双马来酰亚胺的紫外光固化研究
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摘要
双马来酰亚胺(BMI)是耐热热固性树脂的典型代表,是制备高性能结构/功能材料最具竞争力的树脂品种之一,在国防军事、电子信息、交通运输等尖端工业领域中扮演着不可或缺的重要角色。目前BMI固化方式为热固化,其最大的缺点是固化温度高、生产周期长,由此易造成固化树脂的残余应力大,树脂的优异性能难以充分发挥等缺点。因此,如何获得更好的固化工艺条件成为BMI改性研究的重要内容之一。
     与其他固化方法相比,紫外光(UV)固化技术具有固化速度快、生产效率高、污染小、节省能源、降低成本、满足户外等特殊要求的优点,因此,作为“面向21世纪的绿色工业新技术”,UV固化得到了学术界和工业界的广泛关注。无疑,积极开展可紫外光固化的高性能BMI树脂的研究具有重要的理论意义和应用价值。本文旨在探讨BMI实现紫外光固化的最佳条件,建立BMI紫外光固化的方法,获得经紫外光固化的高性能BMI树脂,同时制备可紫外光固化BMI树脂。
     本文采取高温溶解的方法制备了N,N'-4,4'-二苯甲烷双马来酰亚胺(BDM)/1,6己二醇二丙烯酸酯(HDDA)/光引发剂体系,采用红外光谱分析法对体系UV固化反应性进行了表征,采用凝胶转化率曲线法、表干时间法以及热重分析法研究了光引发剂和BDM对体系UV固化凝胶率和热稳定性的影响。研究结果表明,BDM/HDDA体系需要在光引发剂的引发下才能进行UV固化,光引发剂中2,4,6-三甲基苯甲酰基-二苯基氧化磷(TPO)的综合引发效果要好于同类引发剂安息香乙醚(BE)和提氢型光引发剂二苯甲酮-三乙醇胺(BP-TEA)体系。
     研究了光引发剂对BDM/苯乙烯(St)体系UV固化反应性和UV固化效率的影响,并探讨了BDM含量对BDM/St体系UV固化的影响。研究表明,BDM/St体系只有在自由基裂解型光引发剂的引发剂下才能进行UV固化,光引发剂中TPO的综合引发效果要优于BE。
     制备了可UV固化的BDM/4-羟丁基乙烯基醚(HBVE)体系,研究了光引发剂的种类和含量以及BDM含量对BDM/HBVE体系UV固化的影响。研究结果表明,BDM/HBVE体系在自由基裂解型光引发剂的引发下可以进行UV固化,BDM的含量过低会造成体系无法达到表干,相同条件下BDM的含量越高体系UV固化凝胶率就越大。
Bismaleimide (BMI) is one kind of typical high performance thermosetting resin,which has been considered as one kind of the most competitive structural/functional materials, and playing more and more important role in many industries including defense and military, electronic information and transportation. The biggest drawback of BMI is its high curing temperature and long curing time, causing big residual stress in cured network and thus declining the performance of the material. Therefore, how to overcome the disadvantage has been the main subject on investigations of BMI.
     Compared to other curing methods, ultra-violet (UV) curing technology exhibits many advantages such as fast curing speed, high production efficiency, environmental protection, energy-saving and low cost as well as the possible end-usage in outdoors. Therefore, as the "new technology of green industries in the 21st century", UV curing has been received wide attentions in both academic and industrial fields. It is no doubt that there are important theoretical significance and application value in investigating UV-curable BMI resin. This thesis aims to investigate the possibility to develop UV-curable BMI resin.
     In this thesis, N,N'-4,4'-diphenylmethane bismaleimide(BDM)/1,6-hexamethylene diacrylate(HDDA)/photoinitiator system was prepared, the UV-curable reactivity of the system was characterized by infrared spectroscopy, gel content and dry time. The influences of the contents of photoinitiator and BDM on UV curing and thermal stability of the system were investigated. Results show that in order to achieve UV curing, BDM/HDDA system needs to be carried out with photoinitiators, 2,4,6-trimethyl benzoyl-diphenyl phosphate oxidation (TPO) shows more effective role than benzoin ethyl ether (BE), and benzophenone-triethanolamine (BP-TEA) system.
     The influence of photoinitiators on the UV-curability and UV curing efficiency of BDM/styrene (St) system was studied, and the influence of BDM content on the UV curing of the BDM/St system was also investigated. Results show that BDM/St system is UV-curable with radical cleavage-type photoinitiator, and TPO has bigger induced effect than BE.
     The UV-curable BDM/4-hydroxyl butyl vinyl ether (HBVE) system was prepared. The UV curing of BDM/HBVE system is affected by the type and content of photoinitiators as well as the content of BDM. It shows that BDM/HBVE system is UV-curable with radical cleavage-type photoinitiator. If the content of BDM is too low, BDM/HBVE is unable to reach dry. Under the same conditions, the higher the content of BDM, the greater the gel content is.
引文
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