一种阻燃型铜基金属有机框架材料的制备及在环氧树脂中的性能

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

摘要

采用超声辅助法与水热合成法， 利用席夫碱配体4，4'-(1，4-苯二甲亚基二次亚氨基)二苯甲酸(TBPA)制备了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， 制备了阻燃型Cu-MOF， 即Cu-MOF@DOPO. 通过扫描电子显微镜、 透射电子显微镜及X射线衍射等手段对其进行表征， 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.

Abstract

A copper-based metal-organic framework（Cu-MOF） with schiff base organic ligand 4, 4'-［1, 4-phenyl-enebis（methanylylidene）bis（nitrilo）］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%（mass fraction） 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 the 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.

关键词

环氧树脂 / 金属-有机框架 / 阻燃性能 / 力学性能 / 热性能

Key words

Epoxy resin / Metal-organic framework / Flame retardancy / Mechanical property / Thermal property

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基金资助

国家自然科学基金(21975185)