环氧树脂微胶囊合成及其反应动力学

doi:10.11949/j.issn.0438-1157.20170619

摘要/Abstract

摘要：

将环氧树脂E-51分散在水中形成稳定的乳液，使用三乙烯四胺固化剂，在环氧树脂液滴表面形成交联结构作为环氧树脂微胶囊囊壁，这种微胶囊为环氧树脂复合材料的科学研究和工程应用提供了无界面差异囊壁的研究模型。采用扫描电子显微镜（SEM）和光学显微镜（OM）分析了乳化剂种类及用量、反应温度和搅拌速率等工艺条件对这种微胶囊的形成过程、表面形貌、粒径大小及分布和壁厚的影响。采用红外光谱（FTIR）研究了环氧树脂微胶囊的化学结构。当合成条件为乳化剂Tween 80浓度为1%，固化剂三乙烯四胺浓度为2.5%，反应温度90℃，搅拌速度600～1000 r·min^-1，合成的环氧树脂微胶囊形状规整，表面光滑致密，平均粒径为103 μm，囊芯含量为44.65%，壁厚为5 μm。研究三乙烯四胺固化剂中伯胺和仲胺的反应速率常数和活化能等反应动力学参数，定量分析环氧树脂-三乙烯四胺的化学反应中伯胺和仲胺的反应活性差异。

关键词: 环氧树脂, 微胶囊, 自修复材料, 三乙烯四胺, 反应动力学

Abstract:

A series of microcapsules were prepared by interfacial polymerization, epoxy resin E-51 as core materials and the condensation of triethylenetetramine and epoxy resin E-51 to wall materials. The kind of epoxy microcapsules provide an investigation model for scientific research and engineering applications of the epoxy resin self-healing composites with no different interfaces. The microcapsule formation process, particle size and size distribution, morphology and chemical structure were analyzed by optical microscopy (OM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), etc. Optimum synthetic conditions are obtained as the following:emulsifier (Tween 80) dosage is 1%, dosage of triethylenetetramine is 2.5%, reaction temperature is 90℃, and agitation rate is 600-1000 r·min^-1. The reaction kinetic parameters such as reaction rate constant and activation energy of primary and secondary amines in triethylenetetramine curing agent were studied in details. Quantitative analysis was conducted for the reactive difference of primary and secondary amine groups between these amines in the chemical condesation of epoxy resin and triethylene tetramine.

Key words: epoxy resin, microcapsules, self-healing materials, triethylenetetramine, reaction kinetics

中图分类号:

TQ323.5

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.

NI Zhuo, LIN Yuhao, HUANG Weiying, LIN Lirong. Preparation and reaction kinetics of epoxy resin microcapsules[J]. CIESC Journal, 2018, 69(4): 1790-1798.

参考文献 30

[1]	OLLIER R P, PENOFF M E, ALVAREZ V A. Microencapsulation of epoxy resins:optimization of synthesis conditions[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2016, 511:27-38.
[2]	李成功. 新材料研究发展与产业化趋势[J]. 中国机械工程, 2000, 11(2):154-156. LI C G. Research and development of advanced materials and advanced material industry[J]. China Mechanical Engineering, 2000, 11(2):154-156.
[3]	MAY C A, TANAKA Y. Epoxy Resins:Chemistry and Technology[M]. Dutch:M. Dekker, 1973:19-20.
[4]	李兴旺, 张玉奇, 廖亮, 等. 智能型混凝土修补材料体系研究进展[J]. 土木建筑与环境工程, 2006, 28(4):142-145. LI X W, ZHANG Y Q, LIAO L, et al. Progress of intelligent concrete repair materials[J]. Journal of Civil, Architectural & Environmental Engineering, 2006, 28(4):142-145.
[5]	叶三男, 王培, 孙阳超, 等. 微胶囊填充型自修复涂层材料研究进展[J]. 表面技术, 2016, 45(6):19-25. YE S N, WANG P, SUN Y C, et al. Research advances in microcapsuled self-healing coatings materials[J]. Surface Technology, 2016, 45(6):19-25.
[6]	MAULDIN T C, KESSLER M R. Enhanced bulk catalyst dissolution for self-healing materials[J]. Journal of Materials Chemistry, 2010, 20(20):4198-4206.
[7]	WHITE S R, SOTTOS N R, GEUBELLE P H, et al. Autonomic healing of polymer composites[J]. Nature, 2001, 409(6822):794.
[8]	LIU X, ZHANG H, WANG J, et al. Preparation of epoxy microcapsule based self-healing coatings and their behavior[J]. Surface and Coatings Technology, 2012, 206(23):4976-4980.
[9]	FAN H B, YUEN M M F. Material properties of the cross-linked epoxy resin compound predicted by molecular dynamics simulation[J]. Polymer, 2007, 48(7):2174-2178.
[10]	WU C, XU W. Atomistic molecular simulations of structure and dynamics of crosslinked epoxy resin[J]. Polymer, 2007, 48(19):5802-5812.
[11]	汪海平, 容敏智, 章明秋. 微胶囊填充型自修复聚合物及其复合材料[J]. 化学进展, 2010, 22(12):2397-2407. WANG H P, RONG M Z, ZHANG M Q. Self-healing polymers and polymer-based composites containing microcapsules[J]. Progress in Chemistry, 2010, 22(12):2397-2407.
[12]	冯建中, 明耀强, 张宇帆, 等. 异氰酸酯胶囊型自修复高分子材料研究进展[J]. 化工进展, 2016, 35(1):175-181. FENG J Z, MING Y Q, ZHANG Y F, et al. Progress of research on encapsuled isocyanate self-healingpolymeric materials[J]. Chemical Industry and Engineering Progress, 2016, 35(1):175-181.
[13]	DRY C, CORSAW M. A comparison of bending strength between adhesive and steel reinforced concrete with steel only rein forced concrete[J]. Cement and Concrete Research, 2003, 33(11):1723-1727.
[14]	RULE J D, BROWN E N, SOTTOS N R, et al. Wax-protected catalyst microspheres for efficient self-healing materials[J]. Advanced Materials, 2005, 17(2):205-208.
[15]	CHO S, ANDERSSON H, WHITE S, et al. Polydimethylsiloxane-based self-healing materials[J]. Advanced Materials, 2006, 18(8):997-1000.
[16]	WHITE S R, SOTTOS N R, GEUBELLE P H, et al. Autonomic healing of polymer composites[J]. Nature, 2002, 415(6873):794-797.
[17]	方雷, 石光, 李国明, 等. 环氧树脂微胶囊的制备研究[J]. 中国胶粘剂, 2005, 14(11):9-12. FANG L, SHI G, LI G M, et al. Preparation and research of epoxy resin microcapsules[J]. China Adhesives, 2005, 14(11):9-12.
[18]	刘云鹏. 微胶囊型自修复聚硅氧烷弹性体的结构与性能研究[D]. 广州:华南理工大学, 2015. LIU Y P. Structure and properties of microcapsuled self-healing polysiloxane elastomer[D]. Guangzhou:South China University of Technology, 2015.
[19]	姚开安, 赵登山. 仪器分析[M]. 南京:南京大学出版社, 2014:172-184. YAO K A, ZHAO D S. Instrumental Methods[M]. Nanjing:Nanjing University Press, 2014:172-184.
[20]	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 增塑剂环氧值的测定GB/T 1677-2008[S]. 北京:中国标准出版社, 2008. General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Determinating the epoxy value of plasticizers GB/T 1677-2008[S]. Beijing:Standardization Administration of the People's Republic of China, 2008.
[21]	刘竞超. 二胺基二苯基砜/环氧树脂固化动力学研究[J]. 高分子材料科学与工程, 1993, 5:7. LIU J C. Study on the reaction kinetics of epoxy resin and DDS[J]. Polymeric Materials Science & Engineering, 1993, 5:7
[22]	倪卓, 杜学晓, 王帅, 等. UF微胶囊合成反应的动力学研究[J]. 深圳大学学报(理工版), 2011, 28(3):249-254. NI Z, DU X X, WANG S, et al. Kinetics of synthesis of UF microcapsules[J]. Journal of Shenzhen University(Science and Engineering), 2011, 28(3):249-254.
[23]	MONTSERRAT S, MÁLEK J. A kinetic analysis of the curing reaction of an epoxy resin[J]. Thermochimica Acta, 1993, 228:47-60.
[24]	罗光华, 郑典模, 李广梅. 水乳液乳化剂的选择[J]. 广东化工, 2008, 35(11):62-64. LUO G H, ZHENG D M, LI G M. Choice of emulsifier for O/W emulsion[J]. Guangdong Chemical Industry, 2008, 35(11):62-64.
[25]	WANG J P. Preparation and response behavior of blue electronic ink microcapsules[J]. Optical Materials, 2008, 30(8):1268-1272.
[26]	倪卓, 杜学晓, 邢锋, 等. 表面活性剂对自修复环氧树脂微胶囊的影响[J]. 深圳大学学报(理工版), 2008, 25(4):25-31. NI Z, DU X X, XING F, et al. Effects of surfactant on MUF encapsulated epoxy in self-healing[J]. Journal of Shenzhen University (Science and Engineering), 2008, 25(4):25-31.
[27]	李祎彧. 乳化剂用量对石蜡微胶囊性能的影响[J]. 广州化工, 2011, 39(22):30-32. LI Y Y. The effect of emulsifier dosage on the performance of microencapsulated paraffin[J]. Guangzhou Chemical Industry, 2011, 39(22):30-32.
[28]	倪卓, 杜学晓. 自修复环氧胶黏剂分子设计[J]. 高分子材料科学与工程, 2009, (7):133-136. NI Z, DU X X. Materials design for self-healingepoxy adhesive[J]. Polymer Materials Science & Engineering, 2009, (7):133-136.
[29]	汤小平, 黄翠华. 环氧树脂固化行为研究[J]. 广州化工, 2013, 41(8):86-87. TANG X P, HUANG C H. Curing kinetics of epoxy resin by amine-containing agents[J]. Guangzhou Chemical Industry, 2013, 41(8):86-87.
[30]	洪晓东, 秦昌强, 赵娜, 等. DCPD微胶囊的制备及EP/微胶囊复合材料的力学性能[J]. 工程塑料应用, 2014, 42(1):112-115. HONG X D, QIN C Q, ZHAO N, et al. Preparation of dicyclopentadiene microcapsules and mechanical properties of epoxy/microcapsules composites[J]. Engineering Plastics Application, 2014, 42(1):112-115.