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Temperature-dependent size exclusion chromatography for the in situ investigation of dynamic bonding/debonding reactions

Abstract

Polymers capable of dynamic bonding/debonding reactions are of great interest in modern day research. Potential applications can be found in the fields of self-healing materials or printable networks. Since temperature is often used as a stimulus for triggering reversible bonding reactions, an analysis operating at elevated temperatures is very useful for the in situ investigation of the reaction mechanism, as unwanted side effects can be minimized when performing the analyses at the same temperature at which the reactions occur. A temperature-dependent size exclusion chromatographic system (TD SEC) has been optimized for investigating the kinetics of retro Diels−Alder-based depolymerization of Diels−Alder polymers. The changing molecular weight distribution of the analyzed polymers during depolymerization gives valuable quantitative information on the kinetics of the reactions. Adequate data interpretation methods were developed for the correct evaluation of the chromatograms. The results are confirmed by high-temperature dynamic light scattering, thermogravimetric analysis, and time-resolved nuclear magnetic resonance spectroscopy at high temperatures. In addition, the SEC system and column material stability under application conditions were assessed using thermoanalysis methods, infrared spectroscopy, nitrogen physisorption, and scanning electron microscopy. The findings demonstrate that the system is stable and, thus, we can reliably characterize such dynamically bonding/debonding systems with TD SEC.

3D illustration of chromatograms of a polymer after different times of a depolymerization reaction

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Acknowledgments

A.L., J.B., N. G., and C.B.-K. thank Evonik Industries AG for continued financial support and the excellent collaboration. Kerstin Arnhold is acknowledged for help with the thermoanalysis, and Mikhail Malanin for the IR analysis and interpretation, while Viktoria Albrecht is thanked for nitrogen physisorption studies and Hartmut Komber for the NMR measurements. C.B.-K. is grateful for continued support from the Karlsruhe Institute of Technology and the Helmholtz association in its Science and Technology of Nanosystems and BioInterfaces programs.

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Correspondence to Albena Lederer.

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Published in the topical collection Separation and Characterization of Natural and Synthetic Macromolecules with guest editors Albena Lederer and Peter J. Schoenmakers.

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Brandt, J., Guimard, N.K., Barner-Kowollik, C. et al. Temperature-dependent size exclusion chromatography for the in situ investigation of dynamic bonding/debonding reactions. Anal Bioanal Chem 405, 8981–8993 (2013). https://doi.org/10.1007/s00216-013-7203-8

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Keywords

  • Self-healing
  • Retro Diels−Alder
  • High-temperature SEC
  • Temperature-dependent SEC