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Solvent-free, supersoft and superelastic bottlebrush melts and networks

Nature Materials volume 15, pages 183–189 (2016)Cite this article

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Abstract

Polymer gels are the only viable class of synthetic materials with a Young’s modulus below 100 kPa conforming to biological applications1,2,3, yet those gel properties require a solvent fraction4,5,6,7. The presence of a solvent can lead to phase separation, evaporation and leakage on deformation, diminishing gel elasticity and eliciting inflammatory responses in any surrounding tissues. Here, we report solvent-free, supersoft and superelastic polymer melts and networks prepared from bottlebrush macromolecules. The brush-like architecture expands the diameter of the polymer chains, diluting their entanglements without markedly increasing stiffness. This adjustable interplay between chain diameter and stiffness makes it possible to tailor the network’s elastic modulus and extensibility without the complications associated with a swollen gel. The bottlebrush melts and elastomers exhibit an unprecedented combination of low modulus (∼100 Pa), high strain at break (∼1,000%), and extraordinary elasticity, properties that are on par with those of designer gels8,9.

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Figure 1: Transitioning from polymer molecules to mesoscopic filaments.
Figure 2: Theoretically predicted and experimentally visualized bottlebrush conformations.
Figure 3: Analysis of dynamic mechanical master curves and universal behaviour.
Figure 4: Supersoft and superextendable elastomers.

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References

  1. Levental, I., Georges, P. C. & Janmey, P. A. Soft biological materials and their impact on cell function. Soft Matter 3, 299–306 (2007).

    Article  CAS  Google Scholar 

  2. Williams, D. F. On the mechanisms of biocompatibility. Biomaterials 29, 2941–2953 (2008).

    Article  CAS  Google Scholar 

  3. Rus, D. & Tolley, M. T. Design, fabrication and control of soft robots. Nature 521, 467–475 (2015).

    Article  CAS  Google Scholar 

  4. Wichterle, O. & Lím, D. Hydrophilic gels for biological use. Nature 185, 117–118 (1960).

    Article  Google Scholar 

  5. Discher, D. E., Janmey, P. & Wang, Y. L. Tissue cells feel and respond to the stiffness of their substrate. Science 310, 1139–1143 (2005).

    Article  CAS  Google Scholar 

  6. Anseth, K. S., Bowman, C. N. & Brannon-Peppas, L. Mechanical properties of hydrogels and their experimental determination. Biomaterials 17, 1647–1657 (1996).

    Article  CAS  Google Scholar 

  7. Baumberger, T., Caroli, C. & Martina, D. Solvent control of crack dynamics in a reversible hydrogel. Nature Mater. 5, 552–555 (2006).

    Article  CAS  Google Scholar 

  8. Sun, J. Y. et al. Highly stretchable and tough hydrogels. Nature 489, 133–136 (2012).

    Article  CAS  Google Scholar 

  9. Sun, T. L. et al. Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity. Nature Mater. 12, 932–937 (2013).

    Article  CAS  Google Scholar 

  10. Edwards, S. F. & Doi, M. The Theory of Polymer Dynamics (Oxford Univ. Press, 1986).

    Google Scholar 

  11. de Gennes, P. G. J. Reptation of a polymer chain in the presence of fixed obstacles. Chem. Phys. 55, 572–579 (1971).

    Google Scholar 

  12. Patel, S. K., Malone, S., Cohen, C., Gillmor, J. R. & Colby, R. H. Elastic modulus and equilibrium swelling of poly(dimethylsiloxane) networks. Macromolecules 25, 5241–5251 (1992).

    Article  CAS  Google Scholar 

  13. Everaers, R. Entanglement effects in defect-free model polymer networks. New J. Phys. 1, 12.1–12.54 (1999).

    Article  Google Scholar 

  14. Urayama, K., Kawamure, T. & Kohjiya, S. Elastic modulus and equilibrium swelling of networks crosslinked by end-linking oligomethysiloxne at solutions state. J. Chem. Phys. 105, 4833–4840 (1996).

    Article  CAS  Google Scholar 

  15. Rubinstein, M. & Colby, R. H. Network modulus and superelasticity. Macromolecules 27, 3191–3198 (1994).

    Article  Google Scholar 

  16. Zhang, K., Lackey, M., Cui, J. & Tew, G. N. Gels based on cyclic polymers. J. Am. Chem. Soc. 133, 4140–4148 (2011).

    Article  CAS  Google Scholar 

  17. Landau, L. D. & Lifshitz, E. M. Theory of Elasticity Vol. 7 (Pergamon, 1986).

    Google Scholar 

  18. Boal, D. H. Mechanics of Cell 2nd edn (Cambridge Univ. Press, 2002).

    Google Scholar 

  19. Inkson, N. J., Graham, R. S., McLeish, T. C. B., Groves, D. J. & Fernyhough, C. M. Viscoelasticity of monodisperse comb polymer melts. Macromolecules 39, 4217–4227 (2006).

    Article  CAS  Google Scholar 

  20. Kapnistos, M., Vlassopoulos, D., Roovers, J. & Leal, L. G. Linear rheology of architecturally complex macromolecules: Comb polymers with linear backbones. Macromolecules 38, 7852–7862 (2005).

    Article  CAS  Google Scholar 

  21. Fetters, L. J., Lohse, D. J., Garcia-Franco, C. A., Brant, P. & Richter, D. Prediction of melt state Poly(R-olefin) rheological properties: The unsuspected role of the average molecular weight per backbone bond. Macromolecules 35, 10096–10101 (2002).

    Article  CAS  Google Scholar 

  22. Yamazaki, H. et al. Dynamic viscoelasticity of poly(butyl acrylate) elastomers containing dangling chains with controlled lengths. Macromolecules 44, 8829–8834 (2011).

    Article  CAS  Google Scholar 

  23. Pakula, T. et al. Molecular brushes as super-soft elastomers. Polymer 47, 7198–7206 (2006).

    Article  CAS  Google Scholar 

  24. Hu, M., Xia, Y., McKenna, G. B., Kornfield, J. A. & Grubbs, R. H. Linear rheological response of a series of densely branched brush polymers. Macromolecules 44, 6935–6943 (2011).

    Article  CAS  Google Scholar 

  25. Dalsin, S. J., Hillmyer, M. A. & Bates, F. S. Linear rheology of polyolefin-based bottlebrush polymers. Macromolecules 48, 4680–4691 (2015).

    Article  CAS  Google Scholar 

  26. Zhen, C., Carillo, J. M., Sheiko, S. S. & Dobrynin, A. V. Computer simulations of bottlebrushes: From melts to soft networks. Macromolecules 48, 5006–5015 (2015).

    Article  Google Scholar 

  27. Kavassalis, T. A. & Noolandi, J. Entanglement scaling in polymer melts and solutions. Macromolecules 22, 2709–2720 (1989).

    Article  CAS  Google Scholar 

  28. Matyjaszewski, K. Atom transfer radical polymerization (ATRP): Current status and future perspectives. Macromolecules 45, 4015–4039 (2012).

    Article  CAS  Google Scholar 

  29. Sumerlin, B. S., Neugebauer, D. & Matyjaszewski, K. Initiation efficiency in the synthesis of molecular brushes by grafting from via atom transfer radical polymerization. Macromolecules 38, 702–708 (2005).

    Article  CAS  Google Scholar 

  30. Sheiko, S. S. et al. Measuring molecular weight by atomic force microscopy. J. Am. Chem. Soc. 125, 6725–6728 (2003).

    Article  CAS  Google Scholar 

  31. Lomellini, P. Effect of chain length on the network modulus and entanglement. Polymer 33, 1255–1259 (1992).

    Article  CAS  Google Scholar 

  32. van Gurp, M. & Palmen, J. Time-temperature superposition for polymeric blends. Rheol. Bull. 67, 5–8 (1998).

    Google Scholar 

  33. des Cloizeaux, J. Double reptation vs. simple reptation in polymer melts. Europhys. Lett. 5, 437–442 (1988).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge financial support from the National Science Foundation (DMR 1409710, DMR 1122483, DMR 1407645 and DMR 1436201). J.P. acknowledges financial support provided by a Polish Ministry of Science and Higher Education Grant (IP2012 005072). We also thank E. Zhulina for illuminating discussion, R. Colby of Penn State University for training in rheological techniques, and E. T. Samulski for reviewing the paper.

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Author notes

  1. Jarosław Paturej

    Present address: Present address: Institute of Physics, University of Szczecin, Wielkopolska 15, 70451 Szczecin, Poland.,

Authors and Affiliations

  1. Department of Chemistry, University of North Carolina at Chapel Hill, North Carolina 27599-3290, USA

    William F. M. Daniel, Mohammad Vatankhah-Varnoosfaderani, Jarosław Paturej, Michael Rubinstein & Sergei S. Sheiko

  2. Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, USA

    Joanna Burdyńska & Krzysztof Matyjaszewski

  3. Department of Polymer Science, University of Akron, Akron, Ohio 44325-3909, USA

    Andrey V. Dobrynin

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Contributions

W.F.M.D. performed LB-AFM experiments and analysis, rheology experiments and analysis, and wrote the manuscript. J.B. and K.M. synthesized BA bottlebrush polymers and performed GPC and chain cleavage analysis. M.V.-V. synthesized pDMS elastomers, J.P. performed computer simulations of bottlebrush melts, and M.R. and A.V.D. provided theoretical predictions. S.S.S. was the primary investigator.

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Correspondence to Sergei S. Sheiko.

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The authors declare no competing financial interests.

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Daniel, W., Burdyńska, J., Vatankhah-Varnoosfaderani, M. et al. Solvent-free, supersoft and superelastic bottlebrush melts and networks. Nature Mater 15, 183–189 (2016). https://doi.org/10.1038/nmat4508

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