Keywords :
adhesive; click chemistry; pressure-sensitive; switchable; thiol-ene; Base catalyzed; Click chemistry; Cohesion properties; Microphase separated; On demands; Pressure sensitive; Switchable; Thermo-switchable; Thiol/ene; Vinyl ethers; Electronic, Optical and Magnetic Materials; Chemistry (all); Biomaterials; Materials Science (all); Condensed Matter Physics; Electrochemistry
Abstract :
[en] Switchable adhesives are materials of utmost importance due to their capability of having their adhesion/cohesion properties reversibly triggered upon stimuli, allowing on-demand surface attaching/detaching. Still, several challenges mainly associated with complex uncontrolled chemical processes hinders their production. In this study, it is found that unexpectedly vinyl ethers are able to react with thiols in the presence of a catalytic concentration of base, which allows the preparation of well-defined phase-separated switchable adhesives. Indeed, these findings show that base-catalyzed thiol-acrylate and thiol-vinyl ether are highly orthogonal, making the acrylate reaction faster. This is explored to react in the first stage thiols with acrylates in the presence of vinyl ethers to end-cap all the oligomers with stable vinyl ethers and suppress undesirable disulfide formation. In a second stage the UV-triggered thiol-ene “click reaction” is carried out, forming the network. It is shown that the network prepared by this approach presents superior adhesion due to greater backbone length, a controlled crosslinking motif, and better-defined microphase separation. Additionally, the adhesives made by this strategy are thermo-switchable due to the temperature-triggered base-catalyzed thioether dynamic covalent character at 200 °C. Despite providing superior adhesive properties, the proposed technology endows scalable, thermo-switchable, and O2-resistant adhesives with huge industrialization potential.
Funding text :
The authors acknowledge grant TED2021-129852B-C22 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR and the grant PID2022-138199NB-I00 funded by MCIN/AEI/10.13039/501100011033. The authors acknowledge grant TED2021-129852B-C22 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR and the grant PID2022-138199NB-I00 funded by MCIN/AEI/10.13039/501100011033. L.P.F. thanks the ADAGIO: Advanced Manufacturing Research Fellowship Programme in the Basque e New Aquitaine Region. The authors would like to thank the financial support provided by the NIPU-EJD project; this project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sk\u0142odowska-Curie grant agreement No 955700. The authors acknowledge the financial support from the European Union's Horizon 2020 research and innovation program, under the Marie Sk\u0142odowska-Curie grant agreement no. 101034379. MX acknowledges the grant from the Gipuzkoa Fellows Programme (G75067454). SAXS experiments were performed at BL11-NCD-SWEET beamline exp.2023027561 at ALBA Synchrotron with the collaboration of ALBA staff and Dr. Daniele Mantione. Grupos consolidados grant, Basque Government (IT1503-22). The authors acknowledge the technical and human support provided by SGIker (UPV/EHU/ERDF, EU) for the TEM and AFM images. MCIN/AEI/10.13039/501\u00A0100\u00A0011\u00A0033, and European Union NextGenerationEU/PRTR.The authors acknowledge grant TED2021\u2010129852B\u2010C22 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR and the grant PID2022\u2010138199NB\u2010I00 funded by MCIN/AEI/10.13039/501100011033. The authors acknowledge grant TED2021\u2010129852B\u2010C22 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR and the grant PID2022\u2010138199NB\u2010I00 funded by MCIN/AEI/10.13039/501100011033. L.P.F. thanks the ADAGIO: Advanced Manufacturing Research Fellowship Programme in the Basque e New Aquitaine Region. The authors would like to thank the financial support provided by the NIPU\u2010EJD project; this project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sk\u0142odowska\u2010Curie grant agreement No 955700. The authors acknowledge the financial support from the European Union's Horizon 2020 research and innovation program, under the Marie Sk\u0142odowska\u2010Curie grant agreement no. 101034379. MX acknowledges the grant from the Gipuzkoa Fellows Programme (G75067454). SAXS experiments were performed at BL11\u2010NCD\u2010SWEET beamline exp.2023027561 at ALBA Synchrotron with the collaboration of ALBA staff and Dr. Daniele Mantione. Grupos consolidados grant, Basque Government (IT1503\u201022). The authors acknowledge the technical and human support provided by SGIker (UPV/EHU/ERDF, EU) for the TEM and AFM images. MCIN/AEI/10.13039/501 100 011 033, and European Union NextGenerationEU/PRTR.
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