Hostname: page-component-5d59c44645-kw98b Total loading time: 0 Render date: 2024-03-02T07:02:45.667Z Has data issue: false hasContentIssue false

Block copolymers with stable radical and fluorinated groups by ATRP

Published online by Cambridge University Press:  03 July 2015

Clemens Liedel
Affiliation:
Materials Science and Engineering, 214 Bard Hall, Cornell University, Ithaca, New York 14853
Austin Moehle
Affiliation:
Applied and Engineering Physics, 271 Clark Hall, Cornell University, Ithaca, New York 14853
Gregory D. Fuchs
Affiliation:
Applied and Engineering Physics, 271 Clark Hall, Cornell University, Ithaca, New York 14853
Christopher K. Ober*
Affiliation:
Materials Science and Engineering, 214 Bard Hall, Cornell University, Ithaca, New York 14853
*
Address all correspondence to Christopher K. Ober atcko3@cornell.edu
Get access

Abstract

Polymers with stable radical groups are promising materials for organic electronic devices due to their unique redox activity. Block copolymers with one redox active block could be used in nanostructured devices for electronic applications. We report on the synthesis and characterization of such multifunctional block copolymers in which phase separation on the 10 nm (half pitch) scale is achieved by using fluorinated blocks. Fluorination of one block increases the degree of phase separation and leads to smaller accessible domain sizes. Block copolymers with 60%, 80% and 90% of a stable radical containing block and either fluorinated or non-fluorinated second blocks were made by atom transfer radical polymerization, and their microstructure formation as a function of fluorine content is described after solvent vapor or thermal annealing. Electrical characterization of such a partly fluorinated block copolymer shows their potential for electronic devices.

Type
Polymers/Soft Matter Research Letters
Copyright
Copyright © Materials Research Society 2015 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1.Griffith, O.H., Keana, J.F.W., Rottschaefer, S., and Warlick, T.A.: Preparation and magnetic resonance of nitroxide polymers. J. Am. Chem. Soc. 89, 5072 (1967).Google Scholar
2.Nakahara, K., Iwasa, S., Satoh, M., Morioka, Y., Iriyama, J., Suguro, M., and Hasegawa, E.: Rechargeable batteries with organic radical cathodes. Chem. Phys. Lett. 359, 351 (2002).Google Scholar
3.Oyaizu, K. and Nishide, H.: Radical polymers for organic electronic devices: a radical departure from conjugated polymers? Adv. Mater. 8555, 2339 (2009).CrossRefGoogle Scholar
4.Nakahara, K., Oyaizu, K., and Nishide, H.: Organic radical battery approaching practical use. Chem. Lett. 40, 222 (2011).Google Scholar
5.Janoschka, T., Hager, M.D., and Schubert, U.S.: Powering up the future: radical polymers for battery applications. Adv. Mater. 24, 6397 (2012).Google Scholar
6.Li, H-Q., Zou, Y., and Xia, Y-Y.: A study of nitroxide polyradical/activated carbon composite as the positive electrode material for electrochemical hybrid capacitor. Electrochim. Acta 52, 2153 (2007).Google Scholar
7.Kamachi, M., Tamaki, M., Morishima, Y., Nozakura, S-i, Mori, W., and Kishita, M.: Electron exchange phenomena of polymers containing nitroxyl radicals. Polym. J. 14, 363 (1982).Google Scholar
8.MacCorquodale, F., Crayston, J.A., Walton, J.C., and Worsfold, D.J.: Synthesis and electrochemical characterization of poly(TEMPO-Acrylate). Tetrahedron Lett. 31, 771 (1990).Google Scholar
9.Yonekuta, Y., Susuki, K., Oyaizu, K., Honda, K., and Nishide, H.: Battery-inspired, nonvolatile, and rewritable memory architecture: a radical polymer-based organic device. J. Am. Chem. Soc. 129, 14128 (2007).Google Scholar
10.Sukegawa, T., Omata, H., Masuko, I., Oyaizu, K., and Nishide, H.: Anionic polymerization of 4-methacryloyloxy-TEMPO using an MMA- capped initiator. ACS Macro Lett. 3, 240 (2014).Google Scholar
11.Oyaizu, K., Ando, Y., Konishi, H., and Nishide, H.: Nernstian adsorbate-like bulk layer of organic radical polymers for high-density charge storage purposes. J. Am. Chem. Soc. 130, 14459 (2008).CrossRefGoogle ScholarPubMed
12.Suga, T., Sakata, M., Aoki, K., and Nishide, H.: Synthesis of pendant radical- and ion-containing block copolymers via ring-opening metathesis polymerization for organic resistive memory. ACS Macro Lett. 3, 703 (2014).Google Scholar
13.Rostro, L., Baradwaj, A.G., and Boudouris, B.W.: Controlled radical polymerization and quantification of solid state electrical conductivities of macromolecules bearing pendant stable radical groups. ACS Appl. Mater. Interfaces 5, 9896 (2013).Google Scholar
14.Zhuang, X., Xiao, C., Oyaizu, K., Chikushi, N., Chen, X., and Nishide, H.: Synthesis of amphiphilic block copolymers bearing stable nitroxyl radicals. J. Polym. Sci. Part A Polym. Chem. 48, 5404 (2010).Google Scholar
15.Janoschka, T., Teichler, A., Krieg, A., Hager, M.D., and Schubert, U.S.: Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques. J. Polym. Sci. Part A Polym. Chem. 50, 1394 (2012).Google Scholar
16.Uemukai, T., Hioki, T., and Ishifune, M.: Thermoresponsive and redox behaviors of poly(N-isopropylacrylamide)-based block copolymers having TEMPO groups as their side chains. Int. J. Polym. Sci. 2013, 196145 (2013).Google Scholar
17.Saito, K., Hirose, K., Okayasu, T., Nishide, H., Milton, T., and Hearn, W.: TEMPO radical polymer grafted silicas as solid state catalysts for the oxidation of alcohols. RSC Adv. 3, 9752 (2013).Google Scholar
18.Wang, Y., Hung, M., and Lin, C.: Patterned nitroxide polymer brushes for thin-film cathodes in organic radical batteries. Chem. Commun. 47, 1249 (2011).CrossRefGoogle ScholarPubMed
19.Lin, H., Li, C., and Lee, J.: Nitroxide polymer brushes grafted onto silica nanoparticles as cathodes for organic radical batteries. J. Power Sources 196, 8098 (2011).Google Scholar
20.Lin, C-H., Chou, W-J., and Lee, J-T.: Three-dimensionally ordered macroporous nitroxide polymer brush electrodes prepared by surface-initiated atom transfer polymerization for organic radical batteries. Macromol. Rapid Commun. 33, 107 (2012).Google Scholar
21.Lin, C., Chau, C., and Lee, J.: Polymer Chemistry Synthesis and characterization of polythiophene grafted with a nitroxide radical polymer via atom transfer radical polymerization. Polym. Chem. 1467 (2012).Google Scholar
22.Hung, M-K., Wang, Y-H., Lin, C-H., Lin, H-C., and Lee, J-T.: Synthesis and electrochemical behaviour of nitroxide polymer brush thin-film electrodes for organic radical batteries. J. Mater. Chem. 22, 1570 (2012).Google Scholar
23.Hauffman, G., Rolland, J., Bourgeois, J., and Vlad, A.: Synthesis of nitroxide-containing block copolymers for the formation of organic cathodes. J. Polym. Sci. Part A Polym. Chem. 51, 101 (2013).Google Scholar
24.Behrends, F., Wagner, H., Studer, A., Niehaus, O., Pöttgen, R., and Eckert, H.: Polynitroxides from Alkoxyamine Monomers: Structural and Kinetic Investigations by Solid State NMR. Macromolecules 46, 2553 (2013).Google Scholar
25.Matsen, M.W., and Bates, F.S.: Unifying weak- and strong-segregation block copolymer theories. Macromolecules 29, 1091 (1996).Google Scholar
26.Nunns, A., Gwyther, J., and Manners, I.: Inorganic block copolymer lithography. Polymer (Guildf). 54, 1269 (2013).Google Scholar
27.Hillmyer, M.A., and Lodge, T.P.: Synthesis and self-assembly of fluorinated block copolymers. J. Polym. Sci. Part A Polym. Chem. 40, 1 (2002).Google Scholar
28.Nishide, H., Iwasa, S., Pu, Y-J., Suga, T., Nakahara, K., and Satoh, M.: Organic radical battery: nitroxide polymers as a cathode-active material. Electrochim. Acta 50, 827 (2004).Google Scholar
Supplementary material: PDF

Liedel supplementary material

Liedel supplementary material 1

Download Liedel supplementary material(PDF)
PDF 242 KB