新型有机纤维素溶剂_NMMO的研究

:100025889(2005)0220073204NMMO1,2,1,3,2(1.,712081;2.,730050;3.,510300):NMMO,.,,,,.:;;N22N2(NMMO):TQ35:AStudyofneworganiccellulosesolvent:N2methylmorpholine2N2oxide(NMMO)WUCui2ling1,2,LIXin2ping1,QINSheng2li3,WANGJian2yong2(1.ShanxiProvinceKeyLaboratoryofPapermakingTechnologyandSpecialtyPaper,ShanxiUniversityofScience&Technology,Xianyang712081,China;2.CollegeofMechano2ElectronicEngineering,LanzhouUniv.ofTech.,Lanzhou730050,China;3.GuangdongIndustryTechnicalCollege,Guangzhou510300,China)Abstract:Thedevelopinghistory,structuralcharacteristicsandgeneralpropertiesofN2methylmorpho2line2N2oxide(NMMO)wereintroduced.Itsdissolutionmechanismandprocesstechnologywerealsoana2lyzed.Asacellulosesolvent,NMMOshowedseveraladvantagessuchassimpleprocessingmethod,noenvi2ronmentpollution,recycledsolvent,andpurephysicaldissolvingprocess,beingagoodsolventofcellulose.Keywords:cellulose;solvent;N2methylmorpholine2N2oxide(NMMO)10001500t[1],,D2()21,4,,.;,,.,,,,.2060,:2004206223:(2003C103016),(0210),2001:(19672),,,,.,N22N2(NMMO).,NMMO.NMMO,.Lyocell,[2].1NMMO19361939GranacherSALLMANN.30,JOHNSON.2080,Enka(AEC)Akzo(ARLO)31220054JournalofLanzhouUniversityofTechnologyVol.31No.2Apr.2005©1994-2007ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[3]Lyocell.,N22N2(NMMO).CourtauldsLenzingTITKAkzoNobel.,,,NMMO,(BISFA)Lyocell.Lyocell,,NMMO.2NMMO[1]2.1NMMON22N2(NMMO).(),,.,,(1).1(R=)Fig.1Differenttypesofamineoxides(R=alkyl),sp3,.NMMONO,4.38mD[4],,NO.NMMO,(N,),(),,(2).,N22N2,NMMNOMMNONMO,,NMMO,IUPAC().2NMMO3Fig.2ThreepossiblemolecularformulationofN2methyl2morpholine2N2oxide2.2NMMONO,NMMO,,,.NO,.222kJ/mol[1],NMMO3:1)NMMO,,NO;2)NMMO,;3)NMMON2(NMM)(M)[5,6],.NO()NONMMO.2.3NMMONMMO2:NMMOH2O(13.3%)NMMO2.5H2O(28%).2NMMO,.NMMOH2ONMMO2.5H2ONMMO,NMMO[7,8]NMMO.NMMOH2ONMMO2.5H2ONMMO,NMMO1[9].2.4NMMONMMO,[10],NMMODegussaBASFAGTexaco.NMMO40%50%,4731©1994-2007ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(gmol-1)117.1135.2324.4/(gcm-3)1.251.281.33,,,,tP/184767839,PZ1/m,PZ1/c,PZ1/cabc/nm398.8666.2151.1225.4860.491.86128.0365219.13/()110.5499.88109.99()CAS75292222870187232258091326521,NMMO.3NMMO3.1NMMONMMO[11],,.NMMONO12(),NMMOH2O[12],(CellOH)CellOHON,-NMMO.,,NMMO,,,.3.3NMMOFig.3MechanismofNMMOdissolvingcelluloseNMMO,NMMO,NMMO2.5H2O.NMMO2.5H2O,,[1].ROMANOVVV,NMMO,(184),NMMO,.17%,13.3%(NMMOH2O),76.3.22[13]:1).NMMO50%,.,13%.13%,NMMO.2).,..,NMMO50%60%,20%30%,10%15%;,NMMO76%,10%,14%.2.2NMMOTab.2InfluencingfactorsofdissolutionofcelluloseinNMMO/water72120,21%,,.,,.,,.572:NMMO©1994-2007ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(Fe3+),[14].,,,,NMMO,,N2.,,.NMMO,.[15].[16],.4NMMO/NMMO[11].NMMO,.85120,,,,NMMO/H2O,.,NMMO,;,;NMMO,,99.5%99.7%,.,.521,.NMMO,,,,,,.NMMO.:[1]THOMASR,ANTJEP,HERBERTS,etal.ThechemistryofsidereactionsandbyproductformationinthesystemNMMO/cellulose(lyocellprocess)[J].ProgressinPolymerScience,2001,26:176321837.[2],,.NMMO[J].,2000,15(3):25227.[3]CHANZYH,NAWROTS,PEGUYA,etal.Thephasebe2haviorofthequasitemarysystemN2methylmorpholine2N2ox2ide,waterandcellulose[J].PolymSci,1982,20:190921924.[4]LINTONEP.Thedipolemomentofamineoxides[J].AmChemSoc,1940,62:194521948.[5]DAVISMM,HETZERHB.Therelativebasicitiesoftrialkyl2amineandtrialkylamineoxideinbenzeneandwater[J].AmChemSoc,1954,76:424724260.[6]KRUGERTL,WHITEWN,WHITEH,etal.PreparationandbasicitiesofN,N2diethylandN,N2dimethylanilineoxides[J].OrgChem,1975,40:77281.[7]KosterR,MORITAY.QuantitativebestimmungverschiedenerB2funktioneninorganischenborverbindungendurchoxydationmittrimethylamin2N2oxyd[J].LiebigsAnnChem,1967(704):70290.[8]SONDERQUISTJA,ANDERSONCL.CrystallineanhydroustrimethylamineN2oxide[J].TetrahedronLett,1986,27:396123962.[9]MAIAE,PEGUYA,PEREZS.Celluloseorganicsolvents():ThestructureofanhydrousN2methylmorpholine2N2ox2ideandN2methylmorpholine2N2oxidemonohydrate[J].ActaCrystB,1981,37:185821862.[10].Tencel[J].,1998,15(2):127.[11],,,.NMMO[J].,2000(4):124.[12]CHANZYH,MAIAE,PEREZS.Celluloseorganicsolvents():ThestructureofN2methylmorpholine2N2oxide2trans21,22cyclohexanediolcomplex[J].ActaCrystB,1982,38:8522855.[13],,,./NMMO[J].,2001,27(5):1272131.[14]BUIJTENHUIJSFA,ABBASM,WITTEVEENAJ.ThedegradationandstabilizationofcellulosedissolvedinN2me2thylmorpholin2N2oxide(NMMO)[J].Papier,1986,40(12):6152619.[15]KALT,WOLFRAM,MANNER,etal.Mouldingmaterialsandspinningmaterialcontainingcellulose[P].USA:5556452,1996209217.[16]DUCHARMEJr,PAULEDMUND.Methodofmakingacel2lulosefoodcasingincludingsolventrecovery[P].USA:5942167,1999208224.6731©1994-2007ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.