Injectable, Recyclable, and Highly Filled Al<sub>2</sub>O<sub>3</sub>/Unsaturated Polyester Thermal Composites Based on Diels-Alder Bonds

Yuan Cao; Wei-jie Mo; Chun-lei Wu; Xian-jian Duan; Ze-ping Zhang; Min-zhi Rong

doi:10.11777/j.issn1000-3304.2025.25298

您当前的位置：

首页 >

文章列表页 >

Injectable, Recyclable, and Highly Filled Al₂O₃/Unsaturated Polyester Thermal Composites Based on Diels-Alder Bonds

Research Article | 更新时间：2026-03-23

- Injectable, Recyclable, and Highly Filled Al₂O₃/Unsaturated Polyester Thermal Composites Based on Diels-Alder Bonds
- Acta Polymerica Sinica Vol. 57, Issue 3, Pages: 666-683(2026)
- 作者机构：
  
  1.中山大学化学学院聚合物复合材料及功能材料教育部重点实验室广州 510275
  2.广东省安全生产和应急管理科学技术研究院广州 510060
  3.广州汇富研究院有限公司广州 510663
- 作者简介：
  
  Ze-ping Zhang, E-mail: zhangzp8@mail.sysu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25298
  CLC：
- CSTR：32057.14.GFZXB.2025.7535
- Received：10 November 2025，
  
  Accepted：11 December 2025，
  
  Online First：27 January 2026，
  
  Published：20 March 2026
- 稿件说明：
移动端阅览
曹园, 莫伟杰, 吴春蕾, 段先健, 张泽平, 容敏智. 基于Diels-Alder键的可注塑、可回收、高填充Al₂O₃/不饱和聚酯导热复合材料. 高分子学报, 2026, 57(3), 666-683.

Cao, Y.; Mo, W. J.; Wu, C. L.; Duan, X. J.; Zhang, Z. P.; Rong, M. Z. Injectable, recyclable, and highly filled Al₂O₃/unsaturated polyester thermal composites based on Diels-Alder bonds. Acta Polymerica Sinica (in Chinese), 2026, 57(3), 666-683.
曹园, 莫伟杰, 吴春蕾, 段先健, 张泽平, 容敏智. 基于Diels-Alder键的可注塑、可回收、高填充Al₂O₃/不饱和聚酯导热复合材料. 高分子学报, 2026, 57(3), 666-683. DOI： 10.11777/j.issn1000-3304.2025.25298. CSTR： 32057.14.GFZXB.2025.7535.

Cao, Y.; Mo, W. J.; Wu, C. L.; Duan, X. J.; Zhang, Z. P.; Rong, M. Z. Injectable, recyclable, and highly filled Al₂O₃/unsaturated polyester thermal composites based on Diels-Alder bonds. Acta Polymerica Sinica (in Chinese), 2026, 57(3), 666-683. DOI： 10.11777/j.issn1000-3304.2025.25298. CSTR： 32057.14.GFZXB.2025.7535.

摘要

随着5G通信和高端芯片等技术的快速发展，电子器件的热管理问题日益严峻. 高填充导热聚合物复合材料是实现高效散热的理想材料之一，但其开发长期受困于高填充量导致的加工流动性差、界面结合弱及不可回收等难题. 本研究基于Diels-Alder (DA)可逆共价化学，构建了一种具有可逆交联基体与动态界面键合的共价自适应复合网络. 以DA交联的不饱和聚酯为基体，并采用马来酰亚胺改性Al

为填料，实现填料与基体的DA键合，提升两者的界面相容性. 结果显示，复合材料在70 wt%高填充下仍具有良好流动性，120 ℃

平衡扭矩仅2.77 N·m，显著低于共价交联对照样. 界面DA键合减少了填料团聚，增强了应力传递，使拉伸强度达17.7 MPa，较对比体系提升38%~149%. 复合材料同时具备较高热导率(1.50 W·m

-1

·K

-1

)、自修复效率(93.2%)和可重复回收性. 该研究为发展易加工、可循环的高填充导热复合材料提供了新途径.

Abstract

With the rapid advancement of 5G communication and high-end chip technologies

thermal management in electronic devices has become increasingly critical. Highly filled thermally conductive polymer composites are considered promising candidates for efficient heat dissipation

yet their development has long been hindered by challenges such as poor processability due to high filler loading

weak interfacial adhesion

and lack of recyclability. Based on Diels-Alder (DA) reversible covalent chemistry

this study constructed a covalent adaptive composite network featuring a reversibly cross-linked matrix and dynamic interfacial bonding. Using a DA-cross-linked unsaturated polyester as the matrix and maleimide-modified Al

as the filler

DA bonding between the filler and matrix was achieved

thereby improving interfacial compatibility. The results showed that the composite maintained good fluidity even at a high filler loading of 70 wt% (balanced t

orque=2.77 N·m

120 ℃)

which was significantly lower than that of the covalently cross-linked control sample. The interfacial DA bonding reduced filler agglomeration and enhanced stress transfer

resulting in a tensile strength improvement of 38% to 149% compared with reference systems. The composite also exhibited high thermal conductivity (1.50 W·m

-1

·K

-1

)

self-healing efficiency (93.2%)

and recyclability. This research provides a new approach for developing easily processable

recyclable

and highly filled thermal conductive composites.

关键词

Keywords

references

Chen H. Y. ; Ginzburg V. V. ; Yang J. ; Yang Y. F. ; Liu W. ; Huang Y. ; Du L. B. ; Chen B. Thermal conductivity of polymer-based composites: Fundamentals and applications . Prog. Polym. Sci. , 2016 , 59 , 41 - 85 . doi: 10.1016/j.progpolymsci.2016.03.001 http://dx.doi.org/10.1016/j.progpolymsci.2016.03.001

李俊伟 , 张泽平 , 容敏智 , 章明秋 . 基于图案化方法制备高导热氮化硼/液晶环氧复合材料 . 高分子学报 , 2025 , 56 ( 2 ), 306 - 321 .

Zhang L. ; Gao S. X. ; Wang S. Y. ; Xia Y. ; Wang B. T. ; Zhu Y. K. ; Chen J. Q. ; Guo Z. H. ; Fang Z. P. ; Li J. Roles of multi-hierarchical char in flame retardancy for epoxy composites induced by modified thermal conductive fillers and flame-retardant assembly . Compos. Part B Eng. , 2025 , 292 , 112092 . doi: 10.1016/j.compositesb.2024.112092 http://dx.doi.org/10.1016/j.compositesb.2024.112092

Pak S. Y. ; Kim H. M. ; Kim S. Y. ; Youn J. R. Synergistic improvement of thermal conductivity of thermoplastic composites with mixed boron nitride and multi-walled carbon nanotube fillers . Carbon , 2012 , 50 ( 13 ), 4830 - 4838 . doi: 10.1016/j.carbon.2012.06.009 http://dx.doi.org/10.1016/j.carbon.2012.06.009

Choi S. ; Kim J. Thermal conductivity of epoxy composites with a binary-particle system of aluminum oxide and aluminum nitride fillers . Compos. Part B Eng. , 2013 , 51 , 140 - 147 . doi: 10.1016/j.compositesb.2013.03.002 http://dx.doi.org/10.1016/j.compositesb.2013.03.002

Mosanenzadeh S. G. ; Khalid S. ; Cui Y. ; Naguib H. E. High thermally conductive PLA based composites with tailored hybrid network of hexagonal boron nitride and graphene nanoplatelets . Polym. Compos. , 2016 , 37 ( 7 ), 2196 - 2205 . doi: 10.1002/pc.23398 http://dx.doi.org/10.1002/pc.23398

Yu L. Y. ; Yang D. ; Wei Q. G. ; Zhang L. Q. Constructing of strawberry-like core-shell structured Al 2 O 3 nanoparticles for improving thermal conductivity of nitrile butadiene rubber composites . Compos. Sci. Technol. , 2021 , 209 , 108786 . doi: 10.1016/j.compscitech.2021.108786 http://dx.doi.org/10.1016/j.compscitech.2021.108786

Jin H. ; Zhong X. X. ; Zhong C. C. ; Dai W. S. ; Xiang H. P. ; Zhang L. Y. UV-curable, 3D printable, thermally conductive polysiloxane composites for thermal interface devices . Addit. Manuf. , 2025 , 99 , 104658 . doi: 10.1016/j.addma.2025.104658 http://dx.doi.org/10.1016/j.addma.2025.104658

Cao B. ; Zhou Y. B. ; Wu Y. C. ; Cai J. N. ; Guan X. X. ; Liu S. M. ; Zhao J. Q. ; Zhang M. Q. Simultaneous improvement of processability and toughness of highly filled MH/LLDPE composites by using fluorine-containing flow modifiers . Compos. Part A Appl. Sci. Manuf. , 2020 , 134 , 105900 . doi: 10.1016/j.compositesa.2020.105900 http://dx.doi.org/10.1016/j.compositesa.2020.105900

Wolff M. F. H. ; Salikov V. ; Antonyuk S. ; Heinrich S. ; Schneider G. A. Novel, highly-filled ceramic-polymer composites synthesized by a spouted bed spray granulation process . Compos. Sci. Technol. , 2014 , 90 , 154 - 159 . doi: 10.1016/j.compscitech.2013.11.006 http://dx.doi.org/10.1016/j.compscitech.2013.11.006

Lejeail M. ; Fischer H. R. Development of a completely recyclable glass fiber-reinforced epoxy thermoset composite . J. Appl. Polym. Sci. , 2021 , 138 ( 3 ), 49690 . doi: 10.1002/app.49690 http://dx.doi.org/10.1002/app.49690

张泽平 , 容敏智 , 章明秋 . 基于可逆共价化学的交联聚合物加工成型研究: 聚合物工程发展的新挑战 . 高分子学报 , 2018 , 49 ( 7 ), 829 - 852 .

Zhang Z. P. ; Rong M. Z. ; Zhang M. Q. Polymer engineering based on reversible covalent chemistry: a promising innovative pathway towards new materials and new functionalities . Prog. Polym. Sci. , 2018 , 80 , 39 - 93 . doi: 10.1016/j.progpolymsci.2018.03.002 http://dx.doi.org/10.1016/j.progpolymsci.2018.03.002

Bose R. K. ; Kötteritzsch J. ; Garcia S. J. ; Hager M. D. ; Schubert U. S. ; van der Zwaag S. A rheological and spectroscopic study on the kinetics of self-healing in a single-component Diels-alder copolymer and its underlying chemical reaction . J. Polym. Sci. Part A Polym. Chem. , 2014 , 52 ( 12 ), 1669 - 1675 . doi: 10.1002/pola.27164 http://dx.doi.org/10.1002/pola.27164

Adzima B. J. ; Aguirre H. A. ; Kloxin C. J. ; Scott T. F. ; Bowman C. N. Rheological and chemical analysis of reverse gelation in a covalently cross-linked Diels-Alder polymer network . Macromolecules , 2008 , 41 ( 23 ), 9112 - 9117 . doi: 10.1021/ma801863d http://dx.doi.org/10.1021/ma801863d

Chen X. X. ; Dam M. A. ; Ono K. ; Mal A. ; Shen H. B. ; Nutt S. R. ; Sheran K. ; Wudl F. A thermally re-mendable cross-linked polymeric material . Science , 2002 , 295 ( 5560 ), 1698 - 1702 . doi: 10.1126/science.1065879 http://dx.doi.org/10.1126/science.1065879

Cao Y. ; Rong M. Z. ; Zhang M. Q. Covalent adaptable networks impart smart processability to multifunctional highly filled polymer composites . Compos. Part A Appl. Sci. Manuf. , 2021 , 151 , 106647 . doi: 10.1016/j.compositesa.2021.106647 http://dx.doi.org/10.1016/j.compositesa.2021.106647

Tian Q. ; Rong M. Z. ; Zhang M. Q. ; Yuan Y. C. Synthesis and characterization of epoxy with improved thermal remendability based on Diels-Alder reaction . Polym. Int. , 2010 , 59 ( 10 ), 1339 - 1345 . doi: 10.1002/pi.2872 http://dx.doi.org/10.1002/pi.2872

朱广超 , 王贵友 , 胡春圃 . 交联密度对脂肪族聚氨酯弹性体结构与性能的影响 . 高分子学报 , 2011 , 42 ( 3 ), 274 - 280 .

Kuang X. ; Liu G. M. ; Zheng L. C. ; Li C. C. ; Wang D. J. Functional polyester with widely tunable mechanical properties: the role of reversible cross-linking and crystallization . Polymer , 2015 , 65 , 202 - 209 . doi: 10.1016/j.polymer.2015.03.074 http://dx.doi.org/10.1016/j.polymer.2015.03.074

Grein C. ; Gahleitner M. On the influence of nucleation on the toughness of iPP/EPR blends with different rubber molecular architectures . Express Polym. Lett. , 2008 , 2 ( 6 ), 392 - 397 . doi: 10.3144/expresspolymlett.2008.47 http://dx.doi.org/10.3144/expresspolymlett.2008.47

Perchacz M. ; Rozanski A. ; Kargarzadeh H. ; Galeski A. Cavitation in high density polyethylene/Al 2 O 3 nanocomposites . Compos. Sci. Technol. , 2020 , 199 , 108323 . doi: 10.1016/j.compscitech.2020.108323 http://dx.doi.org/10.1016/j.compscitech.2020.108323

Dhanola A. ; Bisht A. S. ; Kumar A. ; Kumar A. Influence of natural fillers on physico-mechanical properties of luffa cylindrica/polyester composites . Mater. Today Proc. , 2018 , 5 ( 9 ), 17021 - 17029 . doi: 10.1016/j.matpr.2018.04.107 http://dx.doi.org/10.1016/j.matpr.2018.04.107

Han Z. D. ; Fina A. Thermal conductivity of carbon nanotubes and their polymer nanocomposites: a review . Prog. Polym. Sci. , 2011 , 36 ( 7 ), 914 - 944 . doi: 10.1016/j.progpolymsci.2010.11.004 http://dx.doi.org/10.1016/j.progpolymsci.2010.11.004

Wen Y. F. ; Chen C. ; Feng Y. Z. ; Xue Z. G. ; Zhou X. P. ; Xie X. L. ; Mai Y. W. Effects of selective distribution of alumina micro-particles on rheological, mechanical and thermal conductive properties of asphalt/SBS/alumina composites . Compos. Sci. Technol. , 2020 , 186 , 107917 . doi: 10.1016/j.compscitech.2019.107917 http://dx.doi.org/10.1016/j.compscitech.2019.107917

Kim Y. S. ; Kim J. K. ; Jeon E. S. Effect of the compounding conditions of polyamide 6, carbon fiber, and Al 2 O 3 on the mechanical and thermal properties of the composite polymer . Materials , 2019 , 12 ( 18 ), 3047 . doi: 10.3390/ma12183047 http://dx.doi.org/10.3390/ma12183047

Zhang S. ; Cao X. Y. ; Ma Y. M. ; Ke Y. C. ; Zhang J. K. ; Wang F. S. The effects of particle size and content on the thermal conductivity and mechanical properties of Al 2 O 3 /high density polyethylene (HDPE) composites . Express Polym. Lett. , 2011 , 5 ( 7 ), 581 - 590 . doi: 10.3144/expresspolymlett.2011.57 http://dx.doi.org/10.3144/expresspolymlett.2011.57

Zhang S. ; Ke Y. C. ; Cao X. Y. ; Ma Y. M. ; Wang F. S. Effect of Al 2 O 3 fibers on the thermal conductivity and mechanical properties of high density polyethylene with the absence and presence of compatibilizer . J. Appl. Polym. Sci. , 2012 , 124 ( 6 ), 4874 - 4881 . doi: 10.1002/app.35579 http://dx.doi.org/10.1002/app.35579

Lule Z. ; Ju H. ; Kim J. Thermomechanical properties of alumina-filled plasticized polylactic acid: effect of alumina loading percentage . Ceram. Int. , 2018 , 44 ( 18 ), 22767 - 22776 . doi: 10.1016/j.ceramint.2018.09.066 http://dx.doi.org/10.1016/j.ceramint.2018.09.066

Lule Z. ; Ju H. ; Kim J. Effect of surface-modified Al 2 O 3 on the thermomechanical properties of polybutylene succinate/Al 2 O 3 composites . Ceram. Int. , 2018 , 44 ( 12 ), 13530 - 13537 . doi: 10.1016/j.ceramint.2018.04.184 http://dx.doi.org/10.1016/j.ceramint.2018.04.184

Huang H. ; Yan L. ; Guo Y. ; Lin H. L. ; Chen L. ; Yang L. F. ; Xie Y. J. ; Bian J. Morphological, mechanical and thermal properties of PA6 nanocomposites Co-Incorporated with Nano-Al 2 O 3 and graphene oxide fillers . Polymer , 2020 , 188 , 122119 . doi: 10.1016/j.polymer.2019.122119 http://dx.doi.org/10.1016/j.polymer.2019.122119

Jiang L. ; Huang Z. G. ; Wang X. K. ; Lai M. L. ; Zhang Y. ; Zhou H. M. Influence of reactive compatibilization on the mechanical, thermal and rheological properties of highly filled PBT/Al 2 O 3 composites . Mater. Des. , 2020 , 196 , 109175 . doi: 10.1016/j.matdes.2020.109175 http://dx.doi.org/10.1016/j.matdes.2020.109175

Lee W. ; Wie J. ; Kim J. Enhancement of thermal conductivity of alumina/epoxy composite using poly(glycidyl methacrylate) grafting and crosslinking . Ceram. Int. , 2021 , 47 ( 13 ), 18662 - 18668 . doi: 10.1016/j.ceramint.2021.03.198 http://dx.doi.org/10.1016/j.ceramint.2021.03.198

Chen F. ; Xiao H. ; Peng Z. Q. ; Zhang Z. P. ; Rong M. Z. ; Zhang M. Q. Thermally conductive glass fiber reinforced epoxy composites with intrinsic self-healing capability . Adv. Compos. Hybrid Mater. , 2021 , 4 ( 4 ), 1048 - 1058 . doi: 10.1007/s42114-021-00303-3 http://dx.doi.org/10.1007/s42114-021-00303-3

Chen F. ; Pang X. Y. ; Zhang Z. P. ; Rong M. Z. ; Zhang M. Q. Thermally conductive, healable glass fiber cloth reinforced polymer composite based on β -hydroxyester bonds crosslinked epoxy with improved heat resistance . Chinese J. Polym. Sci. , 2024 , 42 ( 5 ), 643 - 654 . doi: 10.1007/s10118-024-3076-x http://dx.doi.org/10.1007/s10118-024-3076-x

Schäfer S. ; Kickelbick G. Self-healing polymer nanocomposites based on Diels-Alder-reactions with silica nanoparticles: the role of the polymer matrix . Polymer , 2015 , 69 , 357 - 368 . doi: 10.1016/j.polymer.2015.03.017 http://dx.doi.org/10.1016/j.polymer.2015.03.017

Views

454

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Preparation and Self-healing Performance Study of Thermoplastic Polyimide Films Based on Flexible Hydrazide

High-strength, Tough, and Self-healing Epoxidized Natural Rubber Enabled by Synergistic Rigid Segments and Multiple Hydrogen Bonds

Fabrication and Thermal Conductivity of Flexible, Tear-resistant, and Self-healing Polyurethane/Boron Nitride Laminated Composites

Electrospinning of Polyetherketoneketone: Strategy of Fiber Refinement and High Temperature Filtration Application

Liquid-Phase Exfoliation of Pyridine-Based Covalent Organic Framework Nanosheets for High-Performance H2/CO2 Gas Separation Membrane Fabrication

Related Author

Wei-ping Guo

Guang He

Qing-song Xu

Jia-lin Zhang

Xiu-ting Li

Jie Dong

Xin Zhao

Qing-hua Zhang

Related Institution

State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Technology, Donghua University

School of Materials Science and Engineering, Hubei University, Key Laboratory of Green Preparation and Application of Functional Materials, Ministry of Education, Hubei Key Laboratory of Polymer Materials

Testing Center, Yangzhou University

School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology

Department of Polymer Materials, Dalian University of Technology

AI脑图

AI问答

Postal code：100190
Tel：010-62588927 Email：gfzxb@iccas.ac.cn
Technical support is provided by Beijing Founder electronics co., LTD 京ICP备05002797号-8 京公网安备11010802046899号
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.

⁰

Injectable, Recyclable, and Highly Filled Al2O3/Unsaturated Polyester Thermal Composites Based on Diels-Alder Bonds

DOI：10.11777/j.issn1000-3304.2025.25298

摘要

Abstract

关键词

Keywords

references

Injectable, Recyclable, and Highly Filled Al₂O₃/Unsaturated Polyester Thermal Composites Based on Diels-Alder Bonds