改性脂肪族胺类环氧树脂固化剂:非等温固化反应
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摘要
采用DSC法研究了改性脂肪族胺(DTP)/双酚A二缩水甘油醚(DGEBA)体系的非等温固化过程,结果表明,该固化反应是一个放热过程,且仅有一个对称的放热峰,对应于环氧胺开环加成反应.采用Flynn-Wall-Ozawa(FWO)模型关联活化能Eα与转化率α的关系,结果显示,该固化反应显示出与其他环氧树脂体系类似的反应规律.在反应开始时,该系统具有最高的表观活化能;但随着反应的进行,表观活化能逐渐降低.利用Málek模型研究该固化反应的动力学性质,根据模型特征参数αM、αp、α∞p确定了反应速率模型,即esták-Berggren(SB(m,n))经验模型.模型化研究表明,该固化反应过程具有自催化反应的特性,且模型与实验数据拟合情况较好.本文对DTP/DGEBA体系固化反应的研究有助于理解环氧-胺反应的机理和反应条件,为DTP/DGEBA固化工艺的选择提供了参考.
The non-isothermal curing reaction of the modification of aliphatic amines(DTP)/bisphenol A diglycidyl ether(DGEBA)system was investigated by using differential scanning calorimetry(DSC)method.The results indicate that the reaction is an exothermic process,and only one single and fairly symmetric exothermic peak can be found,which corresponds to the opening reaction of epoxy amine.The relationship between the effective activation energy and the conversion rate was established with Flynn-Wall-Ozawa(FWO)model.It is found that the reaction is similar to other epoxy resin systems following the same rules.In the initial stage,the system has the highest effective activation energy,while the effective activation energy decreases gradually as the reaction proceeds.Furthermore,the reaction rate model was determined asesták-Berggren(SB(m,n))empirical model according to the characteristic parameters of the model ofαM 、αp、α∞p,and the kinetics properties of the reaction was confirmed by Málek model.The simulated model discloses that the reaction is of autocatalytic characteristic,and the calculated reaction rates are in good agreement with the experimental values.The research on the curing reaction of DTP/DGEBA system contributes to the understanding of the reaction mechanism and the condition,and provides a reference for the selection of DTP/DGEBA curing process.
The non-isothermal curing reaction of the modification of aliphatic amines(DTP)/bisphenol A diglycidyl ether(DGEBA)system was investigated by using differential scanning calorimetry(DSC)method.The results indicate that the reaction is an exothermic process,and only one single and fairly symmetric exothermic peak can be found,which corresponds to the opening reaction of epoxy amine.The relationship between the effective activation energy and the conversion rate was established with Flynn-Wall-Ozawa(FWO)model.It is found that the reaction is similar to other epoxy resin systems following the same rules.In the initial stage,the system has the highest effective activation energy,while the effective activation energy decreases gradually as the reaction proceeds.Furthermore,the reaction rate model was determined asesták-Berggren(SB(m,n))empirical model according to the characteristic parameters of the model ofαM 、αp、α∞p,and the kinetics properties of the reaction was confirmed by Málek model.The simulated model discloses that the reaction is of autocatalytic characteristic,and the calculated reaction rates are in good agreement with the experimental values.The research on the curing reaction of DTP/DGEBA system contributes to the understanding of the reaction mechanism and the condition,and provides a reference for the selection of DTP/DGEBA curing process.
引文
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[15]PRIME R B,SACHER E.Kinetics of epoxy cure:2.The system bisphenol-A diglycidyl ether/polyamide[J].Polymer,1972,13(9):455-458.
[16]WAN J,BU Z Y,XU C J,et al.Preparation,curing kinetics,and properties of a novel low-volatile starlike aliphaticpolyamine curing agent for epoxy resins[J].Chemical Engineering Journal,2011,171(1):357-367.
[17]MLEK J.The kinetic analysis of non-isothermal data[J].Thermochimica acta,1992,200:257-269.
[18]MONTSERRAT S,MLEK J.A kinetic analysis of the curing reaction of an epoxy resin[J].Thermochimica acta,1993,228:47-60.
[19]SENUM G I,YANG R T.Rational approximations of the integral of the Arrhenius function[J].Journal of thermal analysis,1977,11(3):445-447.
[20]FLYNN J H,WALL L A.General treatment of the thermogravimetry of polymers[J].Journal of Research of the National Bureau Standards,1966,70(6):487-523.
[21]OZAWA T.A new method of analyzing thermogravimetric data[J].Bulletin of the chemical society of Japan,1965,38(11):1881-1886.
[22]VYAZOVKIN S,SBIRRAZZUOLI N.Isoconversional kinetic analysis of thermally stimulated processes in polymers[J].Macromolecular Rapid Communications,2006,27(18):1515-1532.
[23]SWIER S,VAN ASSCHE G,VAN MELE B.Reaction kinetics modeling and thermal properties of epoxy-amines as measured by modulated-temperature DSC.I.Linear step-growth polymerization of DGEBA+aniline[J].Journal of applied polymer science,2004,91(5):2798-2813.
[24]VYAZOVKIN S,SBIRRAZZUOLI N.Effect of viscosity on the kinetics of initial cure stages[J].Macromolecular Chemistry and Physics,2000,201(2):199-203.
[25]KOGA N,SˇESTK J,MLEK J.Distortion of the Arrhenius parameters by the inappropriate kinetic model function[J].Thermochimica acta,1991,188(2):333-336.
[26]MLEK J.The applicability of Johnson-Mehl-Avrami model in the thermal analysis of the crystallization kinetics of glasses[J].Thermochimica Acta,1995,267:61-73.
[27]MLEK J,CRIADO J M.Is the2esták-berggren equation a general expression of kinetic models[J].Thermochimica acta,1991,175(2):305-309.
[28]GIESS E A.Equations and tables for analyzing solid-state reaction kinetics[J].Journal of the American Ceramic Society,1963,46(8):374-376.
[2]DURGA G,KUKREJA P,NARULA A K.Studies on curing kinetics and thermal behavior of phosphorylated epoxy resin in the presence of aromatic amide-amines[J].Journal of applied polymer science,2010,118(6):3612-3618.
[3]KHURANA P,AGGARWAL S,NARULA A K,et al.Studies on the curing kinetics of epoxy resins using silicon containing amide-amines[J].Journal of thermal analysis and calorimetry,2003,71(2):613-622.
[4]SMITH A K,STARNER W E,WALKER F H.Polyamide curing agents based on mixtures of polyethyleneamines and piperazine derivatives.US Patent 6,008,313[P].1999-12-28.
[5]GHAEMY M,RIAHY M H.Kinetics of anhydride and polyamide curing of bisphenol A-based diglycidyl ether using DSC[J].European Polymer Journal,1996,32(10):1207-1212.
[6]CORNFORTH D A,DARWEN S P.Water dispersible polyamine-epoxy adduct and epoxy coating composition.US Patent5,246,984[P].1993-9-21.
[7]HEFNER JR R E,DRUMRIGHT R E.Epoxy resin adducts and thermosets thereof.US Patent Application 14,200,421[P].2014-3-7.
[8]MENARD K P.Dynamic mechanical analysis:apractical introduction[M].CRC press,2008.
[9]BABAYEVSKY P G,GILLHAM J K.Epoxy thermosetting systems:dynamic mechanical analysis of the reactions of aromatic diamines with the diglycidyl ether of bisphenol A[J].Journal of Applied Polymer Science,1973,17(7):2067-2088.
[10]BARTON J M.The application of differential scanning calorimetry(DSC)to the study of epoxy resin curing reactions[M].Epoxy resins and composites I.Springer Berlin Heidelberg,1985:111-154.
[11]WATSON E S,ONEILL M J,JUSTIN J,et al.A Differential Scanning Calorimeter for Quantitative Differential Thermal Analysis[J].Analytical Chemistry,1964,36(7):1233-1238.
[12]KISSINGER H E.Reaction kinetics in differential thermal analysis[J].Analytical chemistry,1957,29(11):1702-1706.
[13]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].第二版.北京:科学出版社,2008.HU R Z,GAO S L,ZHAO F Q,et al.Thermal analysis clynamics[M].(Second edition),Beijing,Science press,2008.
[14]张予东,徐祥民,郭有刚,等.聚乳酸/纳米石墨薄片复合材料的热分解动力学[J].河南大学学报(自然科学版),2010,40(1):31-35.ZHANG Y D,XU X M,GUO Y G,ZHANG P Y.Thermal decomposition kinetics of polylactide/nano-graphite sheets composites.[J].Journal of Henan University(Natural Science),2010,40(1):31-35.
[15]PRIME R B,SACHER E.Kinetics of epoxy cure:2.The system bisphenol-A diglycidyl ether/polyamide[J].Polymer,1972,13(9):455-458.
[16]WAN J,BU Z Y,XU C J,et al.Preparation,curing kinetics,and properties of a novel low-volatile starlike aliphaticpolyamine curing agent for epoxy resins[J].Chemical Engineering Journal,2011,171(1):357-367.
[17]MLEK J.The kinetic analysis of non-isothermal data[J].Thermochimica acta,1992,200:257-269.
[18]MONTSERRAT S,MLEK J.A kinetic analysis of the curing reaction of an epoxy resin[J].Thermochimica acta,1993,228:47-60.
[19]SENUM G I,YANG R T.Rational approximations of the integral of the Arrhenius function[J].Journal of thermal analysis,1977,11(3):445-447.
[20]FLYNN J H,WALL L A.General treatment of the thermogravimetry of polymers[J].Journal of Research of the National Bureau Standards,1966,70(6):487-523.
[21]OZAWA T.A new method of analyzing thermogravimetric data[J].Bulletin of the chemical society of Japan,1965,38(11):1881-1886.
[22]VYAZOVKIN S,SBIRRAZZUOLI N.Isoconversional kinetic analysis of thermally stimulated processes in polymers[J].Macromolecular Rapid Communications,2006,27(18):1515-1532.
[23]SWIER S,VAN ASSCHE G,VAN MELE B.Reaction kinetics modeling and thermal properties of epoxy-amines as measured by modulated-temperature DSC.I.Linear step-growth polymerization of DGEBA+aniline[J].Journal of applied polymer science,2004,91(5):2798-2813.
[24]VYAZOVKIN S,SBIRRAZZUOLI N.Effect of viscosity on the kinetics of initial cure stages[J].Macromolecular Chemistry and Physics,2000,201(2):199-203.
[25]KOGA N,SˇESTK J,MLEK J.Distortion of the Arrhenius parameters by the inappropriate kinetic model function[J].Thermochimica acta,1991,188(2):333-336.
[26]MLEK J.The applicability of Johnson-Mehl-Avrami model in the thermal analysis of the crystallization kinetics of glasses[J].Thermochimica Acta,1995,267:61-73.
[27]MLEK J,CRIADO J M.Is the2esták-berggren equation a general expression of kinetic models[J].Thermochimica acta,1991,175(2):305-309.
[28]GIESS E A.Equations and tables for analyzing solid-state reaction kinetics[J].Journal of the American Ceramic Society,1963,46(8):374-376.