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Peer-reviewedCC BYAngewandte Chemie International Edition

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

  • Xueheng Dai1
  • Kenny Lee1,2
  • Yuan Xiu1
  • Nathaniel Alan Corrigan3
  • Kun Zhou1
  • Xichuan Li1
  • Christopher M. Bates2
  • Craig J. Hawker2
  • Cyrille Andre Boyer1
  1. 1Cluster for Advanced Macromolecular Design (CAMD) and Australian Centre for Nanomedicine (ACN) School of Chemical Engineering University of New South Wales Sydney NSW Australia
  2. 2Materials Research Laboratory and Materials Department University of California Santa Barbara Santa Barbara California USA
  3. 3Centre for Advanced Manufacturing Technology (CfAMT) School of Engineering Western Sydney University Sydney NSW Australia
Open at sourceDOICite

Abstract

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.

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Cite

BibTeXRIS
BibTeX
@article{dai20263dprintable,
  title = {{3D‐Printable Nanoporous Thermosets via Disulfide‐Based Polymerization‐Induced Microphase Separation}},
  author = {Xueheng Dai and Kenny Lee and Yuan Xiu and Nathaniel Alan Corrigan and Kun Zhou and Xichuan Li and Christopher M. Bates and Craig J. Hawker and Cyrille Andre Boyer},
  journal = {Angewandte Chemie International Edition},
  year = {2026},
  month = jun,
  doi = {10.1002/anie.8227484},
  url = {https://doi.org/10.1002/anie.8227484},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - 3D‐Printable Nanoporous Thermosets via Disulfide‐Based Polymerization‐Induced Microphase Separation
AU  - Xueheng Dai
AU  - Kenny Lee
AU  - Yuan Xiu
AU  - Nathaniel Alan Corrigan
AU  - Kun Zhou
AU  - Xichuan Li
AU  - Christopher M. Bates
AU  - Craig J. Hawker
AU  - Cyrille Andre Boyer
PY  - 2026
DA  - 2026/06/13
JO  - Angewandte Chemie International Edition
DO  - 10.1002/anie.8227484
UR  - https://doi.org/10.1002/anie.8227484
AB  - 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.
SN  - 1433-7851
SN  - 1521-3773
ER  -