3D Printable Hydrogel with a Controlled Hierarchical Network through Aqueous PhotoATRP Using a Well-Defined
Xiaoguang Qiao1,2, Xuzheng Guo2, Menghan Si2
1College of Materials Engineering, Henan International Joint Laboratory of Rare Earth Composite Materials, Henan Engineering Technology Research Center for Fiber Preparation and Modification, Henan University of Engineering, Zhengzhou 451191, China.
ACS Macro Letters
|December 5, 2025
Summary
This study introduces a novel method using atom transfer radical polymerization (ATRP) to create hydrogels with tunable hierarchical network structures. This allows for precise control over pore size and improved material properties.
Area of Science:
- Polymer Chemistry
- Materials Science
- Biomaterials Engineering
Background:
- Reversible-deactivation radical polymerization (RDRP) enables homogeneous hydrogel synthesis.
- Controlling hydrogel microstructure via RDRP remains challenging.
- Atom transfer radical polymerization (ATRP) offers precise polymer synthesis and uniform network formation.
Purpose of the Study:
- To develop a strategy for constructing hydrogel structures with controlled hierarchical networks.
- To leverage ATRP for creating well-defined polymers and uniform hydrogel networks.
- To enable tunable macropore sizes within hydrogel structures.
Main Methods:
- Utilized a presynthesized, well-defined telechelic bromide macroinitiator.
- Initiated photoATRP of vinyl monomers and divinyl cross-linkers.
- Grafted a covalently linked secondary cross-linked network onto a primary polymer network.
Main Results:
- Achieved a hierarchical architecture with embedded, uniformly sized macropores within a homogeneous network.
- Demonstrated tunable macropore size by adjusting macroinitiator molecular weight.
- Observed significantly altered swelling behavior and mechanical properties in the hydrogels.
Conclusions:
- The developed hierarchical hydrogel architecture offers tunable properties.
- This approach provides new insights into hydrogel microstructure regulation.
- Fabrication via digital light processing (DLP) 3D printing is feasible using aqueous photoATRP.
