低黏度混合酸酐固化环氧树脂的设计与性能  

Design and Properties of Low-Viscosity Mixed Anhydride Cured Epoxy Resins

作　　者：陈可祥 向芮 滕皓卿 马鹏琛 王少红 安乐 明小庆 张彦峰 王铁军[2] CHEN Kexiang;XIANG Rui;TENG Haoqing;MA Pengchen;WANG Shaohong;AN Le;MING Xiaoqing;ZHANG Yanfeng;WANG Tiejun(School of Chemistry,Xi’an Jiaotong University,Xi'an 710049,China;School of Aerospace Engineering,Xi’an Jiaotong University,Xi'an 710049,China;School of Mathematics Physics and Optoelectronic Engineering,Hubei University of Automotive Technology,Shiyan 442002,Hubei,China)

机构地区：[1]西安交通大学化学学院,西安710049 [2]西安交通大学航天航空学院,西安710049 [3]湖北汽车工业学院,数理与光电工程学院,湖北十堰442002

出　　处：《功能高分子学报》2024年第6期516-525,共10页Journal of Functional Polymers

基　　金：科技部重点研发项目(2019YFA0706801);国家自然科学基金(52173079);中央高校基本科研业务费资助项目(xtr052023001,xzy022024024)。

摘　　要：以低黏度三官能环氧化合物为环氧单体,并借鉴“杂质降低熔点”概念设计混合酸酐固化剂,设计了一种兼具力学性能与低黏度的环氧树脂。采用旋转流变仪对环氧树脂预聚物黏度进行分析,用差示扫描量热仪和动态热机械仪对环氧树脂进行热分析,用万能试验机对环氧树脂的力学性能进行研究。结果表明:环氧树脂预聚物在室温下储存3 h后黏度保持在1000 mPa·s,适用于单向带预浸料工艺;随着酸酐与环氧基团物质的量之比增加,树脂交联密度从2000 mol/m^(3)增加到6000 mol/m^(3),但综合力学性能先高后低;此外环氧树脂中存在的动态酯键赋予材料可降解性。Epoxy resin has many advantages.However,as a matrix resin for composites,epoxy resin has the weakness of high viscosity,poor fluidity and low processing time.Considering the high viscosity and poor storage ability of the traditional epoxy prepolymer,we designed an epoxy resin formulation possessing both certain mechanical strength and fluidity.We utilized a low-viscosity trifunctional epoxy compound,N,N-diglycidyl-4-glycidyloxyaniline(AFG),and a solid-liquid mixture of low-eutectic anhydrides,specifically 4-methyl tetrahydro phthalic anhydride and 1,2,3,6-tetrahydrophthalic anhydride,as the epoxy monomers and curing agents,respectively.More importantly,when stored at room temperature for 3 h,this mixture exhibited a low viscosity(1000 mPa·s),which was attributed to the solid-liquid mixed anhydrides remaining in a liquid state at room temperature without recrystallizing.Then,a series of epoxy resins were designed by controlling the mole ratio of epoxide groups to anhydride groups.These resins were analyzed through mechanical property experiments and thermal analysis.The results showed a wide range of adjustable crosslink density in the epoxy resin,from 2000 mol/m^(3)to 6000 mol/m^(3),and the establishment of a relationship between network,mechanical,and thermal properties of the epoxy resin.This epoxy resin was successfully applied to prepare composites by the unidirectional tape prepreg process.Moreover,the ester bonds can be triggered with transesterification behavior under the zinc(Ⅱ)acetylacetonate catalyst with hydroxyl group.Therefore,epoxy resins can be completely degraded by ethylene glycol at 180℃for 6 h.A wide range of mechanical and thermal properties can be achieved by controlling the ratio of epoxide groups to anhydride groups in epoxy resins,which provides a certain reference for the development of low-viscosity epoxy resins.

关 键 词：环氧树脂 混合酸酐 低黏度 交联密度 力学调控 

分 类 号：O631[理学—高分子化学] TB324[理学—化学]