烷二胺基环氧Vitrimer的制备及其应用研究  

Preparation of Menthane Diamine Based Epoxy Vitrimer and Its Application

作　　者：马慧茹 张海波[1] 陈玉湘[1] 赵振东[1] 李海兵 冯盛 MA Huiru;ZHANG Haibo;CHEN Yuxiang;ZHAO Zhendong;LI Haibing;FENG Sheng(Institute of Chemical Industry of Forest Products,CAF/Key Lab.of Biomass Energy and Material,Jiangsu Province/Key Lab.of Chemical Engineering of Forest Products,National Forestry and Grassland Administration/National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass,Nanjing 210042,China;Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources,Nanjing Forestry University,Nanjing 210037,China;Pu'er Simao Sensheng Forest and Chemical Product Company,Pu'er 665009,China)

机构地区：[1]中国林业科学研究院林产化学工业研究所,江苏省生物质能源与材料重点实验室,国家林业和草原局林产化学工程重点实验室,林木生物质低碳高效利用国家工程研究中心,江苏南京210042 [2]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 [3]普洱市思茅区森盛林化有限责任公司,云南普洱665099

出　　处：《林产化学与工业》2024年第6期64-72,共9页Chemistry and Industry of Forest Products

基　　金：国家自然科学基金资助项目(32271808);江苏省生物质能源与材料重点实验室基本科研业务费(JSBEM-S-202205)。

摘　　要：以D-樟脑酸(CPA)、䓝烷二胺(MDA)为原料,制备了樟脑酸缩水甘油酯(GECPA-MDA)vitrimer材料,并进一步与碳纤维(CF)复合,制得碳纤维增强复合材料(CFRP)。通过红外光谱、核磁共振氢谱、热重分析、动态热机械分析等对GECPA-MDA vitrimer,以及以GECPA-MDA为基体和CF复合制备的CFRP(GECPA-MDA-CF)进行性能分析。研究结果表明:由于MDA中刚性松节油萜环的引入,GECPA-MDA vitrimer材料具有优异的机械性能((61.0±2.1)MPa)、储能模量(1959 MPa)、玻璃化转变温度(T_(g),144.76℃)和高交联密度(70.7 mol/m^(3)),且热稳定性随MDA用量增加而增加。在叔胺的催化下GECPA-MDA vitrimer可实现应力松弛,氨基活泼氢/环氧基物质的量比值为1.0时的复合材料(GECPA-MDA 1.0)机械性能高、热稳定性好且易降解。复合材料GECPA-MDA 1.0涂层的自修复率为96.30%,可热压重塑,且具有三重形状记忆特性。GECPA-MDA-CF材料的拉伸强度达到(658±72)MPa,可以在90℃的乙醇胺(EA)溶液中完全降解,实现CF的无损回收。D-camphoric acid(CPA)and menthane diamine(MDA)were used as raw materials to prepare menthane diamine camphoric acid(GECPA-MDA)vitrimer materials that were further composited with carbon fiber(CF)to obtain carbon fiber-reinforced composites(CFRP).The properties of GECPA-MDA vitrimer and GECPA-MDA-based CFRP(GECPA-MDA-CF)were analyzed by Fourier-transform infrared spectroscopy,nuclear magnetic resonance hydrogen spectroscopy,thermogravimetric analyzer and dynamic thermomechanical analyzer.The results showed that GECPA-MDA vitrimer materials exhibited excellent mechanical properties((61.0±2.1)MPa),storage modulus(1959 MPa),glass transition temperature(T_(g),144.76℃),and high crosslinking density(70.7 mol/m^(3))due to the introduction of rigid turpentine terpenes.Moreover,the thermal stability increased with the increase in the amount of MDA used.The GECPA-MDA vitrimer catalyzed by tertiary amines could achive stress relaxation,and the composite material(GECPA-MDA 1.0)with the amino active hydrogen/epoxy group ratio of 1.0 had high mechanical properties,good thermal stability and easy degradability.The composite GECPA-MDA 1.0 coating had a self-healing rate of 96.30%,and it could be remoulded by hot pressing,and had triple shape memory properties.The tensile strength of the GECPA-MDA-CF material prepared by compounding the GECPA-MDA vitrimer material with CF reached(658±72)MPa,and it could be completely degraded in an ethanolamine(EA)solution at 90℃,enabling the non-destructive recovery of CF.

关 键 词：环氧vitrimer 松节油 生物基 自修复 回收 

分 类 号：TQ35[化学工程]