高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

一种阻燃型铜基金属有机框架材料的制备及其在环氧树脂中的性能

万松涛1，曹志林1，王正洲1,2   

  1. 1. 同济大学材料科学与工程学院，高分子材料系 2. 先进土木工程材料教育部重点实验室

  • 收稿日期:2026-03-21 修回日期:2026-05-23 网络首发:2026-05-28 发布日期:2026-05-28
  • 通讯作者: 王正洲
  • 基金资助:
    国家自然科学基金(批准号：21975185)资助

Fabrication of a Flame-retardant Cu-based Metal Organic Framework and Its Effect on Properties of Epoxy Resin

WAN Songtao1, CAO Zhilin1, WANG Zhengzhou1,2*   

  1. 1. Department of Polymeric Materials,School of Materials Science and Engineering,Tongji University 2. Key Laboratory of Advanced Civil Engineering Materials,Tongji University,Ministry of Education
  • Received:2026-03-21 Revised:2026-05-23 Online First:2026-05-28 Published:2026-05-28
  • Supported by:
    Supported by the National Nature Science Foundation of China(No.21975185)

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摘要： 采用超声辅助法与水热合成法制备一种铜基金属有机框架(Cu-MOF)，再用其与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)反应，成功制备出阻燃型Cu-MOF，即(Cu-MOF@DOPO)。经过扫描电子显微镜、透射电子显微镜及X射线衍射等手段对其进行表征，证实了Cu-MOF@DOPO的成功合成。探讨了Cu-MOF@DOPO对环氧树脂(EP)阻燃性能、力学性能及热性能等的影响。研究结果表明，与纯EP相比，添加2%(质量分数)Cu-MOF@DOPO的EP复合材料综合性能显著提升：极限氧指数由23.2%(纯EP)提升至29.6%，UL-94等级达到V-0级；峰值热释放速率降低14.2%，总热释放量降低8.1%，且总烟释放量也有所降低。机理分析表明，Cu-MOF@DOPO的引入可促进EP在燃烧时形成致密的炭层，同时具有气相成分的协同阻燃作用，显著提升了EP的阻燃性能。此外，与未改性Cu-MOF及阻燃改性有机配体TBPA-DOPO相比，Cu-MOF@DOPO改性EP复合材料呈现出更高的玻璃化转变温度与更优异的力学性能。

关键词: 环氧树脂, 阻燃金属-有机框架材料, 阻燃性能, 力学性能, 热性能

Abstract: A copper-based metal-organic framework(Cu-MOF) with the reactive organic ligand 4,4'-{[(1E,1'E)-1,4-phenylene]bis(methylene)}bis(azanediyl)dibenzoic acid(TBPA) was first synthesized via ultrasound-assisted and hydrothermal methods. Then, a flame-retardant Cu-MOF derivative(Cu-MOF@DOPO) was prepared by reacting Cu-MOF with a reactive flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO). The Cu-MOF@DOPO was confirmed by multiple characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy(TEM), and X-ray diffraction(XRD). The effect of Cu-MOF@DOPO on flame retardant, mechanical and thermal properties of epoxy resin(EP) was investigated. The results indicated that EP containing 2 wt% Cu-MOF@DOPO(EP/2MD) had a limiting oxygen index(LOI) of 29.6% and achieved a UL-94 V-0 rating. Meanwhile, the peak heat release rate(pHRR) and total heat release(THR) of EP/2MD decreased by 14.2% and 8.1%, respectively, while the total smoke production(TSP) slightly deceased compared with those of pure EP. During combustion, Cu-MOF@DOPO in EP exerted its flame-retardant action both in the condensed phase and the gas phase. Compared with EP composites filled with Cu-MOF or the flame-retardant ligand TBPA-DOPO, the EP/Cu-MOF@DOPO composites exhibited a higher glass transition temperature and enhanced mechanical properties.

Key words: Epoxy resin, Flame-retardant metal-organic framework, Flame retardancy, Mechanical property, Thermal property

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