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Vat photopolymerization 3D printing with light-responsive thiol-norbornene photopolymers

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Abstract

The present study highlights the synthesis of a photosensitive norbornene monomer containing an o-nitrobenzyl ester (o-NBE) group, which undergoes controlled bond cleavage upon UV exposure. As the o-NBE chromophores are transparent in the visible light region, photopolymers are readily formed by visible light-induced thiol-ene chemistry using a long-wavelength absorbing photoinitiator. Selective photolysis of the o-NBE moieties is then obtained by irradiation with light in the UV-A spectral region. The sequence-dependent orthogonality of the curing and cleavage reaction are confirmed by FT-IR spectroscopy. Owing to their constrained ring system, norbornene moieties are highly reactive in radical-induced thiol-ene reactions, which enables the vat photopolymerization 3D printing of functional structures with reasonable build speed. Once printed, the wettability of the 3D objects’ surface was conveniently tuned by UV-induced cleavage of the o-NBE groups (release of free carboxylic acids) and related photo-oxidation of the non-reacted thiol moieties (formation of sulfonic acids). With this approach, we were able to introduce wettability gradients onto 3D-printed objects, which is interesting for microfluidic devices and lab-on-chip technologies.

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All data generated or analysed during this study are included in this published article (and its supplementary information files).

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Acknowledgements

Part of the research work was performed with the “SMART” project. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 860108. Part of the research work was performed also within the COMET-Module “Chemitecture“ (project-no.: 21647048) at the Polymer Competence Center Leoben GmbH (PCCL, Austria) within the framework of the COMET-program of the Federal Ministry for Transport, Innovation and Technology and the Federal Ministry for Digital and Economic Affairs with contributions by the Institute of Chemistry of Polymeric Materials (Montanuniversitaet Leoben, Austria). The PCCL is funded by the Austrian Government and the State Governments of Styria, Upper and Lower Austria.

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Authors and Affiliations

  1. Polymer Competence Center Leoben GmbH, Leoben, Austria

    Elisabeth Rossegger, Yang Li, Heike Frommwald & Sandra Schlögl

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  1. Elisabeth Rossegger
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  2. Yang Li
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  3. Heike Frommwald
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  4. Sandra Schlögl
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Correspondence to Sandra Schlögl.

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Rossegger, E., Li, Y., Frommwald, H. et al. Vat photopolymerization 3D printing with light-responsive thiol-norbornene photopolymers. Monatsh Chem 154, 473–480 (2023). https://doi.org/10.1007/s00706-022-03016-5

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