Effect of composition of PDMAEMA-b-PAA block copolymers on their pH- and temperature-responsive behaviors

A series of poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) homopolymers and poly(2-(dimethylamino)ethyl methacrylate)-b-poly(acrylic acid) (PDMAEMA-b-PAA) diblock copolymers were synthesized by atomic transfer radical polymerization. Thanks to a fine-tuning of the hydrophobic-hydrophilic balance by varying the molecular weight of the polymers and the pH of the aqueous solutions, as well as the composition for the block copolymers, the lower critical solution temperature (LCST) and the aggregation-dissolution kinetics of PDMAEMA homopolymers and PDMAEMA-b-PAA block copolymers can be adjusted. For the block copolymers, the results show that larger relative size of the PDMAEMA blocks leads to an increasing tendency to form micellar aggregates and a decrease of the LCST of the aqueous solution, which is consistent with the increasing copolymer hydrophobicity. A significant difference of the stimuli-responsive behavior between PDMAEMA-rich and PAA-rich copolymers is observed, because the former exhibit thermo-responsive behavior in a broad temperature range of 40-60 °C in basic media, while the pH-responsive behavior is dominant, and only a weak thermo-responsive behavior is exhibited around the specific isoelectric point (IEP) in the latter case. The aggregation rate is strongly influenced by temperature, molecular weight, structure, and composition of the polymer. Specifically, temperature has a stronger effect than the molar ratio of the PDMAEMA segment in the copolymer (related to its hydrophobicity) and the chain molecular weight, although the PDMAEMA-b-PAA copolymers show faster aggregation rate than do the PDMAEMA homopolymers.