Curing kinetics of epoxy resins/amine system and epoxy/episulfide resin/amine system

doi:10.3969/j.issn.0438-1157.2013.11.022

›› 2013, Vol. 64 ›› Issue (11): 4046-4053.DOI: 10.3969/j.issn.0438-1157.2013.11.022

Previous Articles Next Articles

Curing kinetics of epoxy resins/amine system and epoxy/episulfide resin/amine system

LIU Xiaodong¹, CHENG Jue¹, LIN Xin², ZHANG Junying^1,2

1. Key Laboratory of Carbon Fiber and Function Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, China;
2. Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164, Jiangsu, China

Received:2013-03-25 Revised:2013-05-21 Online:2013-11-05 Published:2013-11-05
Supported by:
supported by the National Natural Science Foundation of China(21176017)and the High-tech Research and Development Program of China(2012AA03A205).

环氧树脂和环氧/环硫树脂与胺的固化反应动力学

刘晓东¹, 程珏¹, 林欣², 张军营^1,2

1. 北京化工大学, 教育部碳纤维及功能高分子教育部重点实验室, 北京 100029;
2. 北京化工大学常州先进材料研究院, 江苏常州 213164

通讯作者: 张军营
作者简介:刘晓东(1982-),女,硕士研究生。
基金资助:
国家自然科学基金项目(21176017);国家高技术研究发展计划项目(2012AA03A205);江苏省科技支撑项目(BE2010066);常州微电子化学材料公共工业技术平台项目(CZ2010003)。

Abstract

Abstract: The curing kinetics of a low viscosity epoxy resin system CY184/IPDA and an epoxy-episulfide resin system CY184/ES184/IPDA were studied by non-isothermal DSC.An advanced isoconversional method proposed by Vyazovkin was used to solve the activation energy of these resin systems.Based on the Málek method,curing mechanism functions and reaction kinetic parameters were obtained and the curing kinetic equations of these systems were determined.Average activation energy values for CY184/IPDA and CY184/ES184/IPDA epoxy/episulfide resin system were 47.04 kJ·mol^-1 and 48.97 kJ·mol^-1 respectively.The calculated curves fitted well with experimental DSC curves of these systems which could be described by Šesták-Berggren(m,n)model.

Key words: epoxy/episulfide resins, non-isothermal DSC, Vyzaovkin method, Má, lek method

摘要： 采用非等温DSC法对低黏度体系CY184/IPDA环氧树脂体系及对CY184/ES184/IPDA环氧/环硫树脂体系的固化反应动力学进行了研究。用高级等转化率Vyazovkin积分法求取活化能E_a,通过Málek法确定了固化反应机理函数和动力学参数,得到固化反应动力学方程。结果表明:CY184/IPDA环氧树脂体系的平均活化能为47.04 kJ·mol^-1;CY184/ES184/IPDA环氧/环硫树脂体系的活化能为48.97 kJ·mol^-1。两种体系的模型拟合曲线与实验得到的DSC曲线吻合得较好,均符合esták-Berggren(m,n)模型。

关键词: 环氧/环硫树脂, 非等温DSC, Vyazovkin法, Málek法

CLC Number:

TQ323.5

LIU Xiaodong, CHENG Jue, LIN Xin, ZHANG Junying. Curing kinetics of epoxy resins/amine system and epoxy/episulfide resin/amine system[J]. , 2013, 64(11): 4046-4053.

刘晓东, 程珏, 林欣, 张军营. 环氧树脂和环氧/环硫树脂与胺的固化反应动力学[J]. CIESC Journal, 2013, 64(11): 4046-4053.

References 26

[1]

Wenhsiung Ku,Bell J P.Epoxy/episulfide resin//Sedlacek B,Kahovec J.Se Crosslinked Epoxides[C].Berlin:Walter de Gruyter,Inc.,1987:1-10[2] Bell J P,Don T M,Voong S,et al.Synthesis and properties of epoxy-episulfide resins[J].Die Angewandte Makromolekulare Chemie,1996,240(1):67-81[3] Li Y,Cheng J,Zhang J.Study on the synthesis of thiirane[J].Journal of Applied Polymer Science,2006,101(6):4023-4027[4] Chino K,Suga K,Ikawa M,et al.Novel rapid‐cure adhesives for low temperature using thiirane compound[J].Journal of Applied Polymer Science,2001,82(12):2953-2957[5] Vandenberg E J.Mechanism aspects of the ring-opening polymerization of the episulfides compared to epoxides[J].Journal of Polymer Science A Polymer Chemistry,1972,10:329-354[6] Tsuchida K,Bell J P.A new epoxy/episulfide resin system for coating applications:curing mechanism and properties[J].International Journal of Adhesion and Adhesives,2000,20(6):449-456[7] Tsuchida K,Bell J P.A new epoxy/episulfide resin system for electronic applications(Ⅱ):Pot life and prepreg storage life evaluation[J].Journal of Adhesion Science and Technology,2000,14(12):1515-1526[8] Fu Zhonglin(付中林),Yin Wenhua(尹文华),Wu Biyao(吴璧耀).Study on properties of cued compound for bisphenyl F epoxy-episulfide resin sytem[J].Adhesion(粘接),2005,26(3):7-9[9] Li Yafeng(李亚峰).Study on the synthesis and application of thiiran resins[D].Beijing:Beijing University of Chemical Technology,2006[10] Lan Xiaokang,Huang Wei,Yu Yunzhao.Synyhesis,characterization and properties of the polysiloxane-based episulfide resin[J].European Polymer Journal,2010,46:1545-1556[11] Vyazovkin S.Thermal analysis[J].Anal. Chem.,2008,80(12):4301-4316[12] Chu F,McKenna T,Lu S.Curing kinetics of an acrylic resin/epoxy resin system using dynamic scanning calorimetry[J].European Polymer Journal,1997,33(6):837-840[13] Šesták J,Berggren G.Study of the kinetics of the mechanism of solid-state reactions at increasing temperatures[J].Thermochimica Acta,1971,3(1):1-12[14] Ghaemy M,Rostami A A,Omrani A.Isothermal cure kinetics and thermodynamics of an epoxy-nickel-diamine system[J].Polymer International,2006,55(3):279-284[15] Zhou Tianle,Gu Mingyuan,Jin Yanping,et al.Studying on the curing kinetics of a DGEBA/EMI-2,4/nano-sized carborundum system with two curing kinetic methods[J].Polymer,2005,46:6174-6181[16] Zhao Lei,Hu Xiao.A variable reaction order model for prediction of curing kinetics of thermosetting polymers[J].Polymer,2007,48:6125-6133[17] Yoo M J,Kim S H,Park S D,et al.Investigation of curing kinetics of various cycloaliphatic epoxy resins using dynamic thermal analysis[J].European Polymer Journal,2010,46(5):1158-1162[18] Málek J.A computer program for kinetic analysis of non-isothermal thermoanalytical data[J].Thermochimica Acta,1989,138(2):337-346[19] Málek J.The kinetic analysis of non-isothermal data[J].Thermochimica Acta,1992,200:257-269[20] Hseih H K,Su C C,Woo E M.Cure kinetics and inter-domain etherification in an amine-cured phenoxy/epoxy system[J].Polymer,1998,39(11):2175-2183[21] Roşu D,Mustatţă F,Caşcaval C N.Investigation of the curing reactions of some multifunctional epoxy resins using differential scanning calorimetry[J].Thermochimica Acta,2001,370(1):105-110[22] Roşu D,Caşcaval C N,Mustatţă F,et al.Cure kinetics of epoxy resins studied by non-isothermal DSC data[J].Thermochimica Acta,2002,383(1):119-127[23] Sbirrazzuoli N,Vyazovkin S.Learning about epoxy cure mechanisms from isoconversional analysis of DSC data[J].Thermochimica Acta,2002,388(1):289-298[24] Vyazovkin S,Sbirrazzuoli N.Mechanism and kinetics of epoxy-amine cure studied by differential scanning calorimetry[J].Macromolecules,1996,29(6):1867-1873 [25] Vyazovkin S, Dollimore D. Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids[J].Journal of Chemical Information and Computer Sciences,1996,36(1):42-45

[26]

Vyazovkin S.Advanced isoconversional method[J].Journal of Thermal Analysis and Calorimetry,1997,49(3):1493-1499[27] Vyazovkin S.Evaluation of activation energy of thermally stimulated solid-state reactions under arbitrary variation of temperature[J].Journal of Computational Chemistry,1998,18(3):393-402[28] Vyazovkin S.Modification of the integral isoconversional method to account for variation in the activation energy[J].Journal of Computational Chemistry,2000,22(2):178-183[29] Sbirrazzuoli N,Vyazovkin S,Mititelu A,et al.A study of epoxy-amine cure kinetics by combining isoconversional analysis with temperature modulated DSC and dynamic rheometry[J].Macromolecular Chemistry and Physics,2003,204(15):1815-1821[30] Senum G I,Yang R T.Rational approximations of the integral of the Arrhenius function[J].Journal of Thermal Analysis and Calorimetry,1977,11(3):445-447 [31] Koga N.Kinetic analysis of thermoanalytical data by extrapolating to infinite temperature[J].Thermochimica Acta,1995,258:145-159

Curing kinetics of epoxy resins/amine system and epoxy/episulfide resin/amine system

环氧树脂和环氧/环硫树脂与胺的固化反应动力学

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

References 26

Related Articles 2

Recommended Articles

Metrics

Comments

[1]	LIU Huijuan, ZHAN Xibing, ZHU Wenqin, LIN Xin, CHENG Jue, ZHANG Junying. Preparation and curing reaction kinetics of liquid vinyl silicone resin [J]. CIESC Journal, 2014, 65(4): 1509-1516.
[2]	LI Jingrui, LIU Jialin, ZHANG Junying, CHENG Jue. Non-isothermal curing reaction kinetics of TGDDM/1,4-bis(4-diaminobenzene-1-oxygen) n-butane [J]. CIESC Journal, 2013, 64(9): 3421-3427.