Harnessing entropy to direct the bonding/debonding of polymer systems based on reversible chemistry

Guimard, N. K., Ho, J., Brandt, J., Lin, C. Y., Namazian, M., Mueller, J. O., Oehlenschlaeger, K. K., Hilf, S., Lederer, A., Schmidt, F. G., Coote, M. L., & Barner-Kowollik, C. (2013) Harnessing entropy to direct the bonding/debonding of polymer systems based on reversible chemistry. Chemical Science, 4(7).

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The widely accepted approach for controlling polymer debonding/rebonding properties in responsive materials has been to purposefully engineer the functional end-groups responsible for monomer dynamic bonding. Here, however, we evidence that the debonding temperature of a polymer can also be tuned by changing the chain length of the polymer building blocks, thus altering the entropy released on debonding. Entropy driven debonding, as governed by building block chain length, is suggested theoretically and realized experimentally for two Diels-Alder polymer systems, each based on a different difunctional diene and a common difunctional dienophile. In each case a significant decrease (as much as 60 °C) in the retro Diels-Alder temperature was observed when the chain length of the difunctional dienophile building block was increased. These results have the potential to fundamentally change the approach utilized to design materials capable of bonding reversibly on demand. © 2013 The Royal Society of Chemistry.

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ID Code: 99348
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :16 Export Date: 5 September 2016 Correspondence Address: Coote, M.L.; ARC Centre of Excellence for Free-radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia; email: mcoote@rsc.anu.edu.au References: Inglis, A.J., Nebhani, L., Altintas, O., Barner-Kowollik, C., (2010) Macromolecules, 43, pp. 5515-5520; Zhang, Y., Broekhuis, A.A., Picchioni, F., (2009) Macromolecules, 42, pp. 1906-1912; Reutenauer, P., Buhler, E., Boul, P.J., Candau, S.J., Lehn, J.-M., (2009) Chem.-Eur. J., 15, pp. 1893-1900; Chen, X., Dam, M.A., Ono, K., Mal, A., Shen, H., Nutt, S.R., Sheran, K., Wudl, F., (2002) Science, 295, p. 1698; Otsuka, H., Aotani, K., Higaki, Y., Amamoto, Y., Takahara, A., (2007) Macromolecules, 40, pp. 1429-1434; Canadell, J., Goossens, H., Klumperman, B., (2011) Macromolecules, 44, pp. 2536-2541; Syrett, J.A., Mantovani, G., Barton, W.R.S., Price, D., Haddleton, D.M., (2010) Polym. Chem., 1, pp. 102-106; Burnworth, M., Tang, L., Kumpfer, J.R., Duncan, A.J., Beyer, F.L., Fiore, G.L., Rowan, S.J., Weder, C., (2011) Nature, 472, pp. 334-338; Amamoto, Y., Kamada, J., Otsuka, H., Takahara, A., Matyjaszewski, K., (2011) Angew. Chem., 123, pp. 1698-1701; Trenor, S.R., Shultz, A.R., Love, B.J., Long, T.E., (2004) Chem. Rev., 104, pp. 3059-3078; Ghosh, B., Urban, M.W., (2009) Science, 323, pp. 1458-1460; Scott, T.F., Schneider, A.D., Cook, W.D., Bowman, C.N., (2005) Science, 308, pp. 1615-1617; Holten-Andersen, N., Harrington, M.J., Birkedal, H., Lee, B.P., Messersmith, P.B., Lee, K.Y.C., Waite, J.H., (2011) Proc. Natl. Acad. Sci. U. S. A., 108, pp. 2651-2655; Jay, J.I., Langheinrich, K., Hanson, M.C., Mahalingam, A., Kiser, P.F., (2011) Soft Matter, 7, pp. 5826-5835; Deng, G., Tang, C., Li, F., Jiang, H., Chen, Y., (2010) Macromolecules, 43, pp. 1191-1194; Syrett, J.A., Becer, C.R., Haddleton, D.M., (2010) Polym. Chem., 1, pp. 978-987; Mynar, J.L., Aida, T., (2008) Nature, 451, pp. 895-896; Cordier, P., Tournilhac, F., Soulié-Ziakovic, C., Leibler, L., (2008) Nature, 451, pp. 977-980; Watanabe, M., Yoshie, N., (2006) Polymer, 47, pp. 4946-4952; Plaisted, T.A., Nemat-Nasser, S., (2007) Acta Mater., 55, pp. 5684-5696; Koehler, K.C., Durackova, A., Kloxin, C.J., Bowman, C.N., (2012) AIChE J., 58, pp. 3545-3552; Toncelli, C., De Reus, D.C., Picchioni, F., Broekhuis, A.A., (2012) Macromol. Chem. Phys., 213, pp. 157-165; Zhou, J., Guimard, N.K., Inglis, A.J., Namazian, M., Lin, C.Y., Coote, M.L., Spyrou, E., Barner-Kowollik, C., (2012) Polym. Chem., 3, pp. 628-639; Espinosa, E., Glassner, M., Boisson, C., Barner-Kowollik, C., D'Agosto, F., (2011) Macromol. Rapid Commun., 32, pp. 1447-1453
Keywords: Building blockes, Design materials, Diels-Alder, Diels-Alder polymers, Difunctional, Polymer building blocks, Polymer systems, Responsive materials, Chemical bonds, Debonding, Entropy, Materials properties, Polymers, Chain length
DOI: 10.1039/c3sc50642h
ISSN: 20416520
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 29 Sep 2016 22:23

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