具有可控降解与抗菌功能的生物基环氧树脂合成  

Bio-based Epoxy Resin:Controllable Degradation,Chemical Recovery and Antimicrobial Property

作　　者：冯浩洋 胡婧媛 金丹丹 王帅朋 代金月[1] 刘小青[1] Hao-yang Feng;Jing-yuan Hu;Dan-dan Jin;Shuai-peng Wang;Jin-yue Dai;Xiao-qing Liu(Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo 315201)

机构地区：[1]中国科学院宁波材料技术与工程研究所,宁波315201

出　　处：《高分子学报》2022年第9期1083-1094,共12页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号U1909220,52003282);浙江省杰出青年科学基金(基金号LR20E030001)项目资助。

摘　　要：赋予环氧树脂在温和条件下的可控降解与高附加值回收利用,是实现其可持续发展的重要手段.本工作以生物基香草醛为原料设计合成了含有螺环缩醛结构的β-羟丙基胺类环氧树脂固化剂(NVP),以生物基樟脑酸为原料合成了生物基缩水甘油酯类环氧树脂DGECA,通过两者的固化反应形成了一种螺环缩醛结构有序分布在侧链的环氧树脂交联网络.通过降解动力学和实时核磁共振氢谱(1H-NMR)研究了环氧树脂在50℃、0.1 mol/L H~+溶液中的降解行为,结果表明,螺环缩醛的引入可以使交联网络在温和条件下解聚,并促进酯键的水解过程.利用2种可降解键的降解速率差异,用水萃取不同阶段的降解产物分别回收原料单体(季戊四醇收率大于85.5%,樟脑酸大于58.9%),实现了环氧树脂的可控分级降解和原料回收.此外,固化反应原位形成的β-氨基醇结构赋予了树脂优异的抗菌性能(抑菌率大于95%).上述研究结果将有助于更多的具有可控分级降解与抗菌功能树脂的开发.Endowing epoxy resin derived from bio-based glycidyl ester with controllable degradation in mild condition and high-valued recovery is a huge challenge.We design a novel cross-linked network with the degradable spior acetal structure orderly distributed on branch chains through the curing reaction between camphoric acid-based diglycidyl ester and vanillin-based amine curing agent.To investigate degradation mechanism of the epoxy resins,the degradation behaviors in 0.1 mol/L H+acidic aqueous solutions for 48 h at 50℃were monitored by the degradation kinetics and real-time1H-NMR spectra.The result indicated that the cross-linked network with spiro acetal structure was hydrolyzed into pentaerythritol and oligomers,and then camphoric acid was obtained by the hydrolyzation of ester bonds in oligomers.The degradation products in different periods were extracted by water to recover the raw material monomer(yield,pentaerythritol>85.5%,camphoric acid>58.9%),which realized the controllable degradation and chemical recovery of epoxy resin by a green method.The curing agent formulation of the epoxy resin was adjusted to enhance thermal stability and tensile properties of resin samples,and samples with NVP performed excellent antimicrobial property(ratio,>95%)for both E.coli and S.aureus bacteria because ofβ-amino alcohols generated in the curing reaction.The above result will inspire more synthesis of epoxy resin with controllable degradation,chemical recovery and antimicrobial property.

关 键 词：环氧树脂 二缩水甘油酯 可控降解 化学回收 抗菌 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]