Thermoresponsive Stability of Colloids in Butyl Acetate/Ethanol Binary Solvent Realized by Grafting Linear Acrylate Copolymers.

We have developed a new class of thermoresponsive colloids that can exhibit a sharp reversible transition between dispersion and aggregation in binary BuAc/EtOH solvents based on the UCST (upper critical solution temperature)-type phase separation. This is realized by grafting linear PMMA-BA (random) copolymer onto the colloidal particles. We have selected TiO/PS hybrid spheres (HSs) as a model system to demonstrate our general design concept. By grafting the linear PMMA-BA copolymer onto the HS surface, with the molecular weight from 30 to 40 kDa, we found that the thermoresponsive transition between dispersion and aggregation is fast, sharp, and reversible. At high mass fractions of the HSs, we have even observed a sharp transition between dispersion and gelation (or phase separation). The transition temperature can be tuned by varying the binary solvent composition, BuAc/EtOH, and the molecular weight of the grafted linear copolymer in the range from 5 to 55 °C. One of the most important features of this work is that the thermoresponsive materials used in organic solvents are initially synthesized in water with widely applied conventional (instead of research-based) techniques, thus being well suited for industrial production. In addition, the proposed approach is rather general and applicable to realizing the thermoresponsive transition for various types of colloids and nanoparticles.