Zhao Wenzhe, An Le, Wang Shujuan
State Key Laboratory for Strength and Vibration of Mechanical Structures, School of Aerospace Engineering, Xi'an Jiaotong University, Xi'an 710049, China.
School of Chemistry, Xi'an Jiaotong University, Xi'an 710049, China.
Polymers (Basel). 2021 Jan 18;13(2):296. doi: 10.3390/polym13020296.
Epoxy-anhydride resins are widely used in engineering fields due to their excellent performance. However, the insolubility and infusibility make the recycling of epoxy resins challenging. The development of degradable epoxy resins with stable covalent networks provides an efficient solution to the recycling of thermosets. In this paper, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) is incorporated into the epoxy-glutaric anhydride (GA) system to prepare high-performance epoxy resins that can be recycled below 200 °C at ordinary pressure via ethylene glycol (EG) participated transesterification. The tertiary amine groups in DMP-30 can catalyze the curing reaction of epoxy and anhydride, as well as the transesterification between ester bonds and alcoholic hydroxyl groups. Compared with early recyclable anhydride-cured epoxy resins, the preparation and recycling of diglycidyl ether of bisphenol A (DGEBA)/GA/DMP-30 systems do not need any special catalysts such as TBD, Zn(Ac), etc., which are usually expensive, toxic, and have poor compatibility with other compounds. The resulting resins have glass transition temperatures and strengths similar to those of conventional epoxy resins. The influences of GA content, DMP-30 content, and temperature on the dissolution rate were studied. The decomposed epoxy oligomer (DEO) is further used as a reaction ingredient to prepare new resins. It is found that the DEO can improve the toughness of epoxy resins significantly. This work provides a simple method to prepare readily recyclable epoxy resins, which is of low-cost and easy to implement.
环氧-酸酐树脂因其优异的性能而在工程领域得到广泛应用。然而,其不溶性和不熔性使得环氧树脂的回收具有挑战性。开发具有稳定共价网络的可降解环氧树脂为热固性材料的回收提供了一种有效的解决方案。本文将2,4,6-三(二甲基氨基甲基)苯酚(DMP-30)引入环氧-戊二酸酐(GA)体系,制备了高性能环氧树脂,该树脂可在常压下通过乙二醇(EG)参与的酯交换反应在200℃以下进行回收。DMP-30中的叔胺基团可以催化环氧和酸酐的固化反应,以及酯键与醇羟基之间的酯交换反应。与早期的可回收酸酐固化环氧树脂相比,双酚A二缩水甘油醚(DGEBA)/GA/DMP-30体系的制备和回收不需要任何特殊催化剂,如TBD、Zn(Ac)等,这些催化剂通常价格昂贵、有毒,且与其他化合物的相容性较差。所得树脂的玻璃化转变温度和强度与传统环氧树脂相似。研究了GA含量、DMP-30含量和温度对溶解速率的影响。分解后的环氧低聚物(DEO)进一步用作反应原料制备新的树脂。结果发现,DEO可以显著提高环氧树脂的韧性。这项工作提供了一种制备易于回收的环氧树脂的简单方法,成本低且易于实施。