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205Vol.20,No.5 20049POLYMERMATERIALSSCIENCEANDENGINEERINGSept.2004-杨锦宗1,曹亚峰1,2,刘兆丽2,马希晨2(1.,,126012;2.,116034):以淀粉为基材、丙烯酰胺(AM)、丙烯酸(AC)为聚合单体,采用氧化还原引发体系,通过反相乳液聚合技术,合成接枝聚合物。以非离子表面活性剂为乳化剂,讨论了合成工艺条件对产品性能的影响。结果表明,m[(NH4)2S2O3]∶m[(NH2)2CO]=2.5∶1.8为引发体系,m(Span20)∶m(OP4)=40∶60为乳化剂,m(淀粉)∶m(单体)=1∶1.5时,接枝率可达148%,特性粘数可达1520mL/g。:;;;;;:TQ316.343 :A :1000-7555(2004)05-0089-04 ,,。、、,、、、、、、、、、[1,2]。。,。、,,()/(),。,。、、、、。,,,,,,[3]。,,,[4]。,[5]。,,(AM)、(AC),、、。1 :,;:,;:,;。,,,,,,。,,40℃～60℃,。6∶4、:2002-11-07 :(1932-),,,,,. :.DOI:10.16865/j.cnki.1000-7555.2004.05.022,(T)、(G):T=(W1-W0)/WnG=(W2-W0)/W0:W0——(g);Wn——(g);W1——(g);W2——(g)。[Z]:Zsp,,[Z]。(HC):,,,:HC=61×0.05×(V0-V)/1000W:V——(mL);V0——(mL):W——25mL(g);61——;0.05——(mol/L)。Fig.1a Effectofinitiationsystemsongraftingratiot=45℃;t=5h;1:t-butylperoxypivalate;2:(NH4)2S2O8-(NH2)2COFig.1b Effectofinitiationsystemsonspecificviscidityt=45℃;t=5h;1:t-butylperoxypivalate;2:(NH4)2S2O8-(NH2)2CO2 2.1 -(1∶1)、,,Fig.1a、Fig.1b。,AM、AC,(NH4)2S2O8-(NH2)2CO,,,,2.5×10-4mol/L,。2.2 AM、AC,(),()。Span、Tween、OP,(NH4)2S2O8-(NH2)2CO,C(I)=2.5×10-4mol/L,w(E)=6%,、,Fig.2a、Fig.2b。Fig.2,,,,Fig.2a Effectofdifferentemulsifiersonmonomercon-version□:Span20;●:Span60;▲:Tween20;:Tween81;◇:OP4;+:OP10.Fig.2b Effectofdifferentemulsifiersongraftingratio□:Span20;●:Span60;▲:Tween20;:Tween81;◇:OP4;+:OP10.902004 Fig.2c Effectofemulsifierproportionongraftingratiot=45℃;t=5h;□:Span20-Span60;●:Span20-Tween20;▲:Span20-Tween61;:Span20-OP4;◇:Span20-OP10.Fig.3 Effectoftemperatureongraftingratiow(E)=6%;t=5h;■:m(Span20)m(Tween20)=64;●:m(Span20)m(Tween81)=46;▲:m(Span20)m(OP4)=46;:m(Span20)m(OP10)=64.,、,,、。,,,,Span20、Span60、OP4,、,Tween20、OP10。,6%,AM、AC,,Fig.2c。,。OP10、Tween20Span2040∶60,Tween61、OP4Span2060∶40。OP4Span2060∶40,147%。,,-OH、-CO-O-,,,,,,,。2.3 ,,Fig.3。Fig.3,OP10、Tween20Span20,55℃,OP10、Tween20(CH3CH2O),,,,。Tween81、OP4Span2045℃,,。Fig.4 EffectofacrylicacidconcentrationongraftingratioandspecficviscidityC[(NH4)2S2O8]=2.5×10-4mol/L;C(H2NCONH2)=1.8×10-4mol/L;t=45℃;t=5h.2.4 (HC)[Z]Fig.4。Fig.4,HC[Z],AC,[Z]AC,AC10%,[Z]AC。,,。91 5:-Fig.5 EffectofpHongraftingratioandspecficviscidi-tyC[(NH4)2S2O8]=2.5×10-4mol/L;C(H2NCONH2)=1.8×10-4mol/L;t=45℃;t=5h.2.5 pH,pH,Fig.5。pH4,-COOH,pH,-COO-,pH7,,,,,,。3 (1)(NH4)2S2O8-(NH2)2CO,Span、Tween、OP,AM、AC,SpanTween,OP。,。(2)AM、AC,Span20∶OP4=40∶60,。6%,148%,1520mL/g。:[1] KerrRW.ChemistryandIndustryofStarch.NewYork:AcademicPress,1950:325～328.[2] LindstromT,SoermarkCJ.Colloid&InterfaceSci.,1976,55(2):305.[3] (GAOShu-tang),(SHUShu-lin),(YANGJing-chun),.(Polomer-ImprovedOilRecovery).(OilIndustryPress),1996:29.[4] PanlZ,VictorBT.USP4010131(1997).[5] DimonieMV,BoghianCM.Eur.Polym.J.,1982,18(7):639.GRAFTCOPOLYMERIZATIONONTOSTARCHWITHAM-ACININVERSEEMULSIONYANGJin-zong1,CAOYa-feng1,2,LIUZhao-li2,MAXi-chen2(1.TheStateKeyofLab.FineChem.,DalianUniv.ofTechnol.,Dalian116012,China2.Dept.ofChem.Eng.,DalianInst.ofLightInd.,Dalian116034,China)ABSTRACT:Agraftcopolymerwassynthesizedbygraftcopolymerizationofstarchwithacry-lamide(AM)andacrylicacid(AC).Thegraftcopolymerizationwascarriedoutusingredoxinitia-torininverseemulsioninthesystemsofSpan,Tween,OPandtheirmixturerespectivelyasemulsifirs.Thisarticlediscussedtheeffectofinitiationsystemandemulsifyingkindandgraftcopolymerizationtemperatureandmonomerproportiononmonomerconversionandgraftcopoly-merizationandspecificviscidity.ResultshowsthatthemixtureofSpan20andOP4asemulsi-fiers,whenconcentrationofmixtureemulisifieris6%,themixtureof(NH4)2S2O8and(NH2)2COasinitiator,massratioofstarch∶monomerwas1∶1.5,thegraftingratiois148%andspecificviscidityis1520mL/g.Keywords:starch;acrylamide;acrylicacid;graftcopolymerization;inverseemulsion;non-ionicemulsifier922004