低温下己内酰胺低聚物的合成-葛柱立

№.2　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　Apr.2007·20·　　　　　　JOURNALOFSHAANXIUNIVERSITYOFSCIENCE&TECHNOLOGY　　　　　　Vol.25＊　:1000-5811(2007)02-0020-04葛柱立,王鸿儒(,　710021)　:在低温、通氮气的条件下,以浓硫酸为催化剂,以水为引发剂,采用己内酰胺合成了其低聚物,用正丁醇和水对产物进行了萃取分离,通过GPC和IR对己内酰胺低聚物进行了表征,并分别研究了引发剂、温度、分子质量调节剂、时间和浓硫酸对己内酰胺转化率的影响.结果表明,缩聚反应的最佳条件为:氮气作保护气,反应温度170℃,反应时间3h,己内酰胺、水、己二酸和浓硫酸的质量比为:m(C6H11NO)∶m(H2O)∶m(C6H2O4)∶m(H2SO4)=100∶1∶2.25∶1,在此条件下己内酰胺的转化率为80%.GPC分析结果显示,所得缩聚产物的数均分子质量主要为1409和237,其红外光谱在2939.91cm-1、1635.11cm-1和1551.69cm-1处具有明显的聚酰胺的特征吸收.:己内酰胺;聚己内酰胺;水解聚合;低聚物:O633.22+1　　　　　:A0　Schlack1938〔1〕,6-,、,.,,.:〔2〕、〔3-9〕、〔10〕.,200℃,.———(6、6、6)、、、、、,,,.,〔11〕.,.,,,,.1　1.1　主要原料及仪器,,;,,;,,;,,.WATERS2414,;VECTOR-22,.1.2　己内酰胺低聚物的合成,,,＊:2006-12-19:(1980-),,,,:2:,,170℃,,,,.1.3　产物的分离〔12〕,.,.,.1.4　转化率的计算:V=M2M1×100%.　　,V———;M1———(g);M2———(g).1.5　产物的表征5%,;48h,.1　MnMwMPMzMz+1140914311459145214741.0155006596656696706761.0082024614664774714761.0106832372422452472521.020356　(Mn:,Mw:,Mp:,Mz:Z,Mz+1∶Z+1)2　2.1　对检测结果的分析2.1.1　11.,:1409237,1.0155001.020356,140910,、,.2.1.2　2.2939.91cm-1、1551.69cm-1Ⅱ,1635.11cm-1Ⅰ,2939.91cm-1N-H,1551.69cm-1N-H,1635.11cm-1C=O,.图1　聚己内酰胺的液相凝胶色谱图　　　　　图2　聚己内酰胺的红外光谱2.2　影响己内酰胺转化率的因素2.2.1　170℃,200g、2g、4.5g,,2.2,,.·21·25,.,,,.,,,,.:m(C6H11NO)∶m(H2O)=100∶1.2　/g/%1.5h2.0h2.5h3.0h3.5h0.816242833331.223323943431.639515660602.055677378782.453647174743　/℃/%1.5h2.0h2.5h3.0h3.5h155151823343416028333745451654557626666170626774808018061657173734　/g/%1.5h2.0h2.5h3.0h3.5h3.056637073733.556637275754.057647378784.562677480805.057617479795　/g/%1.5h2.0h2.5h3.0h3.5h0.123303235411.536425055622.062677480802.575808180803.07780808080,,,3h.,,,,,.2.2.2　200g、2g、2g、4.5g,,3.3,,,,,.,,.,,.170℃.2.2.3　170℃,200g、2g、2g,,4.4,,.,.,,.:m(C6H11NO)∶m(C6H2O4)=100∶2.25.2.2.4　170℃,200g、2g、4.5g,,5.5,,,,,.:m(C6H11NO)∶m(H2SO4)=100∶1.3　:,170℃,3.0h,、、:m(C6H11NO)∶m(H2O)∶m(C6H2O4)∶m(H2SO4)=100∶1∶2.25∶1.,·22·2:80%.GPC,1409237.[1]　.〔D〕.:,2002.[2]W·,R·J·H·.ε--6〔P〕.CN:2002-01-16.[3]A.Demicheli,S.Russo,A.Marianib.Synthesisandcharacterizationofε-caprolactam-L-phenylalaninecopolymers〔J〕.Polymer,2000,41:1481-1486.[4]LauraRicco,OriettaMonticelli,SaverioRusso,etal.Fast-ActivatedAnionicPolymerizationofε-caprolactaminsuspension.Mac-romol〔J〕.Chem.Phys,2002,203:1436-1444.[5]R.Mateva,P.Petrov,S.Rousseva,etal.Onthestructureofpoly-ε-caprolactams,obtainedwithbifunctionalN-carbamylderiv-ativesoflactams〔J〕.EuropeanPolymerJournal,2000,36:813-821.[6]LauraRicco,SaverioRusso,etal.Caprolactam-laurolactamcopolymers:fastactivatedanionicsynthesis,thermalpropertiesandstructuralinvestigations〔J〕.Macromol.Chem.Phys.,2001,202:2114-2121.[7]LauraRicco,SaverioRusso,OriettaMonticelli,etal.ε-Caprolactampolymerizationinpresenceofpolyhedraloligomericsilsesqui-oxanes(POSS)〔J〕.Polymer,2005,46:6810-6819.[8]DanielCrespy,KatharinaLandfester.Anionicpolymerizationofε-caprolactaminminiemulsion:synthesisandcharacterizationofpolyamide-6nanoparticles.Macromolecules〔J〕.2005,38:6882-6887.[9]JanaMarelova,JanRodaa,JaroslavStehlicek.Anionicpolymerizationofε-caprolactaminthepresenceofsymmetricallysubstitutedureas〔J〕.EuropeanPolymerJournal,1999,35:145-155.[10].20000/〔D〕.:,2001.[11]GeraldM.Brooke,S.Mohammed,MarkC.Whiting.Thesynthesisofoligomersrelatedtonylon46andnylon66〔J〕.Polymer,1999,40:773-788.[12]Achhammer,Gunther,Fuchs,etal.Preparationofcaprolactam〔P〕.US:5495016,1996-02-27.THESYNTHESISOFCAPROLACTAMOLIGOMERATTHELOWTEMPERATUREGEZhu-li,WANGHong-ru(SchoolofResourcesandEnvironment,ShaanxiUniversityofScience&Technology,Xi′an　710021,China)Abstract:Thestudydealswiththesynthesisofcaprolactamoligomerobtainedwithcaprolac-tambyhydrolytricpolymerizationinthepresenceofsulfuricacidasactivator,waterasevo-catorandnitrogenasprotectivegasatthelowtemperature.Theproductwaspurifiedbyn-Butylalcoholanddistilledwater.ThecaprolactamoligomerswerestudiedbyGPCandIR.Anditstudiedthepolymerizationconditionsthatinfluencedthetranslationalratioofcapro-lactamsuchasevocator,temperature,regulatorofthemolecularweightandtime.There-sultshowsthattheoptimumconditionsarenitrogenasprotectivegas,reactiontemperatureat170℃,reactiontimefor3h,themolarproportionofcaprolactam,water,adipicacidandsulfuricacidism(C6H11NO)∶m(H2O)∶m(C6H2O4)∶m(H2SO4)=100∶1∶2.25∶1.Atthiscondition,thetranslationalratioofcaprolactamis80%.TheresultofGPCdisplaysthatthepolymerscontaintwoprimarypartsthattheirNumber-averageMolecularWeightsare1409and237.Theinfraredspectrumhasdistinctdiagnosticbandsofpolyamidelactamat2939.91cm-1,1635.11cm-1and1551.69cm-1.Keywords:caprolactam;polycaprolactam;hydrolytricpolymerization;oligomer·23·