Aqueous Synthesis of Upper Critical Solution Temperature and Lower Critical Solution Temperature Copolymers through Combination of Hydrogen-Donors and Hydrogen-Acceptors.

The synthesis of thermo-responsive polymers from non-responsive and water-soluble monomers has great practical advantages but significant challenges. Herein, the authors report a novel aqueous copolymerization strategy to prepare polymers with tunable upper critical solution temperature (UCST) or lower critical solution temperature (LCST) from non-responsive monomers. Acrylic acid (AAc), N-vinylpyrrolidone (NVP), and acrylamide (AAm) are copolymerized in water, yielding copolymers with UCST behavior. Interestingly, by simply replacing AAm with its methylated homologue, dimethyl acrylamide (DMA), the thermo-responsiveness of the copolymers is converted into LCST-type. The cloud points of the copolymers can be tuned rationally with their monomer ratios and the condition of the solvent. The UCST property of the poly(AAc-NVP-AAm) comes from the AAc-AAm and AAc-NVP hydrogen-bonds, while the LCST property of poly(AAc-NVP-DMA) originates from the hydrophobic aggregation of AAc-NVP complex and DMA, as indicated by temperature-dependent 1 H NMR and dynamic light scattering.