生物基胺固化的可降解、可再加工环氧树脂的合成及性能  

Synthesis and properties of degradable and recycled bio-based amine cured epoxy resin

作　　者：冯浩洋 胡靖媛 陈青 颜世峰[2] 代金月 刘小青 FENG Haoyang;HU Jingyuan;CHEN Qing;YAN Shifeng;DAI Jinyue;LIU Xiaoqing(Polymer and Composite Materials Division,Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Zhejiang Provincial Key Laboratory of Bio-based Polymer Materials Technology and Application,Ningbo 31520l,Zhejiang,China;School of Materials Science and Engineering,Shanghai University,Shanghai 200444,China)

机构地区：[1]中国科学院宁波材料技术与工程研究所、高分子与复合材料事业部,浙江省生物基高分子材料技术与应用重点实验室,浙江宁波315201 [2]上海大学材料科学与工程学院,上海200444

出　　处：《精细化工》2022年第12期2577-2584,共8页Fine Chemicals

基　　金：国家自然科学基金(U1909220,52003283);浙江省杰出青年科学基金(LR20E030001)。

摘　　要：以缩水甘油醚季戊四醇双缩香草醛环氧树脂(DEPVD)为原料,通过胺解反应得到生物基可降解胺(DAPVD),DAPVD与樟脑酸缩水甘油酯(DGECA)固化得到环氧树脂DGECA-DAPVD。利用FTIR对DAPVD的结构进行了表征,通过动态热机械分析仪、拉伸测试机、再加工实验、降解实验、热重分析仪对DGECA-DAPVD的性能进行了表征。结果表明,DGECA-DAPVD具有较好的热机械性能、力学性能及热稳定性,其玻璃化转变温度为91℃,拉伸强度为(72.6±5.1)MPa,杨氏模量为(2493±58)MPa。固化剂中含有的螺环缩醛结构赋予了DGECA-DAPVD可降解的特性,而固化反应中原位形成的叔胺结构促进了邻位活性羟基参与酯交换反应,因此再加工后DGECA-DAPVD可保留75%的拉伸强度(190℃、10 MPa下热压1 h),DGECA-DAPVD及其碳纤维复合材料在H+浓度为0.1 mol/L的乙醇溶液中50℃下处理48 h后,均可完全降解,高价值的碳纤维可以完全回收。Bio-based amine(DAPVD),prepared via amination of glycidyl ether pentaerythritol divanillin epoxy(DEPVD)and characterized by FTIR,was cured with camphoric acid-based diglycidyl ester(DGECA)to synthesize epoxy resin.The properties of epoxy resin obtained were then analyzed by dynamic mechanical analyzer,tensile testing machine,reprocessing experiment,degradation experiment and thermogravimetric analyzer.The results indicated that the epoxy resin showed good thermomechanical,mechanical and thermal stability with a glass transition temperature 91℃,tensile strength(72.6±5.1)MPa and Young’s modulus about(2493±58)MPa.The spiro diacetal structure in the curing agent endowed the epoxy resin with degradable properties,while the tertiary amine structure formed during the curing reaction promoted the participation ofβ-hydroxyl groups in the transesterification reaction.Therefore,the epoxy resin could retain 75%of the tensile strength after being reprocessed(hot pressing at 190℃,10 MPa for1 h).Moreover,both the epoxy resin and its carbon fiber composite could be completely degraded in ethanol solution with a H+concentration of 0.1 mol/L(treatment temperature 50℃,time 48 h)with high-value carbon fibers completely recovered.

关 键 词：生物基环氧树脂 动态酯交换 螺环缩醛 碳纤维复合材料 可降解 建筑用化学品 

分 类 号：TQ322.2[化学工程—合成树脂塑料工业]