Reticulated Nanoporous Polymers by Controlled Polymerization-Induced Microphase Separation

Materials with percolating mesopores are attractive for applications such as catalysis, nanotemplating, and separations. Polymeric frameworks are particularly appealing because the chemical composition and the surface chemistry are readily tunable. We report on the preparation of robust nanoporous polymers with percolating pores in the 4- to 8-nanometer range from a microphase-separated bicontinuous precursor. We combined polymerization-induced phase separation with in situ block polymer formation from a mixture of multifunctional monomers and a chemically etchable polymer containing a terminal chain transfer agent. This marriage results in microphase separation of the mixture into continuous domains of the etchable polymer and the emergent cross-linked polymer. Precise control over pore size distribution and mechanical integrity renders these materials particularly suited for various advanced applications.