Online Monitoring of the Final, Divergent Growth Phase in the Step-Growth Polymerization of Polyamin
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Usingautomatic,continuousonlinemonitoringofpolymerizationreactions(ACOMP)thefinal,divergentgrowthphase(FDGP)ofthecondensationpolymerizationofdimethylamine,epichlorohydrin,andethylenediaminewasmonitored,whichproducedahighlyramified,polyelectrolyticpolyamine.Theweightaveragemass,Mw,increasedexponentiallyduringtheFDGP,whereasweightaveragedintrinsicviscosity[è]wincreasedslowly,reachingaplateau.Multi-detectorgelpermeationchromatography(GPC)revealedthatpolymersofmass20000to106arebranchedandself-similar,butabovethismass,[è]increaseslessstronglywithM.Thisappearstobeduetohigherorderramification,aprecursortogelation.TheACOMPtrendsinMwand[è]wprovidedirectonlineevidenceofthisprocess.Itisshowncomputationallythatamereincreaseinpolydispersitycannotexplainthisbehavior.GPCshowedthemassdistributionbecomeshighlyasymmetricasconversionincreases.Aplausiblekineticmodelforthedistributionasymmetryisintroduced,andacomplementarymodelfortheeffectsofhigherorderramificationon[è]w.
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