Fe2H2O2引发淀粉省略甲基二烯丙基氯化铵接枝共聚的研究陈卓

　184Vol.18,No.4　20027POLYMERMATERIALSSCIENCEANDENGINEERINGJul.2002Fe2+-H2O2-陈　卓(,550001)范　宏,洪　涤(,,310027):采用Fe2+-H2O2氧化还原引发体系进行淀粉与二甲基二烯丙基氯化铵(DMDAAC)接枝聚合,制备了一系列分子中含有阳离子季铵基团的淀粉-DMDAAC接枝共聚物。研究了单体浓度、引发剂用量、反应温度对接枝体系的接枝率、接枝效率、单体转化率和阳离子度等因素的影响,探讨了Fe2+-H2O2引发淀粉接枝DMDAAC共聚反应的基本规律。并用IR和1H-NMR对接枝共聚物进行了分析表征。:Fe2+-H2O2;;;:TQ316.343　　　:A　　　:1000-7555(2002)04-0081-04　　(DMDAAC)—,,[1,2]、[3]、[4][5],。,DMDAAC、,。,DMDAAC,,。Fe2+-H2O2,(DMDAAC),,。1　1.1　(St):;(DMDAAC):,60%;、、(30%)A.R.。1.2　/DMDAAC、、,,N2,,90℃～95℃30min,,,,4h。,、,50℃,。1.3　,50∶50()-50℃,,。1.4　1.4.1　接枝率(G)、接枝效率(E)和单体转化率(C)的测定:[6]:　　　　G=(W1/W0)×100%　　　　E=[W1/(W1+W2)]×100%　　　　C=[(W1+W2)/W]×100%:W1——;W2——;W0——;W——。:2000-09-25　:　,,27,.　:　.DOI:10.16865/j.cnki.1000-7555.2002.04.0201.4.2　阳离子度(DC)的测定:[7]Cl-,:DC=161.5×0.05×(V-V0)1000W×100%:V——AgNO3mL;V0——AgNO3mL;W——;161.5——;0.05——AgNO3。1.5　,,PE-683。D2O,AC-80。2　2.1　2.1.1　引发剂用量对接枝共聚反应的影响:Fe2+-H2O2,Fe2+H2O2HO·,HO·,。,,H2O2,Fe2+,。,,Tab.1。Tab.1　EffectofascorbicacidongraftcopolymerizationAscorbicacid(g)G(%)E(%)C(%)DC(%)045.563.148.134.40.264.373.857.937.6Fig.1　EffectofH2O2addedamountonG(curve1),E(curve2),C(curve3)andDC(curve4),H2O2(),Fe2+1.05×10-3mol/L,9.38×10-3mol/L,DMDAAC/St=1.5/1(),40℃H2O2。Fig.1。Fig.1,H2O2,G、EC,0.4mL,。H2O2,H2O2Fe2+HO·,,,,G、E、C。H2O20.4mL,。H2O2,(HO·),①DMDAAC;②PDMDAAC,;③H2O2HO·。H2O2,G、EC。Cl-,DMDAAC。Fig.1,DC,,DC。。Fig.2　EffectofreactiontemperatureonG(curve1),E(curve2),C(curve3)andDC(curve4)2.1.2　反应温度对接枝共聚反应的影响:,,G、E、CDC,Fig.2。Fig.2,40℃,。40℃,822002　(),,G,,,,G。,,,,C。,DMDAAC,,,,,DMDAAC,E。,40℃,,DC。Fig.3　EffectofmonomerconcentrationonGFig.4　EffectofmonomerconcentrationonE(curve1),C(curve2)andDC(curve3)2.1.3　单体浓度对接枝共聚反应的影响:,Fig.3,,,,;(Fig.4)。,,。,,,,,E,,,E。,,,。,/,,,。Fig.4,,;。Fig.5　IRspectrumofPDMDAAC(curve1)andSt-g-DMDAAC(curve2)Fig.6　1H-NMRspectrumofSt-g-DMDAAC2.2　St-g-DMDAACPDMDAACIRFig.5,Fig.5,3300cm-1、2930cm-11474cm-1PDMDAAC,,1025cm-1～1152cm-1(C-O)930cm-1、760cm-1576cm-1,DMDAAC。Fig.61H-NMR,W=3.23W=3.83DMDAACN+-CH3-CH2-,W=83　4　:Fe2+-H2O2-1.46DMDAAC-CH2-,PDMDAAC1H-NMR;W=2.06-CH2-,DMDAAC。[1]　.(),1990,9:58.[2]　LettermanRD,etal.J.AWWA.,1990,11:87.[3]　EP0251558A2.[4]　U.S.4217425.[5]　U.S.3912808.[6]　(YANRei-xuan).(WaterSolublePolymer).(ChemicalIndustryPress),1998:363.[7]　(XUMian-yi),(FANGGuo-chun),(PANZhu-ting),.(WujiJiFenxiHuaxueShiyan).(WuhanU-niversityPress),1991:84～186.[8]　(GEXue-wu),(XUXiang-lin),(ZHANGZhi-cheng),.(PolymerMaterialsScience&Engineering),1999,15(4):132.GRAFTCOPOLYMERIZATIONOFDIMETHYLDIALLYLAMMONIUMCHLORIDEONTOSTARCHUSINGFe2+-H2O2INITIATORCHENZhuo(ChemistryDepartment,GuizhouNormalUniversity,Guiyang550001,China)FANHong,HOHGDi(InstituteofPolymerEngineering,theStateKeyLaboratoryofPolymerizationReactionEngineering,ZhejiangUniversity,Hongzhou310027,China)ABSTRACT:UsingFe2+-H2O2initiationsystem,aseriesofcationicstarch-DMDAACgraftcopolymerwhichcontainingquaternaryammoniumgroups,werepreparedbythegraftpolymer-izationofDMDAAContosolublestarchinwatermediumunderdifferentcondition.Effectsofvariousfactorssuchasmonomerconcentration,theinitiatoraddedamountandreactiontempera-tureonthepercentageofgrafting,thegraftingefficiency,cationicdegreeandthemonomercon-versionetc.werestudied.ThemechanismofgraftingpolymerizationonstarchinFe2+-H2O2initi-ationsystemwasalsodiscussed.ThegraftcopolymerswerecharacterizedandwereanalyzedbyIRand1H-NMR.Keywords:Fe2+-H2O2initiator;starch;dimethyldiallylammoniumchloride;graftcopolymeriza-tion842002