|194. Mori, H.; Walther, A.; André, X.; Lanzendörfer, M.; Müller, A.H.E.: Synthesis of Highly Branched Cationic Polyelectrolytes via Self-Condensing Atom Transfer Radical Copolymerization with 2-(Diethylamino)ethyl Methacrylate, Macromolecules 37, 2054 (2004)|
Randomly branched (arborescent) cationic polyelectrolytes were synthesized by self-condensing vinyl copolymerization (SCVCP) of a methacrylic AB* inimer, 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM), with (diethylamino)ethyl methacrylate (DEAEMA) via atom transfer radical polymerization (ATRP), followed by quaternization. Homopolymerization of DEAEMA with the CuBr/hexamethyltriethylenetetramine (HMTETA) catalyst system gave a linear polymer having controlled molecular weights and narrow molecular weight distribution, which were evaluated by conventional GPC, GPC-viscosity, and MALDI-TOF mass spectrometry. The catalyst system could be applied to self-condensing vinyl polymerization (homo-SCVP) of BIEM in bulk and in solution to provide hyperbranched architectures, as confirmed by 1H and 13C NMR and GPC-viscosity measurements. SCVCP with CuBr/HMTETA in solution gave a series of tertiary amine methacrylate-based branched polymers, in which the molecular weights, the composition of the DEAEMA segment, and the branched structure can be adjusted by an appropriate choice of the comonomer composition, . Quaternization reaction of the branched poly(DEAEMA)s with methyl iodide led to water-soluble cationic polyelectrolytes with branched structures.