Triphasic Polymer Particles Assembled via Microphase Separation with Multiple Functions.

This work investigated a unique type of triphasic colloidal particles composed of an azo polymer (PCNAZO), a fluorescent pyrene-containing polymer [P(MMA--PyMA)], and a poly(dimethylsiloxane)-based polymer (Hpdca-PDMS), focusing on the synthesis, forming mechanism, morphology control, and functions. The triphasic particles with well-defined morphologies were assembled through the microphase separation of the components in dichloromethane (DCM) droplets in an aqueous medium, induced by the gradual evaporation of the organic solvent. The real-time fluorescence emission spectra of the pyrenyl moieties and microscopic observations show that the formation of the triphasic particles undergoes the segregation of the PCNAZO-rich phase, separation between P(MMA--PyMA)-rich and Hpdca-PDMS-rich phases, coalescence, and solidification in the dispersed droplets. The structure formation is due to the strong phase separation of the polymers as revealed by the calculations based on the Flory-Huggins theory. The morphologies and phase boundaries of the particles are found to be controlled by the interfacial energy between the phases and processing conditions. The triphasic particles thus obtained possess a series of interesting functions stemming from the polymers and the triple-compartmentalized structures. After being deposited on a substrate, the Hpdca-PDMS parts can tightly adhere on the surface, caused by the spreading nature of the polymer when slightly swelled by DCM. Upon irradiation with a linearly polarized laser beam at 488 nm, the azo polymer compartments show a significant elongation along the electric vibration direction of the polarized light, accompanied by the cooperative deformation of the Hpdca-PDMS pads. When dispersed in water and adhered on the substrate surface, the triphasic particles exhibit tunable colors originating from the fluorescence of the pyrenyl fluorophores and light absorption of the azo chromophores. The real-time investigation methods developed here could lead to the deep understanding of the structure formation process in the confined volume and be applied in phase-separation study of other polymers as well.