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

Nature Chemistry volume 2, pages 207212 (2010) | Download Citation

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.

  • Compound C6H8O4

    2,2-Dimethyl-1,3-dioxane-4,6-dione

  • Compound C13H14O4

    5-Benzyl-2,2-dimethyl-1,3-dioxane-4,6-dione

  • Compound C22H22O4

    5-Benzyl-2,2-dimethyl-5-(4-vinylbenzyl)-1,3-dioxane-4,6-dione

  • Compound C12H13NO4

    1-[(2,2-Dimethyl-4,6-dioxo-1,3-dixane-5-yl)methyl]-pyridinium inner salt

  • Compound C12H14O4

    2',2'-Dimethyl-spiro[bicyclo[2.2.1]hept-5-ene-2,5'-[1,3]dioxane]-4',6'-dione

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References

  1. 1.

    & The convergence of synthetic organic and polymer chemistries. Science 309, 1200–1205 (2005).

  2. 2.

    , & Click chemistry: Diverse chemical function from a few good reactions. Angew. Chem. Int. Ed. 40, 2004–2021 (2001).

  3. 3.

    & o-Quinodimethanes: Efficient intermediates in organic synthesis. Chem. Rev. 99, 3199–3246 (1999).

  4. 4.

    , , & Reactivity of disubstituted benzocyclobutenes: Model compounds of cross-linkable high-performance polymers. Macromolecules 27, 2647–2657 (1994).

  5. 5.

    , , , & Covalent attachment of various substituents in closest proximity to the C60-core: A broad synthetic approach to stable fullerene derivatives. Tetrahedron 51, 9927–9940 (1995).

  6. 6.

    et al. A facile approach to architecturally defined nanoparticles via intramolecular chain collapse. J. Am. Chem. Soc. 124, 8653–8660 (2002).

  7. 7.

    , , , & The dramatic effect of architecture on the self-assembly of block copolymers at interfaces. Langmuir 21, 10444–10458 (2005).

  8. 8.

    , , , & Synthesis and direct visualization of block copolymers composed of different macromolecular architectures. Macromolecules 38, 2674–2685 (2005).

  9. 9.

    , , , & A generalized approach to the modification of solid surfaces. Science 308, 236–239 (2005).

  10. 10.

    , , & A thermal and manufacturable approach to stabilized diblock copolymer templates. Macromolecules 38, 7676–7683 (2005).

  11. 11.

    , , & New route to incorporation of [60]fullerene into polymers via the benzocyclobutenone group. Macromolecules 31, 5556–5558 (1998).

  12. 12.

    Ketenes, a new compound class. Ber. Dtsch. Chem. Ges. 38, 1735–1739 (1905).

  13. 13.

    Ketenes (John Wiley & Sons, 2006).

  14. 14.

    Ketene chemistry after 100 years: Ready for a new century. Eur. J. Org. Chem., 563–576 (2006).

  15. 15.

    & Ketenes and bisketenes as polymer intermediates. Prog. Polym. Sci. 16, 173–201 (1991).

  16. 16.

    , , , Helv. Chim. Acta, 8, 322–332 (1925).

  17. 17.

    , Ketene polymers. Enc. Polym. Sci. Technol. 8, 45–57 (1968).

  18. 18.

    , & Development of a living anionic polymerization of ethylphenylketene: A novel approach to well-defined polyester synthesis. Macromolecules 32, 1711–1713 (1999).

  19. 19.

    , & Anionic alternating copolymerization of ketene and aldehyde: Control of enantioselectivity by bisoxazoline-type ligand for synthesis of optically active polyesters. Macromolecules 39, 8898 (2006).

  20. 20.

    , 100 years of the Wolff rearrangement. Eur. J. Org. Chem., 2193–2256 (2002).

  21. 21.

    Diazonaphthoquinone-Based Resists (SPIE Optical Engineering Press, 1993).

  22. 22.

    , et al. Synthetic micelle sensitive to IR light via a two-photon process. J. Am. Chem. Soc. 127, 9952–9953 (2005).

  23. 23.

    , , , , & Two-photon degradable supramolecular assemblies of linear-dendritic copolymers. Chem. Commun. 2007, 2081–2082 (2007).

  24. 24.

    , & Photoinduced crosslinking of polymers containing pendant hydroxyl groups by using bisbenzodioxinones. Macromol. Rapid Commun. 28, 72–77 (2007).

  25. 25.

    , , & Photoinduced cross-linking polymerization of monofunctional vinyl monomer without conventional photoinitiator and cross-linker. Macromolecules 40, 4406–4408 (2007).

  26. 26.

    , , , & Graft copolymers by the combination of ATRP and photochemical acylation process by using benzodioxinones. Macromolecules 42, 3743–3749 (2009).

  27. 27.

    A β-lactonic acid from acetone and malonic acid. J. Chem. Soc. 93, 598–601 (1908).

  28. 28.

    , & Methyleneketenes and methylenecarbenes. I. Formation of arylmethyleneketenes and alkylideneketenes by pyrolysis of substituted 2,2-dimethyl-1,3-dioxan-4,6-diones. Aust. J. Chem. 27, 2373–2384 (1974).

  29. 29.

    , , & Pyrolytic generation of carbonylcyclopropane (dimethylene ketene) and its dimerization to dispiro-[2,1,2,1]-octane-4,8-dione. Tetrahedron Lett. 16, 4283–4284 (1975).

  30. 30.

    & Ketene cycloadditions. Org. React. 45, 159–646 (1994).

  31. 31.

    & Synthesis and utility of a novel methylene Meldrum's acid precursor. Synthesis 215–218 (1996).

  32. 32.

    & Atom transfer radical polymerization. Chem. Rev. 101, 2921–2990 (2001).

  33. 33.

    Photochemistry of glutaric anhydride type polymers. Macromolecules 9, 359–360 (1976).

  34. 34.

    , , & Nucleophilicity toward ketenes: Rate constants for addition of amines to aryl ketenes in acetonitrile solution. J. Org. Chem. 66, 5016–5021 (2001).

  35. 35.

    , , , & Protein nanoarrays generated by dip-pen nanolithography. Science 295, 1702–1705 (2002).

  36. 36.

    , , & Nanocontact printing: A route to sub-50-nm scale chemical and biological patterning. Langmuir 19, 1963–1965 (2003).

  37. 37.

    , , , & Molecular recognition-mediated fabrication of protein nanostructures by dip-pen lithography. Nano Lett. 2, 1203–1207 (2002).

  38. 38.

    , , , , & Positioning multiple proteins at the nanoscale with electron beam cross-linked functional polymers. J. Am. Chem. Soc. 131, 521–527 (2009).

  39. 39.

    & Features of gold having micrometer to centimeter dimensions can be formed through a combination of stamping with an elastomeric stamp and an alkanethiol ‘ink’ followed by chemical etching. Appl. Phys. Lett. 63, 2002–2004 (1993).

  40. 40.

    et al. Highly versatile and robust materials for soft imprint lithography based on thiol-ene click chemistry. Adv. Mater. 20, 3728–3733 (2008).

  41. 41.

    , & Methyleneketenes and methylenecarbenes. VII. Evidence for the pyrolytic generation of methyleneketene (propadienone). Aust. J. Chem. 30, 179–193 (1977).

  42. 42.

    , & Two convenient methods for the generation of ‘methylene Meldrum's acid’ for Diels-Alder reactions. Tetrahedron Lett. 26, 3195–3198 (1985).

  43. 43.

    & Controlled living ring-opening-metathesis polymerization by a fast-initiating ruthenium catalyst. Angew. Chem. Int. Ed. 42, 1743–1746 (2003).

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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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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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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.

Competing interests

The authors declare no competing financial interests.

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Correspondence to Bongjin Moon or Craig J. Hawker.

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DOI

https://doi.org/10.1038/nchem.538

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