Synthesis, Curing and Properties of Flavonoid Based Bio-benzoxazine Resins

Chang-wen Hu; Rui Yang; Kan Zhang

doi:10.11777/j.issn1000-3304.2025.25009

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Synthesis, Curing and Properties of Flavonoid Based Bio-benzoxazine Resins

Research Article | 更新时间：2025-07-28

- Synthesis, Curing and Properties of Flavonoid Based Bio-benzoxazine Resins
- Acta Polymerica Sinica Vol. 56, Issue 8, Pages: 1426-1437(2025)
- 作者机构：
  
  江苏大学材料科学与工程学院高分子材料研究所镇江 212013
- 作者简介：
  
  Kan Zhang, E-mail: zhangkan@ujs.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25009
  CLC：
- CSTR：32057.14.GFZXB.2025.7404
- Received：07 January 2025，
  
  Accepted：28 April 2025，
  
  Published Online：05 June 2025，
  
  Published：20 August 2025
- 稿件说明：
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胡长文, 杨蕊, 张侃. 黄酮类生物基苯并噁嗪树脂的合成、固化机理及性能研究. 高分子学报, 2025, 56(8), 1426-1437

Hu, C. W.; Yang, R.; Zhang, K. Synthesis, curing and properties of flavonoid based bio-benzoxazine resins. Acta Polymerica Sinica, 2025, 56(8), 1426-1437
胡长文, 杨蕊, 张侃. 黄酮类生物基苯并噁嗪树脂的合成、固化机理及性能研究. 高分子学报, 2025, 56(8), 1426-1437 DOI： 10.11777/j.issn1000-3304.2025.25009. CSTR： 32057.14.GFZXB.2025.7404.

Hu, C. W.; Yang, R.; Zhang, K. Synthesis, curing and properties of flavonoid based bio-benzoxazine resins. Acta Polymerica Sinica, 2025, 56(8), 1426-1437 DOI： 10.11777/j.issn1000-3304.2025.25009. CSTR： 32057.14.GFZXB.2025.7404.

摘要

本文设计并合成了一系列黄酮类生物基苯并噁嗪单体，系统研究了不同官能度黄酮类生物基苯并噁嗪分子结构与固化机理及固化后树脂材料热稳定性和阻燃性的关联机制. 首先采用NMR、FTIR等表征手段确认苯并噁嗪单体的分子结构，再通过DSC和原位FTIR谱图来研究苯并噁嗪单体的聚合过程结构演变与固化机理. 该

系列黄酮类苯并噁嗪中的酚羟基与其相邻羰基之间分子内氢键被确定为导致热潜伏催化固化行为的根本原因. 其中，基于芹菜素双官苯并噁嗪树脂制备的热固性树脂具有极高的热稳定性(

为384 ℃)，由木犀草素基三官苯并噁嗪制备的聚苯并噁嗪树脂具有最为优异的阻燃性(HRC

10 J·g

-1

·K

-1

). 以上研究表明黄酮类生物基热固性树脂在高性能材料领域具有巨大的应用潜力.

Abstract

In this study

a series of flavonoid-based benzoxazine monomers were designed and synthesized

and the correlation mechanisms among the molecular structures with different functionalities of resins and their curing mechanisms

as well as the thermal stability and flame retardancy of thermosets were systematically investigated. The molecular structures of the benzoxazine monomers were confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR)

and the structural evolution of the polymerization process and the corresponding curing mechanism of benzoxazine monomers were investigated by differential scanning calorimetry (DSC) and

in situ

FTIR spectroscopy. Intramolecular hydrogen bonding between the phenolic hydroxyl and its adjacent carbonyl group in benzoxazines was identified as the underlying cause of the thermally latent catalytic curing behavior. In addition

the thermoset derived from apigenin-based bi-benzoxazine exhibited remarkably high thermal stability (

= 384 ℃)

while polybenzoxazine obtained from luteolin-based tri-functional benzoxazine showed outstanding flame retardancy (HRC

10 J·g

-1

·K

-1

). The aforementioned studies suggest that thermosetting resins derived from flavonoid bio-based sources hold significant promise for utilization in high-performance applications.

关键词

Keywords

references

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