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Tailoring Properties of 3D-Printable Polyelectrolyte Photopolymer Complexes with Reactive Diluents



Thomas Kolibaba, Callie Higgins, Benjamin Caplins, Elisabeth Mansfield, Caleb Chandler, Jason Killgore


Polyelectrolyte complexes (PECs), ionically bound assemblies of oppositely charged polymers, have wide ranging applications spanning medicine, fire safety, and electronic materials. For years, PECs presented processing challenges owing to their ionic bonds which has limited them to uses as coatings. Chemistry was recently developed to additively manufacture PECs of polyethylenimine and polymethacrylic acid through vat photopolymerization, but the use of solvent compromised the mechanical properties of the parts. Here, two reactive diluents, hydroxyethyl methacrylate and dimethyl acrylamide, are substituted for the previously used solvent in printable PEC resins. Parts printed with these reactive diluents have nearly identical processing parameters but exhibit significant differences in thermomechanical properties and water resistance. Thermally-driven amidization of the carboxylate and ammonium groups yield a further dimension of control over the properties of the parts. The combination of spatial, thermomechanical, and hydrophilic control promises to dramatically expand the application space of polyelectrolyte materials.
ACS Applied Polymer Materials


vat photopolymerization, additive manufacturing, 3D printing, polyethylenimine, methacrylic acid


Kolibaba, T. , Higgins, C. , Caplins, B. , Mansfield, E. , Chandler, C. and Killgore, J. (2024), Tailoring Properties of 3D-Printable Polyelectrolyte Photopolymer Complexes with Reactive Diluents, ACS Applied Polymer Materials, [online],, (Accessed July 12, 2024)


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Created June 14, 2024, Updated June 17, 2024