Synthesis of AB(n)-type colloidal molecules by polymerization-induced particle-assembly (PIPA)

Conventional synthesis of colloidal molecules (CMs) mainly depends on particle-based self-assembly of patchy building blocks. However, direct access to CMs by the self-assembly of isotropic colloidal subunits remains challenging. Here, we report the mass production of AB(n)-type CMs by polymerization-induced particle-assembly (PIPA), using a linear ABC triblock terpolymer system. Starting from diblock copolymer spheres, the association of spheres takes place in situ during the polymerization of the third block. The third blocks aggregate into attractive domains, which connect spheres into CMs. The stability of CMs is ensured, as long as the conversions are limited to ca. 50%, and the pH is low. The valence of AB(n)-type CMs (n = 2–6) is determined by the volume ratio of the polymer blocks. By tuning the volume ratio, 78.5% linear AB(2)-type CMs are yielded. We demonstrate that polymerization-induced particle-assembly is successful for the scalable fabrication of AB(n)-type CMs (50 g L(−1)), and can be easily extended to vastly different triblock terpolymers, for a wide range of applications.