䓝烷二胺基环氧vitrimer的制备及其性能研究
Preparation of dianediamine-based self-catalyzed self-healing epoxy vitrimer
[目的]热固性材料具有质量轻、力学性能强、耐腐蚀性好等优点,广泛应用于航空航天、交通运输、医疗等领域,但是,以化石资源为原料制备的热固性环氧树脂具有永久三维交联结构,一旦加工成型便难以降解、回收以及再加工,造成了资源浪费及环境污染等问题。本研究利用松节油衍生物䓝烷二胺为原料,制备了生物基可回收环氧vitrimer。[方法]以樟脑酸为原料制备了环氧化樟脑酸(EDCA),并与䓝烷二胺(MDA)固化制备了具有无催化、自修复性能的EDCA-MDA vitrimer 材料。通过傅里叶变换红外光谱、核磁共振仪、差示扫描量热仪、动态热机械分析仪、万能试验机、热重分析仪、光学显微镜及平板热压硫化仪等对材料的结构与性能进行了研究。[结果]由于刚性松节油萜环的引入,EDCA-MDA vitrimer 材料具有优异的机械性能(61 MPa)、高储存模量(2266 MPa)和玻璃化转变温度(141℃)。EDCA-MDA vitrimer 材料交联密度高,具有稳定的 3D vitrimer 网络,材料失重 10%的温度为 318℃,800℃的碳残留率为 4.4%。在不添加外部催化剂的情况下,EDCA-MDA vitrimer 材料在叔胺的催化下可实现快速的应力松弛,活化能为 182.908 kJ/mol-1.EDCA-MDA vitrimer材料涂层的自修复率为 91.03%,表现出良好的自修复性能,且 EDCA-MDA vitrimer 具有热压重塑性能。[结论]该研究结果对热固性树脂的回收问题提供了解决思路,对松节油的综合利用具有重要的理论意义。
[Objective]Thermoset materials have the advantages of light weight,strong mechanical properties,good corrosion resistance,etc.,and are widely used in aerospace,transportation,medical and other fields.However,thermoset epoxy resins prepared from fossil resources have a permanent three-dimensional cross-linking structure,and are difficult to be degraded,recycled,and reprocessed once they are processed and molded,which results in a waste of resources and environmental pollution.In this study,bio-based recyclable epoxy vitrimer was prepared using turpentine derivative dianediamine as raw material.[Methods]Epoxidized camphoric acid(EDCA)was prepared from camphoric acid and cured with dianediamine(MDA)to prepare EDCA-MDA vitrimer materials with non-catalytic,self-healing properties.The structure and properties of the materials were investigated by Fourier Transform Infrared Spectroscopy,Nuclear Magnetic Resonance(NMR),Differential Scanning Calorimetry(DSC),Dynamic Thermo-Mechanical Analyzer(DTMA),Universal Testing Machine(UTM),Thermogravimetric Analyzer(TGA),Optical Microscope(OM),and Flat Plate Thermal Pressing and Vulcanizing(FPHPV).[Results]Due to the introduction of a rigid turpentine terpene ring,the EDCA-MDA vitrimer material has excellent mechanical properties(61 MPa),high storage modulus(2266 MPa)and glass transition temperature(141 °C).The EDCA-MDA vitrimer material has a high cross-linking density and a stable 3D vitrimer network,with a material weight loss of 10%at 318 °C and a carbon residual of 4.4%at 800 °C.Without the addition of an external catalyst,the EDCA-MDA vitrimer material achieves rapid stress relaxation catalyzed by tertiary amines with an activation energy of 182.908 kJ/mol-1.The self-repair rate of the EDCA-MDA vitrimer material coating was 91.03%,which showed good self-repair performance,and EDCA-MDA vitrimer has the performance of hot press remodeling.[Conclusion]The results of this study provide a solution to the problem of thermosetting resin recycling,which is of great theoretical significance for the comprehensive utilization of turpentine.
马慧茹;张海波;陈玉湘;赵振东;毕良武;
中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏 南京 210042##南京林业大学 江苏省林业资源高效加工利用协同创新中心,江苏 南京 210037;中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏 南京 210042;中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏 南京 210042;中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏 南京 210042;中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏 南京 210042;
Epoxy vitrimer Turpentine Biobased Self-healing Recycling
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