3D‐Printable Nanoporous Thermosets via Disulfide‐Based Polymerization‐Induced Microphase Separation

Interconnected nanoporous polymer networks are central to applications that demand rapid mass transport, yet their fabrication by polymerization-induced microphase separation (PIMS) remains constrained by fixed macroCTA polarity, limited formulation compatibility, and difficult translation to additive manufacturing. Here, we address these limitations by introducing a PIMS strategy utilizing chemically degradable macroCTAs with systematically tunable hydrophilicity. These macroCTAs were synthesized via reversible addition-fragmentation chain-transfer copolymerization of α-lipoic acid or ethyl lipoate with various acrylates. This diverse library of macroCTAs enabled the preparation of microphase-separated materials across a broad range of monomer and crosslinker chemistries, which were readily converted into nanoporous thermosets with well-defined pore sizes (24-42 nm) via selective disulfide cleavage. Critically, these photocurable resins are compatible with liquid-crystal display 3D printing, allowing the fabrication of complex, hierarchical architectures that can be directly etched to generate embedded nanoscale porosity while preserving structural integrity. Collectively, tunable and degradable macroCTAs bridge 3D-printable form factors with programmable nanoscale structure, providing a general route to hierarchically structured materials for separations, catalysis, and advanced manufacturing.