Upper Critical Solution Temperature of Poly(<i>N</i>-acryloyl glycinamide) in Water: A Concealed Property

Polymers showing an upper critical solution temperature (UCST) in water are rare. Recently, the nonionic homopolymer poly(N-acryloyl glycinamide) (poly(NAGA)) has been shown to exhibit a sharp upper critical solution temperature in pure water as well as in electrolyte solution. Although poly(NAGA) is known for decades the UCST behavior had not been reported. The first controlled radical polymerization of poly(NAGA) by the RAFT (reversible addition–fragmentation transfer) process was also achieved recently, but no UCST was observed. The present study shows that traces of ionic groups in the polymer prevent phase separation. Failure to notice the UCST in the past was because ionic groups have been introduced unintentionally by either acrylate impurities in the monomer, hydrolysis of the polymer side chains, and/or usage of ionic initiators or chain transfer agents. A synthetic procedure for high purity NAGA monomer free of ionic impurities is reported. It is also shown how to obtain stable aqueous solutions of nonionic poly(NAGA) so that the UCST behavior can be exploited in pure water as well as in a physiological milieu. Further, ultrasensitive differential scanning calorimetry and light scattering were used to get insights into the phase separation mechanism. We believe that this knowledge is transferable to other systems and will greatly accelerate research in the field of macromolecules that feature thermally reversible hydrogen bonding.