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Thermoresponsive polymers are of great importance in numerous applications such as bioseparation, drug delivery, diagnostic and microfluidic applications. Only few thermoresponsive polymers that present an upper critical solution temperature (UCST), i.e. phase separate from solution upon cooling, in a relevant temperature range and green solvents such as water or ethanol have been reported.
In this work two novel functional polymers of based on a 2,6-diaminopyridine motif, namely poly(N-(6-aminopyridin-2-yl)acrylamide) (PNAPAAm) and poly(N-(6-acetamidopyridin-2-yl)acrylamide) (PNAcAPAAm), were synthesized by free radical polymerization. The obtained polymers displayed UCST-type reversible thermoresponsive behaviour in water/alcohol mixtures. Insights into this phenomenon will be given based on visual observations, temperature-dependent turbidimetry and dynamic light scattering as well as 1H-NMR measurements. The UCST phase transition behaviour of the polymers was tunable by varying either the concentration of the polymer solution, the nature of the alcohol or the composition of the solvent mixture. The cloud point temperature of PNAcAPAAm was found to decrease with increasing alcohol content (MeOH, EtOH and iPrOH) in water/alcohol mixtures. Past a critical amount of EtOH or iPrOH in water the cloud point temperature of PNAcAPAAm increased by further addition of EtOH or iPrOH. These polymers with UCST behavior below 60°C in water/alcohol mixtures show great promises for the preparation of smart materials for sensing.