Highly Ordered Nanoporous Films from Supramolecular Diblock Copolymers with Hydrogen-Bonding Junctions

We designed efficient precursors that combine complementary associative groups with exceptional binding affinities and thiocarbonylthio moieties enabling precise RAFT polymerization. Well defined PS and PMMA supramolecular polymers with molecular weights up to 30 kg mol−1 are synthesized and shown to form highly stable supramolecular diblock copolymers (BCPs) when mixed, in non‐polar solvents or in the bulk. Hierarchical self‐assembly of such supramolecular BCPs by thermal annealing affords morphologies with excellent lateral order, comparable to features expected from covalent diblock copolymer analogues. Simple washing of the resulting materials with protic solvents disrupts the supramolecular association and selectively dissolves one polymer, affording a straightforward process for preparing well‐ordered nanoporous materials without resorting to crosslinking or invasive chemical degradations. Link for a minute: Supramolecular diblock copolymers self‐assemble from high molecular weight polymers bearing complementary strong hydrogen‐bonding groups. Hierarchical organization affords thin films with excellent lateral order that can be readily transformed into porous membranes, without any degradation, by disruption of the supramolecular links with water/alcohol solutions.