Effect of Synthesis Temperature on Size, Structure, and Volume Phase Transition of Polysaccharide Microgels

High-molecular-weight polysaccharide microgels were synthesized at a range of temperatures above the polymer lower critical solution temperature (LCST) (ΔT = 0.6-18.1 °C), and ΔT was found to strongly influence the structure, dynamics, and volume phase transition temperature of the resulting particles. Static and dynamic light scattering studies and mean field theory analysis of the microgels below and above volume phase transition revealed several distinct regimes. At small ΔT, lower density, larger, and more polydisperse microgels that deswell by a factor 10 in volume were synthesized. At intermediate ΔT = 5-8 °C, the formed microgels were the smallest, densest, and most monodisperse below the transition, but exhibited deswelling only by a factor of 5 above the transition. Synthesis at high ΔT led to the formation of nonuniform microgels with small density, a high degree of polydispersity, and in some cases the apparent presence of the un-cross-linked polymer. Furthermore, the volume phase transition temperature dropped significantly as ΔT increased. This work suggests that synthesis temperature can be used to tune the size, deswelling capacity, and volume phase transition temperature of the polymeric microgels.