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Proof of ether-bridged condensation products in UF resins by 2D NMR spectroscopy

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Abstract

The existence of ether-bridged condensation products in urea-formaldehyde (UF) resins is still disputed in the literature as these products have never been isolated or fully characterized. Using 1H-15N gradient heteronuclear single quantum correlation (gHSQC) experiment, 1H-13C gHSQC experiment and 1H-13C gradient heteronuclear multiple bond correlation (gHMBC) experiment a, methylolurea hemiformal compound (urea compound with oligomeric chains \(-\rm{CH}_{2}\;{\rm O[CH}_{2}{\rm O]}{\mathrm {n}}{\rm H}\) and \(n\geq 1\)) and a symmetrical compound, most likely an ether-bridged condensation product, in a UF resin sample were characterized. The results were confirmed by 2D NMR 13C-13C gradient correlated spectroscopy (gCOSY) experiment using 13C labeled ureaformaldehyde samples. Spectroscopic chemical shifts of the proposed ether-bridged condensation product in 15N, 13C, 1H NMR spectroscopy were assigned. Furthermore, individual peak assignments are provided for the methylolurea hemiformal moiety.

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Acknowledgments

The authors gratefully acknowledge Bernd Seemann and Dr. Peter Dvortsak from Bruker BioSpin GmbH for their advice and technical support. Measurements on the 400 MHz Advance III spectrometer were conducted at Bruker facilities in Rheinstetten, Germany. Financial support for this work by BASF SE, Ludwigshafen, is also gratefully acknowledged.

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Authors and Affiliations

  1. Laboratory of Engineering Thermodynamics, University of Kaiserslautern, Erwin-Schrödinger-Strasse 44, 67663, Kaiserslautern, Germany

    Éléonore J. Kibrik & Hans Hasse

  2. Department of Chemistry, University of Kaiserslautern, Erwin-Schr¨odinger-Strasse 54, 67663, Kaiserslautern, Germany

    Werner R. Thiel

  3. Laboratory of Thermodynamics and Thermal Process Engineering, University of Stuttgart, Pfaffenwaldring 9, 70550, Stuttgart, Germany

    Oliver Steinhof

  4. BASF SE, GMU/C, 67056, Ludwigshafen, Germany

    Günter Scherr

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  1. Éléonore J. Kibrik
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  2. Oliver Steinhof
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  3. Günter Scherr
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  4. Werner R. Thiel
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  5. Hans Hasse
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Correspondence to Éléonore J. Kibrik.

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Kibrik, É.J., Steinhof, O., Scherr, G. et al. Proof of ether-bridged condensation products in UF resins by 2D NMR spectroscopy. J Polym Res 20, 79 (2013). https://doi.org/10.1007/s10965-013-0079-7

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