Photodeformable Azo Polymer Janus Particles Obtained upon Nonsolvent-Induced Phase Separation and Asynchronous...

Photodeformable submicron Janus particles (JPs), containing an epoxy-based azo polymer (BP-AZ-CN) and poly(methyl methacrylate) (PMMA), were fabricated upon nonsolvent-induced phase separation. The formation of the JPs was induced by gradually adding deionized water into a tetrahydrofuran (THF) solution of both polymers. The results show that the two polymers start to precipitate from the solution at almost the same water content and immediately separate into two phases in each particle due to the strong incompatibility between the two components. After the nucleation, the sizes of the aggregates increase with increasing water content in the following growth stage. The amount of BP-AZ-CN molecules assembling into the aggregates is controlled by the water content in the medium, while the aggregation of PMMA molecules is a slow diffusion-controlled process due to the much higher molecular weight of this polymer. With a further increase in the water content in the dispersion medium, the swollen aggregates collapse to form JPs. Interestingly, when a dispersion with a water content of 50 vol % is diluted with a THF/H₂O mixture with the same water content, the shapes of the JPs are significantly modified and vitrified after removal of THF through evaporation. By increasing the dilution multiples adopted to dilute the intermediate dispersions, JPs with more asymmetric shapes are obtained due to the enhanced asynchronous aggregation. Ternary phase diagrams calculated according to the Flory-Huggins theory provide a semi-quantitative description and rationalization of the phase separation behavior related to the thermodynamic factors. The differences in the transport behavior and aggregation dynamics of the two polymers are also proven to be critical for the formation of the asymmetric structures. Upon irradiation, the BP-AZ-CN compartments of JPs exhibit remarkable elongation along the electric vibrational direction of a linearly polarized laser beam at a wavelength of 488 nm.