1-己基-3-甲基咪唑四氯化铁盐固化环氧树脂E-51的反应特性

doi:10.11944/j.issn.1000-0518.2015.06.140375

摘要/Abstract

摘要：

采用差示扫描(DSC)量热分析法研究了1-己基-3-甲基咪唑四氯化铁离子液体([C₆mim]FeCl₄)与双酚A型环氧树脂E-51的固化反应。结果显示,由于[C₆mim]FeCl₄包含多级胺基结构,因此可以作为E-51的高温固化剂使用,其与E-51的反应包含两个阶段:第一个阶段的反应放热峰峰顶温度约在120 ℃,第二个阶段的反应放热峰峰顶温度会随着[C₆mim]FeCl₄用量的增加而发生变化。当[C₆mim]FeCl₄与混合胺复配成新型固化剂时,二者产生明显的协同效应。通过恒温DSC实验发现,复配体系与E-51的固化反应可以在室温下发生,表现为在30 ℃固化反应放热峰峰顶放热时间为5 min左右,且随着恒温固化反应温度的提高,峰顶放热峰时间会缩短。非等温动力学结果显示:复配体系与E-51的反应活化能为979 J/mol,仅是混合胺体系的17%左右。反应级数为0.5表明这一固化反应是无规反应。

关键词: 己基甲基咪唑四氯化铁离子液体, 双酚A型环氧树脂, 高温固化剂, 动力学

Abstract:

Here we investigated the curing reaction between bisphenol epoxy resin E-51 and 1-hexyl-3- methylimidazole iron tetrachloride salt([C₆mim]FeCl₄) by differential scanning calorimetry. It was confirmed that the multi-level amine structure makes [C₆mim]FeCl₄ possible to be used as high-temperature curing agent for E-51. The curing reaction can be divided into two stages:at the first stage, the exothermic peak is about 120 ℃; at the second stage, the exothermic peak changes with the volume of [C₆mim]FeCl₄. When [C₆mim]FeCl₄ reacts with the mixed-amine to form a new curing agent, they exhibit apparent synergistic effect. The DSC results show that the new curing agent can react with E-51 under room temperature. The duration of exothermic peak is about 5 min at 30 ℃, and moreover, the duration decreases with the increasing temperature. The activation energy of the reaction calculated by the method of non-isothermal kinetics is 979 J/mol, which is only about 17% of the mixed-amine system. Finally, as the reaction order of the curing reaction is 0.5, it is believed to be a kind of random reaction.

Key words: hexyl-methylimidazole iron tetrachloride salt, bisphenol epoxy resin, high temperature curing agent, dynamics

中图分类号:

马玉芹, 郑昌梅, 杨天博, 魏巍, 柳美华, 郑春柏, 邓鹏飏, 高莹. 1-己基-3-甲基咪唑四氯化铁盐固化环氧树脂E-51的反应特性[J]. 应用化学, 2015, 32(6): 636-640.

MA Yuqin, ZHENG Changmei, YANG Tianbo, WEI Wei, LIU Meihua, ZHENG Chunbai, DENG Pengyang, GAO Ying. Reaction Characteristics of Epoxy Resins E-51 Cured by 1-Hexyl-3-Methyl Imidazole Iron Tetrachloride Salt[J]. Chinese Journal of Applied Chemistry, 2015, 32(6): 636-640.

参考文献

[1]	HUANG Haijian,HUANG Ying. Physical Properties of Magnetic Ionic Liquids and Their Impact Factors[J]. Magn Mater Devices,2013,44:61-67(in Chinese). 黄海舰,黄英. 磁性离子液体的物性及其影响因素[J]. 磁性材料及器件,2013,44:61-67.
[2]	LI Xiaohua,YANG Fuming,ZHOU Qing,et al.Synthesis and Properties of 1-Methyl-3-Alkylimidazolium Tetrahalogenoferrate Magnetic Ionic Liquids[J]. J Process Eng,2010,10(4):789-794(in Chinese). 李小华,杨富明,周清,等. 磁性离子液体1-甲基-3-烷基咪唑四氯化铁盐的合成及其物性表征[J]. 过程工程学报,2010,10(4):789-794.
[3]	SUN Manling,WU Liangyi. Application of the Principles and Techniques of Epoxy Resin[M]. BeiJing:China Machine Press,2002:4-8(in Chinese). 孙曼灵,吴良义. 环氧树脂应用原理及技术[M]. 北京:机械工业出版社,2002:4-8.
[4]	CHEN Ping,LIU Shengping,WANG Dezhong. Epoxy Resin and Its Application[M]. Beijing:Chemical Industry Press,2011:1-5(in Chinese). 陈平,刘胜平,王德中. 环氧树脂及其应用[M]. 北京:化学工业出版社,2011:1-5.
[5]	Bortolini O,Conte V,Chiappe C. Epoxidation of Electrophilic Alkenes in Ionic Liquids[J]. Green Chem,2002,4:94-96.
[6]	Wang bo,Yang LiMing. Epoxidation of α,β-Unsaturated Carbonyl Compounds in Ionic Liquids/Water Biphasic System under Mild Conditions[J]. J Mol Catal A:Chem,2003,203:29-36.
[7]	Yadav J S, Reddy B V S, Basak A K, et al. [Bmim]BF4 Ionic Liquid:A Novel Reaction Medium for the Synthesis of β-Amino Alcohols[J]. Tetrahedron Lett,2003,(44 ):1047-1050.
[8]	Yu J,Zhang B M. Study of Cure Kinetic Model of Typical Bismelei-mide[J]. Acta Mater Compos Sin,2003,21(1):78-83.
[9]	Guo Z S,Du S Y,Zhang B R. Cure Kinetics and Chemorheological Behavior of Epoxy Resin Used in Advanced Composites[J]. Acta Mater Compos Sin,2004,21(4):146-152.
[10]	DING Jiangping,LIAO Dong,FAN Xinyu. Non-isothermal DSC Method of Composite Materials with Epoxy Curing Reaction[J]. Mater Rev,2011,25(7):139-143(in Chinese). 丁江平,廖栋,范欣愉. 非等温DSC法研究复合材料用环氧树脂的固化反应[J]. 材料导报,2011,25(7):139-143.
[11]	Kissinger H E. Reaction Kinetics in Differential Thermal Analysis[J]. Anal Chem,1957,29(11):1702-1708.
[12]	Crane L W,Dynes P J,Kaelble D H. Analysis of Curing Kinetics in Polymer Composite[J]. J Polym Sci:Polym Lett Ed,1973,11(8):533-537.

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