Physically crosslinked hydrogels based on N-vinylcaprolactam/acrylic acid and N-vinylcaprolactam/methacrylic acid were prepared via free radical polymerization. These temperature responsive hydrogels were characterized in terms of glass transition, phase separation temperature, potentiometric titration and swelling properties. Results showed that phase transition temperature was dependent on the pH value of the solution; increasing pH led to higher lower critical solution temperature (LCST) values which was related to the dissociative behaviors of the carboxylic group of MAc in the buffered solutions. Additionally, with the incorporation of N,N-dimethylacrylamide into the system, cloud point measurements and MDSC showed an increased in the LCST. This increase was based on hydrophilicity, the hydrophilic-hydrophobic balance was disturbed, and consequently, the LCST behavior was shifted. The pKa of the copolymers ranged between 5.6 and 6.5, while for the terpolymers pKa ranged between 5.3 and 6. At high pH (>10), the COOH group is deprotonated and negatively charged (COO-), while at low pH (1-3) the carboxylic group remains protonated which results in hydrogen bonding between the hydroxyl groups (from NaOH) and the excess of HCl. These results correlate with swelling studies where above the pKa value the hydrogels dissolved rapidly compared to below pKa they did not dissolve at all. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1555-1564