Effect of Amide Bond Incorporation on the Chemical Imidization Kinetic Pathways, Structure, and Properties of Colorless Polyimide/Polyamide-imide

Zhao-hua Sheng; Jun-hui Luo; Kang Zhang; Ling-jian Kong; Xiang-yang Liu

doi:10.11777/j.issn1000-3304.2026.26066

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Effect of Amide Bond Incorporation on the Chemical Imidization Kinetic Pathways, Structure, and Properties of Colorless Polyimide/Polyamide-imide

Research Article | 更新时间：2026-07-08

- Effect of Amide Bond Incorporation on the Chemical Imidization Kinetic Pathways, Structure, and Properties of Colorless Polyimide/Polyamide-imide
- Acta Polymerica Sinica Vol. 57, Issue 7, Pages: 1502-1512(2026)
- 作者机构：
  
  四川大学高分子科学与工程学院先进高分子材料全国重点实验室成都 610065
- 作者简介：
  
  Xiang-yang Liu, E-mail: lxy@scu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26066
  CLC：
- CSTR：32057.14.GFZXB.2026.7609
- Received：06 March 2026，
  
  Accepted：21 April 2026，
  
  Online First：18 June 2026，
  
  Published：20 July 2026
- 稿件说明：
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盛朝华, 罗俊慧, 张康, 孔令见, 刘向阳. 酰胺键引入对无色聚酰亚胺/聚酰胺-酰亚胺化学酰亚胺化动力学路径及结构与性能的影响. 高分子学报, 2026, 57(7), 1502-1512.

Sheng, Z. H.; Luo, J. H.; Zhang, K.; Kong, L. J.; Liu, X. Y. Effect of amide bond incorporation on the chemical imidization kinetic pathways, structure, and properties of colorless polyimide/polyamide-imide. Acta Polymerica Sinica (in Chinese), 2026, 57(7), 1502-1512.
盛朝华, 罗俊慧, 张康, 孔令见, 刘向阳. 酰胺键引入对无色聚酰亚胺/聚酰胺-酰亚胺化学酰亚胺化动力学路径及结构与性能的影响. 高分子学报, 2026, 57(7), 1502-1512. DOI： 10.11777/j.issn1000-3304.2026.26066. CSTR： 32057.14.GFZXB.2026.7609.

Sheng, Z. H.; Luo, J. H.; Zhang, K.; Kong, L. J.; Liu, X. Y. Effect of amide bond incorporation on the chemical imidization kinetic pathways, structure, and properties of colorless polyimide/polyamide-imide. Acta Polymerica Sinica (in Chinese), 2026, 57(7), 1502-1512. DOI： 10.11777/j.issn1000-3304.2026.26066. CSTR： 32057.14.GFZXB.2026.7609.

摘要

针对酰胺键引入对聚酰亚胺化学酰亚胺化动力学路径及其后续结构与性能演变影响认识不足的问题，本工作以无色透明聚酰亚胺(CPI)和聚酰胺-酰亚胺(CPAI)为研究对象，系统考察了酰胺键引入及脱水剂用量(60%~160%)对化学酰亚胺化反应动力学、完全酰亚胺化后聚集态结构以及薄膜力学和光学性能的影响. 结果表明，酰胺键的引入显著改变了化学酰亚胺化动力学路径：CPI体系在脱水剂用量达到120%以上时，由二级反应转变为一级反应；CPAI体系则在60%~100%用量下因分子内氢键作用表现为一级反应，而在120%以上因氢键网络被削弱后转为二级反应. 动力学路径差异进一步影响薄膜聚集态结构演变. X射线衍射与双折射结果表明，提高脱水剂用量可促进链堆叠致密化，增强面内取向，从而实现CPI薄膜力学与光学性能的协同提升；当脱水剂用量≥120%时，其拉伸强度、断裂伸长率和550 nm透过率分别达到130.3 MPa、10.3%和89.8%. 相比之下，CPAI薄膜表现出更高韧性，且其光学性能亦因薄膜均匀性提高而得到进一步改善. 本工作为CPI/CPAI薄膜化学酰亚胺化过程调控及综合性能优化提供了理论依据.

Abstract

To address the insufficient understanding of how amide bond incorporation affects the kinetic pathways of chemical imidization and the subsequent evolution of the structure and properties of polyimides

colorless polyimide (CPI) and copolyamide-imide (CPAI) were selected as model systems. The effects of amide bond incorporation and dehydrating agent content (60%~160%) on the kinetics of chemical imidization

the aggregated structure after complete imidization

and the mechanical and optical properties of the films were systematically investigated. The results showed that incorporating amide bonds significantly altered the kinetic pathway of chemical imidization. In the CPI system

the reaction changed from second-order kinetics to first-order kinetics when the dehydrating agent content exceeds 120%. In contrast

the CPAI system exhibited first-order kinetics at 60%~100% due to the intramolecular hydrogen-bonding-induced "built-in catalysis" effect

whereas it reverted to second-order kinetics above 120% as the hydrogen-bonding network was weakened. The difference in the kinetic pathways further affected the evolution of the aggregated structure of the films. X-ray diffraction and birefringence analyses revealed that increasing the dehydrating agent content promoted denser chain packing and enhanced in-plane orientation

thereby enabling the synergistic improvement of the mechanical and optical properties of CPI films. When the dehydrating agent content was ≥120%

the tensile strength

elongation at break

and transmittance at 550 nm of CPI films reached 130.3 MPa

10.3%

and 89.8%

respectively. In contrast

CPAI films exhibited higher toughness

and their optical properties were further improved owing to the enhanced film uniformity. This work provides a theoretical basis for regulating the chemical imidization process and optimizing the overall performance of CPI/CPAI films.

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references

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