Fluorescent, Thermoresponsive Oligo(ethylene glycol) Methacrylate/9-(4-Vinylbenzyl)-9H-carbazole Copolymers Designed with Multiple LCSTs via Nitroxide Mediated Controlled Radical Polymerization

9-(4-Vinylbenzyl)-9 H -carbazole (VBK) was used as the “controlling” comonomer for nitroxide mediated polymerization with 10 mol % SG1 free nitroxide relative to BlocBuilder initiator at 80 °C of oligo(ethylene glycol) methyl ether methacrylate (8–9 ethylene glycol (EG) units) (OEGMA 8–9 ), 2-(2-methoxyethoxy)ethyl methacrylate (MEO 2 MA) and for an OEGMA 8–9 /MEO 2 MA-mixed feed. The synthesis of MEO 2 MA/VBK and OEGMA 8–9 /VBK copolymers and MEO 2 MA/OEGMA 8–9 /VBK terpolymers exhibited linear increases in number-average molecular weight ( M̅ n ) versus conversion X, up until X = 0.6, with final copolymers characterized by relatively narrow, monomodal molecular weight distributions ( M̅ w / M̅ n < 1.4, in most cases). A series of MEO 2 MA/OEGMA 8–9 /VBK terpolymers were synthesized and by varying the OEGMA 8–9:MEO 2 MA feed ratios, the terpolymers exhibited tunable lower critical solution temperatures in water (28 °C < LCST s < 81 °C). MEO 2 MA/OEGMA 8–9 /VBK terpolymers were deemed sufficiently pseudo-“living” to reinitiate a second batch of MEO 2 MA/OEGMA 8–9 /VBK, with few apparent dead chains, as indicated by the monomodal shift in the GPC chromatograms. The resulting MEO 2 MA/OEGMA 8–9 /VBK block copolymers were designed so that each block exhibited a distinct LCST, which was confirmed by UV–vis and dynamic light scattering. In addition to controlling the terpolymerization, the VBK units imparted thermo-responsive fluorescence into the final copolymers.