3D-Printable Nanoporous Thermosets via Disulfide-Based Polymerization-Induced Microphase Separation
Xueheng Dai1, Kenny Lee1,2, Yuan Xiu1
1Cluster for Advanced Macromolecular Design (CAMD) and Australian Centre for Nanomedicine (ACN), School of Chemical Engineering, University of New South Wales, Sydney, NSW, Australia.
Angewandte Chemie (International Ed. in English)
|June 13, 2026
Summary
Chemically degradable macroinitiators enable tunable nanoporous polymer networks via polymerization-induced microphase separation (PIMS). This advance allows for 3D printing of complex hierarchical structures with nanoscale porosity for advanced manufacturing applications.
Area of Science:
- Materials Science
- Polymer Chemistry
- Nanotechnology
Background:
- Interconnected nanoporous polymer networks are crucial for applications requiring rapid mass transport.
- Current fabrication methods using polymerization-induced microphase separation (PIMS) have limitations in polarity, formulation compatibility, and additive manufacturing.
- Existing methods struggle to create tunable, hierarchical structures for advanced applications.
Purpose of the Study:
- To overcome limitations in PIMS fabrication of nanoporous polymer networks.
- To develop a PIMS strategy using tunable and degradable macroinitiators.
- To enable the 3D printing of complex hierarchical architectures with controlled nanoscale porosity.
Main Methods:
- Synthesis of chemically degradable macroinitiators (macroCTAs) via reversible addition-fragmentation chain-transfer copolymerization.
- Tuning macroCTA hydrophilicity by copolymerizing lipoic acid derivatives with acrylates.
- Preparation of microphase-separated materials and subsequent conversion to nanoporous thermosets via disulfide cleavage.
- Utilizing photocurable resins compatible with liquid-crystal display 3D printing.
Main Results:
- Successful synthesis of a diverse library of tunable, degradable macroCTAs.
- Preparation of microphase-separated materials across a wide range of chemistries.
- Fabrication of nanoporous thermosets with controlled pore sizes (24-42 nm) via selective disulfide cleavage.
- Demonstration of 3D printing complex hierarchical architectures with embedded nanoscale porosity using liquid-crystal display technology.
Conclusions:
- Tunable and degradable macroCTAs provide a versatile platform for PIMS.
- This strategy bridges 3D-printable form factors with programmable nanoscale structure.
- The developed method offers a general route to hierarchically structured materials for separations, catalysis, and advanced manufacturing.
