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Mechanically controlled radical polymerization initiated by ultrasound

Nature Chemistry volume 9, pages 135–139 (2017)Cite this article

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Abstract

In polymer chemistry, mechanical energy degrades polymeric chains. In contrast, in nature, mechanical energy is often used to create new polymers. This mechanically stimulated growth is a key component of the robustness of biological materials. A synthetic system in which mechanical force initiates polymerization will provide similar robustness in polymeric materials. Here we show a polymerization of acrylate monomers initiated and controlled by mechanical energy provided by ultrasonic agitation. The activator for an atom-transfer radical polymerization is generated using piezochemical reduction of a Cu(II) precursor complex, which thus converts a mechanical activation of piezoelectric particles to the synthesis of a new material. This polymerization reaction has some characteristics of controlled radical polymerization, such as narrow molecular-weight distribution and linear dependence of the polymeric chain length on the time of mechanical activation. This new method of controlled radical polymerization complements the existing methods to synthesize commercially useful well-defined polymers.

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Figure 1: Ultrasound-induced controlled radical polymerization of n-butyl acrylate 1.
Figure 2: Analysis of the piezoelectric reaction and evidence for reduction and initial polymerization.
Figure 3: Potential mechanisms for the ultrasound-mediated generation of ATRP activator.
Figure 4: Polymerization kinetics in control experiments reveal that continuous ultrasonic agitation is necessary for a growing polymer chain.

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Acknowledgements

SEM work was performed at the Laboratory for Electron and X-ray Instrumentation (LEXI) at UC Irvine, using instrumentation funded in part by the National Science Foundation Center for Chemistry at the Space-Time Limit (CHE-082913). A.P.E.K. acknowledges an AFOSR Young Investigator Grant under FA9550-12-1-0352, FA9550-15-1-0300 and FA9550-16-1-0017, a 3M Non-Tenured Faculty award and a DARPA Young Faculty Award for support. M.K. acknowledges the Israeli council for higher education for support.

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Authors and Affiliations

  1. Department of Chemistry, University of California, Irvine, 92697, California, USA

    Hemakesh Mohapatra, Maya Kleiman & Aaron Palmer Esser-Kahn

  2. Department of Chemical Engineering and Materials Science, University of California, Irvine, 92697, California, USA

    Aaron Palmer Esser-Kahn

  3. Department of Biomedical Engineering, University of California, Irvine, 92697, California, USA

    Aaron Palmer Esser-Kahn

Authors
  1. Hemakesh Mohapatra
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Contributions

H.M., A.P.E.-K. and M.K. conceived and designed the experiments. H.M. and M.K. performed the experiments. M.K. performed the electron microscopy experiments. All the authors analysed the results and co-wrote the manuscript.

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Correspondence to Aaron Palmer Esser-Kahn.

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The authors declare no competing financial interests.

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Mohapatra, H., Kleiman, M. & Esser-Kahn, A. Mechanically controlled radical polymerization initiated by ultrasound. Nature Chem 9, 135–139 (2017). https://doi.org/10.1038/nchem.2633

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