苯并(口恶)嗪改性环氧酸酐体系的固化机理及动力学

doi:10.3969/j.issn.0438-1157.2014.03.023

化工学报 ›› 2014, Vol. 65 ›› Issue (3): 929-933.DOI: 10.3969/j.issn.0438-1157.2014.03.023

• 催化、动力学与反应器 • 上一篇下一篇

苯并(口恶)嗪改性环氧酸酐体系的固化机理及动力学

廖进彬^1,2, 姜其斌^1,2, 曾智¹, 李鸿岩^1,2

1 株洲时代新材料科技股份有限公司, 湖南株洲 412007;
2 湖南工业大学包装与材料工程学院, 湖南株洲 412007

收稿日期:2013-06-13 修回日期:2013-07-14 出版日期:2014-03-05 发布日期:2014-03-05
通讯作者: 姜其斌
作者简介:廖进彬（1989—），男，硕士研究生。

Curing mechanism and kinetics of epoxy/anhydride system modified by benzoxazine

LIAO Jinbin^1,2, JIANG Qibin^1,2, ZENG Zhi¹, LI Hongyan^1,2

1 Zhuzhou Times New Material Technology Co., Ltd., Zhuzhou 412007, Hunan, China;
2 School of Packaging and Materials Engineering, Hunan University of Technology, Zhuzhou 412007, Hunan, China

Received:2013-06-13 Revised:2013-07-14 Online:2014-03-05 Published:2014-03-05

摘要/Abstract

摘要： 利用一种二胺型苯并(口恶)嗪改性环氧酸酐体系。通过FT-IR和DSC分析了改性体系的固化机理。结果表明：共混树脂体系在固化时存在两个反应，首先是环氧树脂与足量的酸酐在咪唑作用下在100℃先开始固化，并在150℃固化2 h后固化完全，之后苯并(口恶)嗪在180℃发生开环聚合。用非等温DSC法研究了该共混体系的固化动力学。采用Flynn-Wall-Ozawa方法求出了共混体系在固化时两个固化反应的活化能，分别为65.27 kJ·mol^-1和92.8 kJ·mol^-1，并利用Friedman方法判断了两个反应都是自催化反应，计算得到自催化模型曲线与实验曲线能较好地吻合。

关键词: 苯并(口恶)嗪, 环氧树脂, 酸酐, 固化机理, 固化反应动力学

Abstract: An epoxy/anhydride system was modified by aromatic diamine-based benzoxazine. The curing mechanism of the system was analyzed with Fourier transform infrared spectroscopy(FT-IR)and differential scanning calorimetry (DSC). The blend system exhibited two curing reactions in the curing process. Epoxy resin first cured with sufficient anhydride catalyzed by imidazole at 100℃, and cured completely at 150℃ for 2 h. Benzoxazine underwent ring-opening polymerization at 180℃. The curing kinetics of modified resin system was studied with non-isothermal DSC at different heating rates. The average activation energies of two reactions were calculated utilizing the Flynn-Wall-Ozawa method to be 65.27 kJ·mol^-1 and 92.8 kJ·mol^-1, respectively. Both curing reactions were found to be autocatalytic processes by the Friedman method, and the predicted curves from the autocatalytic model fitted well with those of experiments.

Key words: benzoxazine, epoxy resin, anhydride, curing mechanism, curing kinetics

中图分类号:

TQ320.2

廖进彬, 姜其斌, 曾智, 李鸿岩. 苯并(口恶)嗪改性环氧酸酐体系的固化机理及动力学[J]. 化工学报, 2014, 65(3): 929-933.

LIAO Jinbin, JIANG Qibin, ZENG Zhi, LI Hongyan. Curing mechanism and kinetics of epoxy/anhydride system modified by benzoxazine[J]. CIESC Journal, 2014, 65(3): 929-933.

参考文献 21

[1]	Hu Yuming(胡玉明),Wu Liangyi(吴良义). Curing Agent(固化剂)[M]. Beijing:Chemical Industry Press,2004
[2]	Montero B, Serra A, Ramírez C, Ramis X. Epoxy/anhydride networks modified with polyhedral oligomeric silsesquioxanes[J]. Polym. Compos., 2013, 34: 96-108
[3]	Mauri A N, Galego N, Riccardi C C, Williams R J. Kinetic model for gelation in the diepoxide-cyclic anhydride copolymerization initiated by tertiary amines[J]. Macromolecules, 1997, 30: 1616-1620
[4]	Li Hongyan(李鸿岩),Fei Ming(费明),Wang Kai(王楷),Jiang Dawei(蒋大伟). Curing kinetics and thermal property epoxy/anhydride system modified by bismaleimide[J]. Insulating Materials (绝缘材料), 2012, 45: 38-41
[5]	Hyum J K,Zdenka B, Ishida H. Molecular characterization of the polymerization of acety-functional benzoxazine resins[J].Polymer, 1999, 40: 1815-1822
[6]	Hong Y L,Ishida H. Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines[J]. Polymer, 1999, 40: 4365-4376
[7]	Yu D S,Chen H,Shi Z X,Xu R W. Curing kinetics of benzoxazine resin by torsional braid analysis[J]. Polymer, 2002, 43: 3163-3068
[8]	Gu Yi(顾宜). Benzoxazine resin—a new kind of thermosetting engineering plastics[J]. Thermosetting Resin(热固性树脂),2002, 17(2): 31-34
[9]	Agag T. Preparation and properties of some thermosets derived from allyl-functional naphthoxazines[J]. J. Appl. Polym. Sci., 2006, 100: 3769-3777
[10]	Liu Y L,Chou C I. High performance benzoxazine monomers and polymers containing furan groups[J]. J. Polym. Sci. Part A: Polym. Chem., 2005, 43: 5267-5282
[11]	Zhuang Tian(庄田),Huang Jianxiang(黄健翔),Yang Fei(杨菲),Xie Kun(谢坤). High-performance and heat-resistant modified epoxy resin[P]: CN, 102153837A. 2011-08-17
[12]	Ishida H,Allen D J. Mechanical characterization of copolymers based on benzoxazine and epoxy[J]. Polymer, 1996, 37: 4487-4495
[13]	Kimura H, Matsumoto A, Hasegawa K, Ohtsuka K, Fukuda A. Epoxy resin cured by bisphenol A based benzoxazine[J]. J. Appl. Polym. Sci., 1998, 68: 1903-1910
[14]	Sbirrazzuoli N, Vyazovkin S. Learning about epoxy cure mechanisms from isoconversional analysis of DSC data[J]. Thermochim Acta, 2002, 388: 289-298
[15]	Vyazovkin S, Mittitelu A, Sbirrazzuoli N. Kinetics of epoxy-amine curing accompanied by the formation of liquid crystalline structure[J]. Macromol. Rapid Commun., 2003, 24: 1060-1065
[16]	Jubsilp C,Punson K,Takeichi T,Rimdusit S. Curing kinetics of benzoxazine-epoxy copolymer investigated by non-isothermal differential scanning calorimetry[J]. Polymer Degradation and Stability, 2010, 95: 918-924
[17]	Jubsilp C,Damrongsakkul S, Takeichi T,Rimdusit S. Curing kinetics of arylamine-based polyfunctional benzoxazine resins by dynamic differential scanning calorimetry[J]. Thermochimica Acta, 2006, 447: 131-140
[18]	Kissinger H E. Reaction kinetics in differential thermal analysis[J]. Anal. Chem., 1957, 29: 1702-1706
[19]	Ozawa T. A new method of analyzing thermogravimetric data[J]. Bull. Chem. Soc. Jpn., 1965, 38:1881-1886
[20]	Flynn J H,Wall L A. A quick direct method for the determination of activation energy from thermogravimetric data[J]. Polym. Lett., 1966, 4: 323-328
[21]	Friedman H L. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to aphenolic plaic[J]. J. Polym. Sci.: Part C, 1965, 6: 183-195

苯并(口恶)嗪改性环氧酸酐体系的固化机理及动力学

Curing mechanism and kinetics of epoxy/anhydride system modified by benzoxazine

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

[1]	孟令玎, 崇汝青, 孙菲雪, 孟子晖, 刘文芳. 改性聚乙烯膜和氧化硅固定化碳酸酐酶[J]. 化工学报, 2023, 74(8): 3472-3484.
[2]	赵婧, 顾程文, 蹇锡高, 翁志焕. 厚朴酚基环氧树脂防腐涂层的制备及性能评价[J]. 化工学报, 2023, 74(7): 3010-3017.
[3]	毛磊, 刘冠章, 袁航, 张光亚. 可捕集CO₂的纳米碳酸酐酶粒子的高效制备及性能研究[J]. 化工学报, 2023, 74(6): 2589-2598.
[4]	郑杰元, 张先伟, 万金涛, 范宏. 丁香酚环氧有机硅树脂的制备及其固化动力学研究[J]. 化工学报, 2023, 74(2): 924-932.
[5]	王哲, 祖愿, 胡方圆, 蹇锡高. 含杂萘联苯结构的环氧树脂固化动力学分析[J]. 化工学报, 2022, 73(2): 681-688.
[6]	韩维辰, 王佳铭, 贺曼罗, 贺高红, 焉晓明, 阮雪华. 潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化[J]. 化工学报, 2021, 72(7): 3832-3838.
[7]	鲁秋实, 叶光华, 周兴贵. 半间歇釜式反应器安全高效操作的数值优化策略[J]. 化工学报, 2021, 72(2): 975-983.
[8]	金晶, 安秋凤, 杨博文, 史书源, 田华鹏. 环氧基POSS改性环氧树脂的研制与性能研究[J]. 化工学报, 2020, 71(5): 2432-2439.
[9]	于守武, 肖淑娟, 赵泽文, 霍晓文, 魏俊富. 蜜胺-环氧树脂双层包覆聚磷酸铵及其阻燃PP的研究[J]. 化工学报, 2019, 70(6): 2370-2376.
[10]	倪卓, 林煜豪, 黄苇颖, 林丽蓉. 环氧树脂微胶囊合成及其反应动力学[J]. 化工学报, 2018, 69(4): 1790-1798.
[11]	陈杨, 史铁钧, 钱莹, 何涛. 新型含硼苯并噁嗪的合成及其与环氧树脂共混热性能[J]. 化工学报, 2017, 68(6): 2604-2610.
[12]	杜朋亚, 边锋, 姚蒙蒙, 常达, 唐二军. 高阻尼性涂层用环氧-丙烯酸酯复合乳液的合成[J]. 化工学报, 2016, 67(10): 4508-4513.
[13]	陈功, 卢滇楠, 吴建中, 刘铮. 水化层影响酸酐酶内CO₂扩散行为的分子动力学模拟[J]. 化工学报, 2015, 66(8): 2903-2910.
[14]	刘建华, 史铁钧, 李明, 徐国梅, 王权, 虞伕. 含双DOPO的双酚A-单苯并(口恶)嗪合成、表征及其与环氧树脂共聚物的阻燃性能[J]. 化工学报, 2015, 66(2): 820-826.
[15]	孔明华, 伍联营, 徐显朕, 胡仰栋. MA/EG与TBPA/EG聚酯化反应动力学[J]. 化工学报, 2015, 66(11): 4446-4451.