
- Accepted：
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Lin, J. H.; Xiao, W. H.; Wu, J. B.; Wu, J. L.; Xu, R. J.; Lei, C. H. Study on the differences in crystallization behavior of poly(lactic acid) (PLA) induced by amide-based and hydrazide-based nucleating agents. Chinese J. Polym. Sci. 2026, 44, 1173–1185

Jiang-Hua Lin, Wen-Hao Xiao, Jing-Bo Wu, et al. Study on the Differences in Crystallization Behavior of Poly(lactic acid) (PLA) Induced by Amide-based and Hydrazide-based Nucleating Agents[J]. Chinese Journal of Polymer Science, 2026, 44(4): 1173-1185.
Lin, J. H.; Xiao, W. H.; Wu, J. B.; Wu, J. L.; Xu, R. J.; Lei, C. H. Study on the differences in crystallization behavior of poly(lactic acid) (PLA) induced by amide-based and hydrazide-based nucleating agents. Chinese J. Polym. Sci. 2026, 44, 1173–1185 DOI： 10.1007/s10118-026-3575-z.

Jiang-Hua Lin, Wen-Hao Xiao, Jing-Bo Wu, et al. Study on the Differences in Crystallization Behavior of Poly(lactic acid) (PLA) Induced by Amide-based and Hydrazide-based Nucleating Agents[J]. Chinese Journal of Polymer Science, 2026, 44(4): 1173-1185. DOI： 10.1007/s10118-026-3575-z.

摘要

Hydrazide-based nucleating agent (DBTA) outperforms amide analogs in promoting PLA crystallization. Simulations reveal that DBTA’s smaller electrostatic potential difference induces stronger intermolecular hydrogen bonds. This accelerates PLA chain ordering into gt conformations

achieving high crystallinity (58.4%) and a rapid crystallization time of 2.9 min.

Abstract

Although amide- and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid) (PLA)

structurally similar nucleating agents exhibit significant differences in their crystallization-promoting efficiency

and the underlying mechanism remains unclear. In this study

a series of nucleating agents

including

-diphenylterephthalamide (DPTA)

-triphenyl-1

5-benzenetricarboxamide (TPTA)

-diphenyl terephthalohydrazide (DBTA)

and

-tribenzoyl-1

5-benzenetricarbohydrazide (TBTA)

were designed and synthesized to investigate the differences in their effects on the crystallization performance of PLA. Density functional theory (DFT) and molecular dynamics (MD) simulations showed that DBTA had a smaller electrostatic potential difference (66.2 kcal/mol). During the cooling process

DBTA could stably form more intermolecular hydrogen bonds with PLA and exhibit a higher interaction energy

thus theoretically enabling more efficient promotion of PLA crystallization. Further differential scanning calorimetry (DSC) results revealed that at a 0.5 wt% loading of DBTA

the crystallization peak temperature of the PLA-DBTA composite reached 118.1 °C during cooling

whereas no distinct crystallization peak was observed for pure PLA under identical conditions. The crystallinity of the composite was significantly increased to 58.4% compared to 14.6% of pure PLA. Moreover

under isothermal crystallization at 130 °C

DBTA reduced the half-crystallization time of PLA to 2.9 min

while the half-crystallization time for pure PLA was 27.4 min. Time-resolved Fourier transform infrared spectroscopy (FTIR) results also confirmed that DBTA promoted the formation of gt conformational isomers of PLA during the crystallization process. This study elucidates the mechanism behind the performance differences between structurally similar nucleating agents in regulating PLA crystallization from the perspective of molecular electrostatic potential and hydrogen bonding interactions

providing a theoretical basis for the molecular design of efficient nucleating agents.

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references

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