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A facile route to ketene-functionalized polymers for general materials applications

Nature Chemistry volume 2, pages 207–212 (2010)Cite this article

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Abstract

Function matters in materials science, and methodologies that provide paths to multiple functionality in a single step are to be prized. Therefore, we introduce a robust and efficient strategy for exploiting the versatile reactivity of ketenes in polymer chemistry. New monomers for both radical and ring-opening metathesis polymerization have been developed, which take advantage of Meldrum's acid as both a synthetic building block and a thermolytic precursor to dialkyl ketenes. The ketene-functionalized polymers are directly detected by their characteristic infrared absorption and are found to be stable under ambient conditions. The inherent ability of ketenes to provide crosslinking via dimerization and to act as reactive chemical handles via addition, provides simple methodology for application in complex materials challenges. Such versatile characteristics are illustrated by covalently attaching and patterning a dye through microcontact printing. The strategy highlights the significant opportunities afforded by the traditionally neglected ketene functional group in polymer chemistry.

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Figure 1: Thermolysis of 5,5-dialkyl Meldrum's acid to a ketene, and subsequent reactivity.
Figure 2: Synthesis of Meldrum's-acid-containing monomers for radical and ring-opening methathesis polymerizations.
Figure 3: Synthesis of Meldrum's-acid-containing polymer 10 and its thermolytic properties.
Figure 4: Spectroscopic evidence for the formation of a ketene from 10.
Figure 5: Covalent attachment of fluorescent dye on µCP surface.
Figure 6: Synthesis of Meldrum's-acid-containing polynorbornene.

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Acknowledgements

M.K. and B.M. gratefully acknowledge the Center for Bioactive Molecular Hybrid (CBMH) of KOSEF, the Sogang University grant (200811016), BK21 program from the Ministry of Education and Human Resources Development. F.A.L. and C.J.H. would like to thank the National Science Foundation (MRSEC Program: DMR-0520415, Chemistry Program: CHE-0514031, Graduate Fellowship) and the DOD (Graduate Fellowship) for financial support. Please address correspondences to C.J.H.

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Authors and Affiliations

  1. Departments of Materials, Chemistry and Biochemistry, Materials Research Laboratory, University of California, Santa Barbara, California, 93106, USA

    Frank A. Leibfarth, Luis M. Campos, Nalini Gupta & Craig J. Hawker

  2. Department of Chemistry, Sogang University, Seoul, 121-742, Korea

    Minhyuk Kang, Myungsoo Ham, Joohee Kim & Bongjin Moon

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  1. Frank A. Leibfarth
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  4. Joohee Kim
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Contributions

F.A.L., B.M., M.K. and C.J.H. developed the concept and conceived the experiments. F.A.L., M.K., B.M., M.H. and J.K. performed the laboratory experiments and analysed the results. L.C. and N.G. provided expertise in μCP and fluorescence microscopy, respectively. F.A.L., B.M. and C.J.H wrote the manuscript.

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Correspondence to Bongjin Moon or Craig J. Hawker.

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Leibfarth, F., Kang, M., Ham, M. et al. A facile route to ketene-functionalized polymers for general materials applications. Nature Chem 2, 207–212 (2010). https://doi.org/10.1038/nchem.538

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