The co-assembly of block copolymers (BCP) with nanoscale inorganic objects through non-covalent interaction is an important approach to fabricate polymer nanocomposites. However, how to improve the miscibility of inorganic/polymeric interface is an important scientific question, particularly for inorganic polyoxometalate (POM)/BCP system. Until now, a general method to incorporate POM into BCP matrices is still lacking. In this work, we present an enthalpy-driven method to realize the co-assembly of POM and BCP, which is generally suitable for common POM and BCP systems. In this method, a POM cluster is embedded as a core in a supramolecular star polymer (SSP). Through the Van der Waals interaction between SSP arms and BCP segments, POM can be incorporated into BCP matrices. By this method, we have realized the co-assembly of POM clusters and poly(styrene-b-ethylene oxide), which leads to the controllable formation of hybrid micelles with spherical, toroidal and bicontinuous morphologies. The mechanism is studied by combining simulations and a new pathway for toroid formation is disclosed. These results not only pave a new way to prepare polymer nanocomposites, but also provide new insights to comprehend the self-assembly behavior of complex polymer systems.

Paper link： http://pubs.acs.org/doi/abs/10.1021/acs.macromol.5b00712