甲基丙烯酸n,n-二烷基氨基乙酯的自引发催化氧化聚合机理分析-mechanism analysis of self-initiated catalytic oxidation polymerization of n, n - dialkylaminoethyl methacrylate.docxVIP

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甲基丙烯酸n,n-二烷基氨基乙酯的自引发催化氧化聚合机理分析-mechanism analysis of self-initiated catalytic oxidation polymerization of n, n - dialkylaminoethyl methacrylate.docx

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甲基丙烯酸n,n-二烷基氨基乙酯的自引发催化氧化聚合机理分析-mechanism analysis of self-initiated catalytic oxidation polymerization of n, n - dialkylaminoethyl methacrylate

关键词：甲基丙烯酸N，N-二甲氨基乙酯；甲基丙烯酸N，N-二乙氨基乙酯；自身还原性引发型单体；催化氧化聚合；氧化还原引发ABSTRACTAsanintrinsicallyreducingmonomer,(N,N-dialkylamino)ethylmethacrylatewasreportedtobeinvolvedinredoxinitiationinthepresenceofproperoxidizingagents.First,Self-initiatedoxidativeradicalpolymerizationofDMAEMAcatalyzedwithCuCl2/PMDETAwereperformedinthepreaenceofO2.ThemonomerconversionwasdeterminedbyGC.TheMW,chainstructureandthermaltransitionwerecharacterizedbyGPC,1H-NMRspectroscopyandDSC,respectively.The1H-NMRspectroscopyimpliedthattheODMAEMAcontainedbothamethacryloylCH2=andaC-Clterminus.TheCuCl/PMDETA-catalyzedATRPofMMAusingtheso-obtainedODMAEMAasthemacroinitiatorwascarriedout.Theresultsshowedthattheprocessproceeded.The1H-NMRspectrashowedthattherelativeintensityofthe-N-CH3moietyto-OCH2-decreasedremarkably,suggestingthatMMAwasalsograft-copolymerizedtoODMAEMA,whichconfirmedthattheN-CH3moietyofDMAEMAwasoxidizedintotheN-CH2·radicalbyCuCl2，andthatATRPmechanismpartiallyresultedintheprocess.Then,oxidativepolymerizationsofDEAEMAasanintrinsicallyreducingmonomercatalyzedbyhigh-oxidationstatetransitionmetals(CuX2/L,FeX3/L,X=ClorBr,L=bPy,TMEDA,PMDETA,CuSO4)weresystematicallyinvestigated.Theresultsshowedthatevenintheabsenceofanychemicalinitiators,thehigh-oxidationstatetransitionmetalscansteadilycatalyzethefreeradicalpolymerizationofDEAEMA.TheMWofthePDEAMEAincreasedgraduallywiththeconversion,whileitmaintainedaratherbroadPDIevenfromlowconversions.TheMALLSresultsshowedthattheabsoluteMWofthePDEAEMAdemonstratedanunusualmulti-modaldistribution.BycomparingtheCuSO4-catalyzedredox-initiationabilityoflower-MWtertiaryamines,itcanbeconclucedthatDEAEMAfunctionsasanintrinsicallyreducingmonomerunderthecatalysisofhigh-oxidationstatetransitionmetals,whichoxidizethealphaC-H(Cα-H)oftheaminegroupofDEAEMAintotheCα·radicals,initiatingtheconventionalradicalpolymerizationofDEAEMAandgivingrisetolinearPDEAEMAprimarychains.Subsequently,thelinearPDEAEMAchainsserveasmacro-initiatorswithhigh-oxidationstatetransitionmetalsandinitiatethegraftpolyme