酚醛型环氧树脂_双酚A型氰酸酯树脂体系固化动力学的研究

37320083AppliedChemicalIndustryVol.37No.3Mar.2008:2007212210:(1982-),,,,,:13570525441,E-mail:[e-mail]/A,,,(,510640):(DSC)/A,KissingerOzawaCrane,21,KissingerOzawa,49.05kJ/mol54.86kJ/mol,Crane12:A;;;DSC:TQ323.5:A:1671-3206(2008)03-0300-04Studyoncuringkineticsofnovolacepoxy/bisphenolAcyanateresinsystemPENGZhen,FUWei2wen,LUOYuan2fang,JIADe2min(GuangdongKeyLaboratoryforHigh2Property&FunctionalPolymericMaterials,CollegeofMaterialScienceandEngineering,SouthChinaUniversityofTechnology,Guangzhou510640,China)Abstract:CuringprocessoftheblendsconsistingofdifferentamountofcyanateesterandepoxyresinisstudiedbymeansofDSC.Curingkineticparametersareevaluatedandtherelationshipbetweenthesystemisinvestigated.ThelowestapparentactivationenergyvaluesofEP/CEblendswithmolecularratioof2/1obtainedbyOzawaandKissingertreatmentofDSCresultequalto54.86kJ/moland49.05kJ/molre2spectively.Thenominalreactionordersarebetween1and2byCranemethod.Keywords:bisphenolAcyanateester;novolacepoxy;curingkinetics;DSC(CE)OCN,,,,[1],,,,[2],[325],,()[6],[729](FTIR),DSC,,,,,11.1A(AroCyB210),79,99.5%,Ciba,;(F244),0.50mol/100g,,DSC2910;MAGNA22R7601.290,n41,21,11,12,14©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(DSC)1.4(FTIR)KBr,5h22.1160,FTIRCH(830cm-1)(RC):RC=I-II830-IIII830CH(830cm-1),930cm-1112,1160Fig.1FTIRspectraofcyanateesterco2curedwithepoxyat1602Fig.2Conversionofepoxygroupatdifferenttime2,,0.250.5,,,,24,,,2.2DSC,DSC5,10,15,2025/minDSC,320/minDSC,320/minDSCFig.3DSCcurvesofdifferentmolecularat20/min1DSCTable1TheresultsofDSCdeterminationunderdifferentratios/(min-1)Tp/4121111214015217.39216.68231.61238.72225.21245.5710240.85234.45243.07256.85247.96259.6015253.65249.74260.76263.25265.02266.6020266.80260.76271.42274.62276.75273.3225277.22277.22284.69285.93288.42292.661,,,DSC,,KissingerCraneOzawa,2.2.1KissingerCraneDSCDSC,,Tp,KissingerKissinger[10211]:,nDSC,103©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[12]:dln(T2p)d(1Tp)=-E/R,K/min;Tp,K;R,8.314J/molK;E,J/molKissingerKissinger,ln(/T)1/Tp,2KissingerTable2KineticparametersbymethodofKissingerEPCE/E/(kJmol-1)075.980.2550.820.563.24159.95249.05451.87nCrane[13]:dlnd(1Tp)=-(EnR+2Tp)E/nR2Tp,2Tp,ln1/Tp,,44Crane11Fig.4Kineticcurvesofblendsatratioof11bycranemethod,:Y=-8290.56X+18.184011,n=1.10,,21,12,4114,n1.27,1.07,1.251.28,2.2.2OzawaOzawa[10,14]E,,,OzawaOzawa,,DSC,[12],Ozawa[10]:lg=lg[AERG()]-2.315-0.4567ERTG();E,J/mol;R;Ai,,G(),lg1/T,Ek=-0.4567E/R,E-kR/0.45673OzawaTable3KineticparametersbymethodofOzawaEPCE/E/(kJmol-1)081.010.2556.430.579.19164.79254.86457.965OzawaFig.5KineticcurvesbyOzawamethod23,KissingerOza2wa,[13],,,203©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[15],[16],25%,,,[17],23,,,;,,,;,,;,[12],,,,,,,,,,,,,,,,FTIR3(1)DSC,KissingerCraneOzawa,,21,12,(2),;,;,:[1].[M].:,1999:47.[2],.[M].:,1999:25.[3],.F/DDM[J].,2007,21(6):1592161.[4],,,./[J].,2006,32(6):7182722.[5],,,.[J].,2006,21(1):12217.[6]XuYouzhiEugene,SungChongSookPark.UV,lumines2cence,andFTIRcharacterizationofcurereactioninbis2phenolAdicyanateesterresin[J].Macromolecules,2002,35(24):904429048.[7]BauerM,BauerJ,KuhnG.Kineticsandmodelingofther2malpolycyclotrimerizationofaromaticdicyanates[J].Ac2taPolym,1986,37:7152719.[8]BauerJ,BauerM.MonteCarlosimulationofpolycyclotri2merizationofdifunctionalaromaticcyanicacidesters[J].ActaPolym,1987,38:16221.[9]SimonSL,GillhamJK.Curekineticsofathermosettingliquiddicyanatesestermonomer/high2Tgpolycyanuratematerial[J].JApplPolymSci,1993,47:4612485.[10],.[M].:,2001.[11]KissingerE.Reactionkineticindifferentialthermalanaly2sis[J].AnalChem,1957,29:170221707.[12].[D].:,2005.[13]CraneLW,DynesPJ,KaelbleDH.Analysisofcuringkineticsinpolymercomposites[J].JournalofPolymerSc2ience,PolymerLettersEdition,1973,11(8):5332534.[14]OzawaT.Kineticanalysisofderivativecurvesinthermalanalysis[J].JournalofThermalAnalysis,1970(2):3012315.[15],,,.[J].,2001,18(3):10.[16],,,./[J].,2001,16(2):26.[17],,,.(2)[J].,1992(2):529.303©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.