Abstract
The surface-initiated graft polymerization of polymer brushes attached to an sp3 random carbon network backbone structure is demonstrated. Poly(ethyl acrylate) (PEA), poly(4-fluorostyrene) (PFS) and poly(acrylonitrile) (PAN) brushes were grafted from the network backbone polymer poly(hydridocarbyne), 1, illustrating the breadth of reactivity of the network backbone. Attachment of polymeric/oligomeric chains to the network backbone was observed through two different methods with different polymer systems. First, selective solvent extraction separated a homogeneous mixture of PEA and 1, dissolving PEA in diethyl ether, but leaving 1 behind as a brown precipitate. In contrast, 1 functionalized with PEA brushes completely dissolved, showing that it was not a homogenous mixture of the substrate and free polymeric chains, but a system of covalently bound polymer chains originating from 1. Formation of short chains of PFS at the surface of 1 allowed the use of 19F nuclear magnetic resonance to observe the change in resonance shift and shape for the polymer side chains. Solvent extraction was used to demonstrate that tetrahydrofuran (THF) was able to separate a homogeneous mixture of PAN and 1, dissolving 1 in THF, but leaving PAN behind as a white precipitate.
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References
Ishizu, K. & Fukukawa, T. Architecture and surfactant behaviors of amphiliphilic prototype and AB-Block type copolymer brushes. in Focus on Polymeric Materials Research (ed. Caruta, B. M.) 29–48 (Nova Science Publishers, Hauppauge, NY, 2006).
Ni, G., Yang, W., He, X., Bo, L. & Lu, W. Advances in surface initiated polymerization. Prog. Chem. 17, 1074–1080 (2005).
Tsujii, Y., Ohno, K., Yamamoto, S., Goto, A. & Fukuda, T. Structure and properties of high-density polymer brushes prepared by surface-initiated living radical polymerization, in Advances in Polymer Science: Surface-Initiated Polymerization I (ed. Jordan, R.), Vol. 197, Ch. 1, 1–45 (Springer, Berlin, 2006).
Arslan, H., Yesilyurt, N. & Hazer, B. The synthesis of poly(3-hydroxybutyrate)-g poly(methylmethacrylate) brush type graft copolymers by atom transfer radical polymerization method,. J. of Appl. Polym. Sci. 106, 1742–1750 (2007).
Liu, P. Modification of polymeric materials via surface-initiated controlled/‘living’ radical polymerization. E-Polymers 062 (2007).
Neugebauer, D. Graft copolymers with poly(ethylene oxide) segments. Polym. Intl. 56, 1469–1498 (2007).
Burkett, S., Ko, N., Stern, N., Caissie, J. & Sengupta, D. Covalently linked nanocomposites: poly(methyl methacrylate) brushes grafted from zirconium phosphonate. Chem. Mater. 18, 5137–5143 (2006).
Shanmugharaj, A., Bae, J., Nayak, R. & Ryu, S. Preparation of poly(styrene-co-acrylonitrile)-grafted multiwalled carbon nanotubes via surface-initiated atom transfer radical polymerization. J. Polym. Sci. Part A: Polym. Chem. 45, 460–470 (2006).
Sengonul, M., Ruzicka, J., Attygalle, A. & Libera, M. Surface modification of protein nanocontainers and their self-directing character in polymer blends. Polymer 48, 3632–3640 (2007).
Zhang, J., Yang, Y., Zhao, C. & Zhao, H. PS/PMMA mixed polymer brushes on the surface of clay layers: preparation and application in polymer blends. J. Polym. Sci. Part A: Polym. Chem. 45, 5329–5338 (2007).
Retsos, H., Kiriy, A., Senkovskyy, V., Stamm, M., Feldstein, M. & Creton, C. Controlling tack with bicomponent polymer brushes. Adv. Mater. 18, 2624–2628 (2006).
Makal, U., Uslu, N. & Wynne, K. Water Makes it hydrophobic: contraphilic wetting for polyurethanes with soft blocks having semifluorinated and 5,5-dimethylhydantoin side chains. Langmuir 23, 209–216 (2007).
Mizutani, A., Kikuchi, A., Yamato, M., Kanazawa, H. & Okano, T. Preparation of thermoresponsive polymer brush surfaces and their interation with cells. Biomaterials 29, 2073–2081 (2008).
Schrinner, M., Polzer, F., Mei, Y., Lu, Y., Haupt, B., Ballauff, M., Goldel, A., Drechsler, M., Preussner, J. & Glatzel, U. Mechanism of the formation of amorphous gold nanoparticles within spherical polyelectrolyte brushes. Macromol. Chem. Phys. 208, 1542–1547 (2007).
Luzinov, I., Minko, S. & Tsukruk, V. V. Responsive brush layers: from tailored gradients to reversibly assembled nanoparticles. Soft Matter 4, 714–725 (2008).
Zdyrko, B., Kinnan, M., Chumanov, G. & Luzinov, I. Fabrication of optically active flexible polymer films with embedded chain-like arrays of silver nanoparticles. Chem. Commun. 1284–1286 (2008).
Zhou, L. & Ma, Y. Phase behavior of nanoparticle–copolymer films confined between polymer-grafted surfaces. J. Phys.—Condensed Matter 20, 095006 (2008).
Brittain, W. & Minko, S. A structural definition of polymer brushes. J. Polym. Sci. Part A: Polym. Chem. 45, 3505–3512 (2007).
Kent, M. A quantitative study of tethered chains in various solution conditions using langmuir diblock copolymer monolayers. Macromol. Rapid Commun. 21, 243–270 (2000).
Parsonage, E., Tirrell, M., Wanatabe, H. & Nuzzo, R. Adsorption of poly(2-vinylpyridine) poly(styrene) block copolymers from toluene solutions. Macromolecules 24, 1987–1995 (1991).
Cosgrove, T., Heath, T., Ryan, K. & Crowley, T. Neutron-scattering from adsorbed polymer layers. Macromolecules 20, 2879–2882 (1987).
Dyer, D. Photoinitiated synthesis of grafted polymers. Adv. Polym. Sci. 197, 47–65 (2006).
Bianconi, P., Joray, S., Aldrich, B., Sumranjit, J., Duffy, D., Long, D., Lazorcik, J., Raboin, L., Kearns, J., Smulligan, S. & Babyak, J. Diamond and diamond-like carbon from a preceramic polymer. J. Am. Chem. Soc. 126, 3191–3202 (2004).
Best, S., Bianconi, P. & Merz, K. Structural analysis of Carbyne network polymers. J. Am. Chem. Soc. 117, 9251–9258 (1995).
Visscher, G. T. & Bianconi, P. A. Synthesis and characterization of polycarbynes, a new class of carbon-based network polymers. J. Am. Chem. Soc. 116, 1805–1811 (1994).
Paquette, L. A., Lagerwall, D. R. & Korth, H. G. The dodecahedryl radical—reactivity analysis by conjugate addition to pi-electron-deficient acceptors and structural investigation by electron-spin-resonance spectroscopy. J. Org. Chem. 57, 5413–5419 (1992).
Jhaveri, S., Beinhoff, M., Hawker, C., Carter, K. & Sogah, D. Chain-end functionalized nanopatterned functionalized polymer brushes grown via in situ nitroxide free radical exchange. ACS Nano. 2, 719–727 (2008).
Tsuji, Y., Ohno, K., Yamamoto, S., Goto, A. & Fukuda, T. Structure and properties of high-density polymer brushes prepared by surface-initiated living radical polymerization. Adv. Polym. Sci. 197, 1–45 (2006).
Zhu, H., Deng, G. & Chen, Y. Amphiphilic polymer brushes with alternating PCL and PEO grafts through radical copolymerization of styrenic and maleimidic macromonomers. Polymer 49, 405–411 (2008).
Juong, M., Ahn, J., Lee, D. & Yoon, N. Coupling reaction of alkenes with r-bromo carboxylic acid derivatives using nickel boride and borohydride exchange resin in methanol. J. Org. Chem. 63, 2755–2757 (1998).
Naji, L., Kaufmann, J., Huster, D., Schiller, J. & Arnold, K. C-13 NMR relaxation studies on cartilage and cartilage components. Carbohydr. Res. 327, 439–446 (2000).
Burrows, H. D., Knaapila, M., Monkman, A. P., Tapia, M. J., Fonseca, S. M., Ramos, M. L., Pyckhout-Hintzen, W., Pradhan, S. & Scherf, U. Structural studies on cationic poly{9,9-bis[6-(N,N,N-trimethylammonium) alkyl]fluorene-co-1,4-phenylene} iodides in aqueous solutions in the presence of the non-ionic surfactant pentaethyleneglycol monododecyl ether. J. Phys.—Condensed Matter 20, 104210 (2008).
Digilov, M., Vilcev, K., Zhikharev, A., Kovalev, A., Maluchkov, O., Sternin, S., Ilizarov, L. & Kostikov, V. Deposition of carbon-based coatings on the surface of carbon-fibers. Carbon 31, 365–371 (1993).
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We acknowledge Hexcel Corporation and DARPA (Contract HR0011-06-C-0011) for support of this research.
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Greco, J., Bianconi, P. A carbon network backbone polymer functionalized with polymer brushes. Polym J 42, 298–303 (2010). https://doi.org/10.1038/pj.2009.343
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DOI: https://doi.org/10.1038/pj.2009.343
