Preparation of block-brush PEG-b-P(NIPAM-g-DMAEMA) and its dual stimulus-response

Well-defined dually responsive block-brush copolymer of poly(ethylene glycol)-b-[poly(N-isopropylacrylamide)-g-poly(N,N-dimethylamino-ethylmethacrylate)], [PEG-b-P(NIPAM-g-PDMAEMA)] was successfully prepared by the combination of atom transfer radical polymerization (ATRP) and click chemistry based on azide-capped PDMAEMA and alkyne-pending PEG-b-PNIPAM copolymer. Azide-capped PDMAEMA was synthesized through ATRP of DMAEMA monomer using an azide-functionalized initiator of β-azidoethyl-2-bromoisobutyrate. Alkyne-pending PEG-b-PNIPAM copolymer was obtained through ATRP copolymerization of NIPAM with propargyl acrylate. The final block-brush copolymer was synthesized by the click reaction between these two polymer precursors. Because of characteristics of three different blocks, the copolymer exhibited dually thermo- and pH-responsive behavior. The responsive behaviors of block-brush copolymer were studied by laser light scattering, temperature-dependent turbidity measurement and micro differential scanning calorimetry. The phase transition temperature of block-brush copolymer increased with the decrease of pH value. At pH = 5.0, the copolymer displayed weak thermo-responsive behavior and might form uni-molecular micelles upon heating. At higher pH values, the block-brush copolymer aggregated intermolecularly into the micelles during the phase transition.