黄酮类生物基苯并噁嗪树脂的合成、固化机理及性能研究

胡长文; 杨蕊; 张侃

doi:10.11777/j.issn1000-3304.2025.25009

您当前的位置：

首页 >

文章列表页 >

黄酮类生物基苯并噁嗪树脂的合成、固化机理及性能研究

研究论文 | 更新时间：2025-07-28

- 黄酮类生物基苯并噁嗪树脂的合成、固化机理及性能研究
- Synthesis, Curing and Properties of Flavonoid Based Bio-benzoxazine Resins
- 高分子学报 2025年56卷第8期页码：1426-1437
- 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：
  
  E-mail: zhangkan@ujs.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25009
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7404
- 收稿日期：2025-01-07，
  
  录用日期：2025-04-28，
  
  网络出版日期：2025-06-05，
  
  纸质出版日期：2025-08-20
- 稿件说明：
移动端阅览
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

Handa N. V. ; Li S. G. ; Gerbec J. A. ; Sumitani N. ; Hawker C. J. ; Klinger D. Fully aromatic high performance thermoset via sydnone-alkyne cycloaddition . J. Am. Chem. Soc. , 2016 , 138 ( 20 ), 6400 - 6403 . doi: 10.1021/jacs.6b03381 http://dx.doi.org/10.1021/jacs.6b03381

Ishida H. ; Agag T. Handbook of Benzoxazine Resins . Elsevier , 2011 . doi: 10.1016/b978-0-444-53790-4.00089-8 http://dx.doi.org/10.1016/b978-0-444-53790-4.00089-8

Ishida H. ; Froimowicz P. Advanced and Emerging Polybenzoxazine Science and Technology . Elsevier , 2017 . doi: 10.1016/b978-0-12-804170-3.09987-x http://dx.doi.org/10.1016/b978-0-12-804170-3.09987-x

Sha X. L. ; Yuan L. ; Liang G. Z. ; Gu A. J. Heat-resistant and robust biobased benzoxazine resins developed with a green synthesis strategy . Polym. Chem. , 2021 , 12 ( 3 ), 432 - 438 . doi: 10.1039/d0py01529f http://dx.doi.org/10.1039/d0py01529f

Zhang K. ; Han M. C. ; Han L. ; Ishida H. Resveratrol-based tri-functional benzoxazines: synthesis, characterization, polymerization, and thermal and flame retardant properties . Eur. Polym. J. , 2019 , 116 , 526 - 533 . doi: 10.1016/j.eurpolymj.2019.04.036 http://dx.doi.org/10.1016/j.eurpolymj.2019.04.036

Higginson C. J. ; Malollari K. G. ; Xu Y. Q. ; Kelleghan A. V. ; Ricapito N. G. ; Messersmith P. B. Bioinspired design provides high-strength benzoxazine structural adhesives . Angew. Chem. Int. Ed. , 2019 , 58 ( 35 ), 12271 - 12279 . doi: 10.1002/anie.201906008 http://dx.doi.org/10.1002/anie.201906008

Wu J. B. ; Xi Y. ; McCandless G. T. ; Xie Y. H. ; Menon R. ; Patel Y. ; Yang D. J. ; Iacono S. T. ; Novak B. M. Synthesis and characterization of partially fluorinated polybenzoxazine resins utilizing octafluorocyclopentene as a versatile building block . Macromolecules , 2015 , 48 ( 17 ), 6087 - 6095 . doi: 10.1021/acs.macromol.5b01014 http://dx.doi.org/10.1021/acs.macromol.5b01014

Chen J. B. ; Zeng M. ; Feng Z. J. ; Pang T. ; Huang Y. W. ; Xu Q. Y. Design and preparation of benzoxazine resin with high-frequency low dielectric constants and ultralow dielectric losses . ACS Appl. Polym. Mater. , 2019 , 1 ( 4 ), 625 - 630 . doi: 10.1021/acsapm.8b00083 http://dx.doi.org/10.1021/acsapm.8b00083

Han L. ; Salum M. L. ; Zhang K. ; Froimowicz P. ; Ishida H. Intrinsic self-initiating thermal ring-opening polymerization of 1 , 3 -benzoxazines without the influence of impurities using very high purity crystals . J. Polym. Sci. Part A Polym. Chem., 2017, 55 ( 20 ), 3434 - 3445 . doi: 10.1002/pola.28723 http://dx.doi.org/10.1002/pola.28723

Ishida H. ; Rodriguez Y. Catalyzing the curing reaction of a new benzoxazine-based phenolic resin . J. Appl. Polym. Sci. , 1995 , 58 ( 10 ), 1751 - 1760 . doi: 10.1002/app.1995.070581013 http://dx.doi.org/10.1002/app.1995.070581013

Sun J. Q. ; Wei W. ; Xu Y. Z. ; Qu J. H. ; Liu X. D. ; Endo T. A curing system of benzoxazine with amine: reactivity, reaction mechanism and material properties . RSC Adv. , 2015 , 5 ( 25 ), 19048 - 19057 . doi: 10.1039/c4ra16582a http://dx.doi.org/10.1039/c4ra16582a

Liu C. ; Shen D. M. ; Sebastián R. M. ; Marquet J. ; Schönfeld R. Mechanistic studies on ring-opening polymerization of benzoxazines: a mechanistically based catalyst design . Macromolecules , 2011 , 44 ( 12 ), 4616 - 4622 . doi: 10.1021/ma2007893 http://dx.doi.org/10.1021/ma2007893

Kim H. D. ; Ishida H. Study on the chemical stability of benzoxazine-based phenolic resins in carboxylic acids . J. Appl. Polym. Sci. , 2001 , 79 ( 7 ), 1207 - 1219 . doi: 10.1002/1097-4628(20010214)79:73.0.CO;2-3 http://dx.doi.org/10.1002/1097-4628(20010214)79:73.0.CO;2-3

Baqar M. ; Agag T. ; Ishida H. ; Qutubuddin S. Methylol-functional benzoxazines as precursors for high-performance thermoset polymers: unique simultaneous addition and condensation polymerization behavior . J. Polym. Sci. Part A Polym. Chem. , 2012 , 50 ( 11 ), 2275 - 2285 . doi: 10.1002/pola.26008 http://dx.doi.org/10.1002/pola.26008

Zhang K. ; Liu Y. Q. ; Han M. C. ; Froimowicz P. Smart and sustainable design of latent catalyst-containing benzoxazine-bio-resins and application studies . Green Chem. , 2020 , 22 ( 4 ), 1209 - 1219 . doi: 10.1039/C9GC03504D http://dx.doi.org/10.1039/C9GC03504D

王汉武 , 贾瑞明 , 冉起超 . 生物基苯并噁嗪作为环氧树脂潜伏性固化剂的研究 . 功能高分子学报 , 2022 , 35 ( 3 ), 236 - 243 . doi: 10.14133/j.cnki.1008-9357. http://dx.doi.org/10.14133/j.cnki.1008-9357.

张鹤 , 陆馨 , 姚红杰 , 周长路 , 辛忠 . 腰果酚型聚苯并噁嗪基超疏水涂层的制备及其性能 . 功能高分子学报 , 2019 , 32 ( 1 ), 90 - 95 . doi: 10.14133/j.cnki.1008-9357.20180124002 http://dx.doi.org/10.14133/j.cnki.1008-9357.20180124002

Zhao W. Q. ; Hao B. R. ; Lu Y. ; Zhang K. Thermal latent and low-temperature polymerization of a bio-benzoxazine resin from natural renewable chrysin and furfurylamine . Eur. Polym. J. , 2022 , 166 , 111041 . doi: 10.1016/j.eurpolymj.2022.111041 http://dx.doi.org/10.1016/j.eurpolymj.2022.111041

Froimowicz P. ; Arza C. R. ; Han L. ; Ishida H. Smart, sustainable, and ecofriendly chemical design of fully bio-based thermally stable thermosets based on benzoxazine chemistry . ChemSusChem , 2016 , 9 ( 15 ), 1921 - 1928 . doi: 10.1002/cssc.201600577 http://dx.doi.org/10.1002/cssc.201600577

Machado I. ; Hsieh I. ; Rachita E. ; Salum M. L. ; Iguchi D. ; Pogharian N. ; Pellot A. ; Froimowicz P. ; Calado V. ; Ishida H. A truly bio-based benzoxazine derived from three natural reactants obtained under environmentally friendly conditions and its polymer properties . Green Chem. , 2021 , 23 ( 11 ), 4051 - 4064 . doi: 10.1039/D1GC00951F http://dx.doi.org/10.1039/D1GC00951F

Zhang K. ; Han M. C. ; Liu Y. Q. ; Froimowicz P. Design and synthesis of bio-based high-performance trioxazine benzoxazine resin via natural renewable resources . ACS Sustain. Chem. Eng. , 2019 , 7 ( 10 ), 9399 - 9407 . doi: 10.1021/acssuschemeng.9b00603 http://dx.doi.org/10.1021/acssuschemeng.9b00603

Wang C. F. ; Sun J. Q. ; Liu X. D. ; Sudo A. ; Endo T. Synthesis and copolymerization of fully bio-based benzoxazines from guaiacol, furfurylamine and stearylamine . Green Chem. , 2012 , 14 ( 10 ), 2799 - 2806 . doi: 10.1039/c2gc35796h http://dx.doi.org/10.1039/c2gc35796h

苗香艳 , 赵颖 , 宋万强 , 任士通 . 全生物基苯并噁嗪树脂的合成及聚合研究 . 中国胶粘剂 , 2019 , 28 ( 1 ), 17 - 19 .

Yang R. ; Han M. C. ; Hao B. R. ; Zhang K. Biobased high-performance tri-furan functional bis-benzoxazine resin derived from renewable guaiacol, furfural and furfurylamine . Eur. Polym. J. , 2020 , 131 , 109706 . doi: 10.1016/j.eurpolymj.2020.109706 http://dx.doi.org/10.1016/j.eurpolymj.2020.109706

Kotzebue L. R. V. ; de Oliveira J. R. ; da Silva J. B. ; Mazzetto S. E. ; Ishida H. ; Lomonaco D. Development of fully biobased high-performance bis-benzoxazine under environmentally friendly conditions . ACS Sustain. Chem. Eng. , 2018 , 6 ( 4 ), 5485 - 5494 . doi: 10.1021/acssuschemeng.8b00340 http://dx.doi.org/10.1021/acssuschemeng.8b00340

Samsonowicz M. ; Regulska E. ; Kalinowska M. Hydroxyflavone metal complexes-molecular structure, antioxidant activity and biological effects . Chem. Biol. Interact. , 2017 , 273 , 245 - 256 . doi: 10.1016/j.cbi.2017.06.016 http://dx.doi.org/10.1016/j.cbi.2017.06.016

Thirukumaran P. ; Manoharan R. K. ; Parveen A. S. ; Atchudan R. ; Kim S. C. Sustainability and antimicrobial assessments of apigenin based polybenzoxazine film . Polymer , 2019 , 172 , 100 - 109 . doi: 10.1016/j.polymer.2019.03.048 http://dx.doi.org/10.1016/j.polymer.2019.03.048

Han M. C. ; You S. J. ; Wang Y. T. ; Zhang K. ; Yang S. F. Synthesis of highly thermally stable daidzein-based main-chain-type benzoxazine resins . Polymers , 2019 , 11 ( 8 ), 1341 . doi: 10.3390/polym11081341 http://dx.doi.org/10.3390/polym11081341

Kissinger H. E. Reaction kinetics in differential thermal analysis . Anal. Chem. , 1957 , 29 ( 11 ), 1702 - 1706 . doi: 10.1021/ac60131a045 http://dx.doi.org/10.1021/ac60131a045

Ozawa T. Kinetics of non-isothermal crystallization . Polymer , 1971 , 12 ( 3 ), 150 - 158 . doi: 10.1016/0032-3861(71)90041-3 http://dx.doi.org/10.1016/0032-3861(71)90041-3

Shan F. ; Ohashi S. ; Erlichman A. ; Ishida H. Non-flammable thiazole-functional monobenzoxazines: synthesis, polymerization, thermal and thermomechanical properties, and flammability studies . Polymer , 2018 , 157 , 38 - 49 . doi: 10.1016/j.polymer.2018.09.061 http://dx.doi.org/10.1016/j.polymer.2018.09.061

Zhang K. ; Liu Y. Q. ; Han L. ; Wang J. Y. ; Ishida H. Synthesis and thermally induced structural transformation of phthalimide and nitrile-functionalized benzoxazine: toward smart ortho -benzoxazine chemistr y for low flammability thermosets . RSC Adv. , 2019 , 9 ( 3 ), 1526 - 1535 . doi: 10.1039/c8ra10009h http://dx.doi.org/10.1039/c8ra10009h

Agag T. ; Liu J. ; Graf R. ; Spiess H. W. ; Ishida H. Benzoxazole resin: a novel class of thermoset polymer via smart benzoxazine resin . Macromolecules , 2012 , 45 ( 22 ), 8991 - 8997 . doi: 10.1021/ma300924s http://dx.doi.org/10.1021/ma300924s

Zhang K. ; Yu X. Y. ; Kuo S. W. Outstanding dielectric and thermal properties of main chain-type poly(benzoxazine- co -imide- co -siloxane)-based cross-linked networks . Polym. Chem. , 2019 , 10 ( 19 ), 2387 - 2396 . doi: 10.1039/c9py00464e http://dx.doi.org/10.1039/c9py00464e

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

高强度、高透明的生物基水性聚氨酯的结构设计与性能

可持续热固性树脂的高性能和功能化设计合成

有机锡低聚倍半硅氧烷催化固化双酚A型苯并噁嗪树脂结构与性能研究