淀粉和丙烯酰胺的辐照接枝共聚反应研究杨波

　176Vol.17,No.6　200111POLYMERMATERIALSSCIENCEANDENGINEERINGNov.2001杨　波,赵榆林,刘　烨(,650224):研究淀粉与丙烯酰胺在60CoV射线引发下的接枝共聚反应规律和反应机理,由实验结果得出了辐照时间与接枝聚合率的关系,辐照剂量率、单体浓度、淀粉浓度和辐照温度对接枝共聚反应速率的影响,并由此关联出接枝反应速率表达式:Rp=k[I]1/2[AM][AGU]1/2。对接枝共聚反应机理进行了初步探讨,推导的接枝共聚反应速率理论式与实验式—致。:;;;:TQ316.343　　　:A　　　:1000-7555(2001)06-0064-03　　,,、、、,[1]。,,。2060,Reyes[2,3]。Varma[4]60CoV-。,,[5]。-,,。1　1.1　:,;:,;。:7.4×1015Bq60Co,,G3+Fe=15.6。1.2　1.2.1　辐照接枝共聚:,,,,,,,。,,,,,,。1.2.2　除去未参加反应的淀粉和单体:,,,,。1.2.3　分离均聚物:Varma[4],1.0000g,。60∶40()-3h,,。1.3　1.3.1　丙烯酰胺接枝聚合率的测定:,:2000-09-05　:(169942015)　:　,,31,,.DOI:10.16865/j.cnki.1000-7555.2001.06.015(A):A(%)=-×100%1.3.2　接枝共聚反应速率的测定:(Rp(mol/minL))[6]。Rp=××2　2.1　Fig.1。S,,。3:①,,;②,,;②,,。Fig.1　RelationshipbetweentandAFig.2　Effectof[I]onRp2.2　(0.3～3)Gy/min,RpFig.2,。2.4Gy/min.Rp[I]1/2;2.4Gy/min,,,;,,,。2.3　Fig.3,。,,。[9],,。,。Fig.3　RelationshipofRpbetween[AM]Fig.4　RelationshipbetweenRpand[AGU]2.4　,Fig.4。,(),。(),。,、。,(),:Rp=k[I]1/2[AM][AGU]1/22.5　:200mim,1.2Gy/min,[AM]=1.0mol/L,[AGU]65　6　:=0.05mol/L。Tab.1。Tab.1　TheinfluenceofTonRpandAT(℃)Rp×103(mol/Lmin)A(%)04.4488.754.8795.5104.7595.0204.8396.5304.8096.0404.8296.5　　Tab.1,5～40℃,0℃,。()[7]:lgRp=lgk-(E/2.303R)(1/T),(E),。[7]:E=(1/2)Ei+Ep-(1/2)EtEi;Ep;Et。Ei,[7]。,E=Ep-0.5Et,Ep0.5Et,E。,Et,E,。2.6　,,Odian[8],:(a)　Cell-HhνCell·(b)　Cell·+MhνCell-M·c)　Cell-M·+MkpCell-M2·MMMn·(d)　Cell-Mn·+Cell-Mm·ktCell-Mn-Mm-Cell,Odian[8]:Ri=GIP/100NG100eV;I;P;N。,,,:Rp=-(d[M]/dt)p=kp[M]΢[Cell-Mi·]=kp[M][Cell-M·],:Rt=-d[M·]/dt=kt[Cell-M·]:d[p·]/dt=Ri-Rt=0[M·]=(Rikt)1/2=(GIP100Nkt)1/2:Rp=(k2pkt)1/2(G100N)1/2[I]1/2[M][P]1/2,1,0.5。。[1]　(DINGYing-jun).(PolymerBul-letin),1993,13(9):140～145.[2]　ReyesZ,etal.J.Polym.Sci.,1969,4:1031.[3]　ReyesZ,etal.Nucl.Apple.,1969,6:509.[4]　VarmaIK,etal.Angew.Makromol.Chemic.,1983,119:183～192.[5]　(DENGHai),.(JournalofRadiationResearchandRadiativeProcessing),1998,16(5):65～69.[6]　(GAOJian-ping),.(PolymerMaterialsScience&Engineering),2000,16(1):63～66.[7]　(HUANGGuang-lin).(RadiationChemistryofPolymers).(SichuanUniversityPress),1993:272～274.[8]　OdianG,SobelM,RossiA,etal.J.Appl.Polym.Sci.,1961,55:663.[9]　BhattacharyyaSN,MaidasD.Prog.Polym.Sci.,1984,10:171～172.(70。tobecontinuedonP.70)662001　[4]　KazimieraSG.Eur.Polym.J.,1989,25(12):1291～1295.STUDIESONTHESYNTHESISANDPROPERTIESOFSTYRENE-METHYLACRYLICACIDCOPOLYMERYANGWei,LIGuang-ji,WANGZhi,SUNLu-yi,SHENJia-rui(StateKeyLaboratoryofPolymerMaterialEngineering,Chengdu610065,China;CollegeofMaterialsScienceandEngineering,SouthChinaUniversityofTechnology,Guangzhou510641,China)ABSTRACT:Styrene-methylacrylicacidcopolymers(PSMAA)weresynthesizedbyasuspensioncopolymerizationwiththedifferentmolecularweightandthecontentofmethylacrylicacid.ThemechanicalandtheprocessingpropertiesofPSM(AAcopolymerswerestudiedbytensiletester,impacttestingmachineandtorquerheometer.Theresultsshowthat:(1)boththeglasstran-sitiontemperatureandthethermalstabilityincreasewiththeincreaseofMAAcontentinPSMAAcopolymer.(2)thetensileandimpactstrengthenhancewiththeincreaseofeithertheMAAcontentorthemolecularweight.(3)TheprocessingpropertiesofPSMAAcopolymersarebetter,eithermolecularweight(M-n)isinrangeof1×105andMAAcontentis18mol%or2×105molecularweightand8mol%MAAcontent.Keywords:styrene-methylacrylicacidcopolymer;suspensionpolymerization;mechanicalproperty;processingproperty(66。continuedfromp.66)STUDYONRADIATIVEGRAFTCOPOLYMERIZATIONOFSTARCH/PAMYANGBo,ZHAOYu-lin,LIUYe(CollegeofBiologyandChemicalEngineering,KunmingUniversityofTechnology,Kunming650224,China)ABSTRACT:Themechanismofstarch/acrylamidegraftcopolymerizationofVraysfromacobalt60(60Co)sourceasinitiatorwasstudied.Theeffectofradiativetimewithpolymerandtherelationshipsbe-tweengraftingrateandradiationdoserate,monomerconcentration,radiativetemperatureandstarchconcentrationwereobtained,basedonwhichtheequationforthegraftcopolymerizationwasderived:Rp=k[I]1/2[AM][AGU]1/2.Ontheotherhand,thereactioncoursewasinvestigated.Theseresultsshowthattheequationbytheoryforthegraftcopolymerizationissamewiththatbyexperiment.Keywords:graft-copolymerization;radiation;acrylamide;starch702001