Asymmetric Colloidal Particles Fabricated by Polymerization-Induced Surface Self-Assembly Approach

In the past decades, the synthesis of asymmetric colloidal particles has been of wide concern in material science because of their anisotropic morphologies and unique properties. However, the synthesis of the asymmetric particles with controllable anisotropy still remains a big challenge because of the lack of effective methods. In this research, polymerization-induced surface self-assembly (PISSA) approach was demonstrated to be an effective method in the synthesis of colloidal particles with tunable asymmetric core–shell structures. Reversible addition–fragmentation chain transfer agents were covalently anchored onto the surfaces of silica particles and coupled onto the ends of methoxy polyethylene glycol (PEG) chains, leading to the synthesis of CTA-modified silica particles (SiO2-CTA) and PEG macro-CTA agents (PEG-CTA), respectively. PISSA process was conducted by using SiO2-CTA and PEG-CTA as co-RAFT agents in RAFT dispersion polymerization of styrene. In the RAFT polymerizations, polymer layers with PS nodules were formed on the surfaces of SiO2 particles. It was demonstrated that the formation of the nodules was related to the production of the PS homopolymer in the PISSA process. In order to control the asymmetric surface structures, RAFT dispersion polymerizations of styrene with added "free" RAFT agents were performed, and it turned out that the eccentrically positioned core–shell structures with silica cores and polymer layers were prepared. The colloidal particles experience morphology changes from surface nodules to snowman-like structures and finally to asymmetric spherical structures, depending on the monomer conversion and the feeding ratio of the co-RAFT agents. Kinetics studies were performed to investigate the mechanism of the formation of the asymmetric particles. After etching the silica cores with HF solution, asymmetric hollow capsules were fabricated.