Gel formation in atom transfer radical polymerization of 2-(N,N-dimethylamino)ethyl methacrylate and ethylene glycol dimethacrylate

Copolymers of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) and ethylene glycol dimethacrylate (EGDMA) were synthesized via atom transfer radical p olymerization using ethyl 2-bromoisobutyrate as the initiator, Cu(I)Br as t he catalyst, and 1,1,4,7,10,10-hexamethyltriethylene tetramine as the ligan d. At low crosslinker levels, the polymerizations followed the first-order kinetics. However, when the crosslinker level was above 10 mol %, the ln([M ](0)/[M]) versus time curves showed deceleration at medium conversions beca use of the higher reactivity of EGDMA than that of DMAEMA. An acceleration at high conversions was also observed and probably caused by the diffusion limitations of catalyst/ligand complex in the polymer network. The hydrogel s were characterized by swelling experiments, and the Sol polymers were cha racterized by the size exclusion chromatographic technique to determine the number-average molecular weight and polydispersity. The gel data were anal yzed and, via a comparison to Flory's gelation theory, found to be more hom ogeneous than similar hydrogels prepared by conventional free-radical polym erization methods. (C) 2001 John Wiley & Sons, Inc.