Abstract
Original telomers based on vinylidene fluoride (VDF), CnF2n+1(VDF)m(CH2CH2)pI, where n=4 or 6, m=5–23 and p=0 or 1, were synthesized, and the piezoelectric properties of the materials were investigated. Low-molecular-weight polyvinylidene fluorides (PVDFs) were prepared in good yields by iodine transfer polymerization of VDF. The polymerization of VDF was conducted in the presence of 1-iodoperfluoroalkanes (C4F9I or C6F13I) and bis(4-tert-butylcyclohexyl) peroxydicarbonate, which were used as a chain transfer agent and initiator, respectively. The microstructures of VDF telomers were carefully characterized by 1H and 19F nuclear magnetic resonance (NMR) spectroscopy to assess the average molecular weights and the percentage of CH2CF2I functionality (that ranged from 47 to 86%). X-ray diffraction patterns of these telomers indicated that PVDFs with <7 VDF units displayed the α-form. Alternatively, telomers containing a higher amount of VDF possessed both α- and β-forms. Ethylene endcapping of CnF2n+1(VDF)mI was also successfully achieved in high yield, and the telomeric precursors were converted quantitatively. Moreover, three VDF telomers were vaporized into films, and the piezoelectric properties of the materials were assessed. The results revealed that C6F13(VDF)23I and C4F9(VDF)21I telomer films displayed piezoelectric responses (d33=268 pC N−1) and high remanent polarizations (Pr=98.2 and 93.4 mC m−2, respectively). In addition, C4F9(VDF)21C2H4I exhibited interesting ferroelectric properties (Pr=89.9 mC m−2).
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References
Seiler, D. A. In: Modern Fluoropolymers; PVDF in the Chemical Process Industry (ed. Scheirs, J.) Ch. 25, 487–506 (Wiley, New York, 1997).
Humphrey, J. S. & Amin-Sanayeid, R Vinylidene fluoride polymers. Encyclop. Polym. Sci. Techn. 4, 510–533 (2004).
Ameduri, B. From vinylidene fluoride (VDF) to the applications of VDF-containing copolymers: recent developments and future trends. Chem. Rev. 109, 6632–6686 (2009).
Lovinger, A. Poly(vinylidene fluoride). Dev. Cryst. Poly. 1, 195–273 (1982).
Bachman, M. A. & Lando, J. B. A reexamination of the crystal structure II of poly(vinylidene fluoride). Macromolecules 14, 40–46 (1981).
Takashima, K., Horie, S., Mukai, T., Ishida, K. & Matsushige, K. Piezoelectric properties of vinylidene fluoride oligomers for use in medical tactile sensor applications. Sens. Actuators A 144, 90–96 (2008).
Takashima, K., Horie, S., Mukai, T., Ishida, K. & Matsushige, K. Piezoelectric properties of vinylidene fluoride oligomers for use in tactile sensor. J. Robotics Soc. Jpn. 26, 243–249 (2008) (in Japanese).
Matsumoto, A., Horie, S., Yamada, H., Matsushige, K., Kuwajima, S. & Ishida, K. Ferro- and piezoelectric properties of vinylidene fluoride oligomer thin film fabricated on flexible polymer film. Appl. Phys. Lett. 90, 202906/1–202906/3 (2007).
Noda, K., Ishida, K., Kubono, A., Horiuchi, T., Yamada, H. & Matsushige, K. Remanent polarization of evaporated films of vinylidene fluoride oligomers. J Appl. Phys. 93, 2866–2870 (2003).
Ameduri, B., Ladavière, C., Delolme, F. & Boutevin, B. First MALDI-TOF mass spectrometry of vinylidene fluoride telomers endowed with low defect chaining. Macromolecules 37, 7602–7609 (2004).
Ameduri, B. & Boutevin, B. In: Well-architectured fluoropolymers: synthesis, properties and applications Ch.1, 1–99 (Elsevier, Amsterdam, 2004).
David, G., Boyer, C., Tonnar, J., Ameduri, B., Lacroix-Desmazes, P. & Boutevin, B. Use of Iodocompounds in Radical Polymerization. Chem. Rev. 106, 3936–3962 (2006).
Boyer, C., Valade, D., Sauguet, L., Ameduri, B. & Boutevin, B. Iodine Transfer Polymerization (ITP) of Vinylidene Fluoride (VDF). Influence of the Defect of VDF on the Control of ITP. Macromolecules 38, 10353–10362 (2005).
Boyer, C., Valade, D., Lacroix-Desmazes, P., Ameduri, B. & Boutevin, B. Kinetics of the iodine transfer polymerization of vinylidene fluoride. J. Polym. Sci. Part A: Polym. Chem. 44, 5763–5777 (2006).
Boyer, C., Ameduri, B., Boutevin, B., Dolbier, W. R., Winter, R. & Gard, G. Radical terpolymerization of 1,1,2-Trifluoro-2-pentafluorosulfanylethylene and pentafluorosulfanylethylene in the presence of vinylidene fluoride and hexafluoropropylene by iodine transfer polymerization. Macromolecules 41, 1254–1263 (2008).
Boyer, C., Ameduri & Hung, M. H. Telechelic diiodopoly(VDF-co-PMVE) copolymers by iodine transfer copolymerization of vinylidene fluoride (VDF) with perfluoromethyl vinyl ether (PMVE). Macromolecules 43, 3652–3663 (2010).
Abel, B., Assmann, J., Buback, M., Grimm, C., Kling, M., Schmatz, S., Schroeder, J. & Witte, T. Ultrafast degradation of carbonyloxy radicals: influence of molecular structure. J. Phys. Chem. A 107, 9499–9510 (2003).
Xu, W. Z., Li, X. & Charpentier, P. A. In situ ATR-FT-IR study of the thermal decomposition of diethyl peroxydicarbonate in supercritical carbon dioxide. Polymer 48, 1219–1228 (2007).
Buback, M., Frauendorf, H., Janssen, O. & Vana, P. Electrospray ionization mass spectrometric study of end-groups in peroxydicarbonate-initiated radical polymerization. J. Polym. Sci. Part A: Polym. Chem. 46, 6071–6081 (2008).
Timmerman, R. & Greyson, W. Predominant reaction of some fluorinated polymers to ionizing radiation. J. Appl. Polym. Sci. 6, 456–459 (1962).
Duc, M., Ameduri, B., Boutevin, B., Kharroubi, M. & Sage, J. M. Telomerization of vinylidene fluoride with methanol. elucidation of the reaction process and mechanism by a structural analysis of the telomers. Macromol. Chem. Phys. 199, 1271–1289 (1998).
Balague, J., Ameduri, B., Boutevin, B. & Caporiccio, G. Controlled step-wise telomerization of vinylidene fluoride, hexafluoropropene and trifluoroethylene with iodofluorinated transfer agent. J. Fluorine Chem. 102, 253–268 (2000).
Guiot, J., Ameduri, B. & Boutevin, B. Radical homopolymerization of vinylidene fluoride initiated by tert-butyl peroxypivalate. Investigation of the microstructure by 19F and 1H NMR spectroscopies and mechanisms. Macromolecules 35, 8694–8707 (2002).
Ameduri, B., Bauduin, G., Boutevin, B., Kostov, G. & Petrova, P. Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. 9. bulk copolymerization of vinylidene fluoride with 4,5,5-trifluoro-4-ene pentyl acetate. Macromolecules 32, 4544–4550 (1999).
Korlacki, R., Johnson, J. T., Kim, J., Ducharme, S., Thompson, D. W., Fridkin, V. M., Ge, Z. & Takacs, J. M. Oligo(vinylidene fluoride) langmuir-blodgett films studied by spectroscopic ellipsometry and the density functional theory. J. Chem. Phys. 129, 064704/1–064704/4 (2008).
Gregorio, R. & Ueno, E. M. Effect of crystalline phase, orientation and temperature on the dielectric properties of poly(vinylidene fluoride) (PVDF). J. Mat. Sci. 34, 4489–4500 (1999).
Ma, W., Zhang, J. & Wang, X. Formation of poly(vinylidene fluoride) crystalline phase from tetrahydrofuran/ N,N-dimethylformamide mixed solvent. J. Mat. Sci. 43, 398–401 (2008).
Manseri, A., Boulahia, D., Ameduri, B., Boutevin, B. & Caporiccio, G. Synthesis of telechelic dienes from fluorinated α,ω-diiodoalkanes. II. Divinyl and diallyl compounds containing tetrafluoroethylene, vinylidene fluoride and hexafluoropropene. J. Fluorine Chem. 81, 103–113 (1997).
Brace, N. O. Addition of perfluoroalkyl iodides to aliphatic olefins. US Patent 3016407 (Dupont De Nemours) 9 January (1962).
Knunyants, I. L., Khrakyan, S. P., Zeifman, Y. Y. & Shokina, V. V. Fluorinated diiodoalkanes and diolefins. Bull. Acad. Sci. USSR Div. Chem. Sci. 359–361 (1964).
Bloechl, W. Organic fluorine compounds. Dutch Patent, 6506069 (Hoescht) 15 November (1965).
Yang, Y. Z. Process using CF2I2 and olefins for producing diiodofluorocompounds, and products thereof. PCT Int. Appl., WO 97/44300 (Dupont De Nemours) 27 November (1997).
Renn, J. A., Toney, A. D., Terjeson, R. J. & Gard, G. L. A facil preparation of ICF2CF2I and its reaction with ethylene. J. Fluorine Chem. 86, 113–114 (1997).
Von Werner, K. Fluoroalkyl-substituted iodoalkanes. German Patent, DE 3338300 A1 (Hoescht), 2 May (1985).
Bargigia, G., Tonelli, C. & Tortelli, V. Process for the synthesis of mono- or dihydroxyfluoroalkanes as intermediates for textile treatment agents. Eur. Patent Appl., EP 0247614 A1 (Ausimont), 27 May (1987).
Fuchikami, T. & Urata, H. Preparation of fluorine-containing α,ω-bifunctional compounds as starting materials for fluorine-containing polymers. Eur. Patent Appl., EP 0383141 A2 (Sagami Chemical Research), 5 February (1990).
Urata, H., Kinoshita, Y., Asanuma, T., Kosukegawa, O. & Fuchikami, T. A facile Synthesis of α,ω-dicarboxylic acids containing perfluoroalkylene groups. J. Org. Chem. 56, 4996–4999 (1991).
Chambers, R. D., Greenhall, M. P., Wright, A. P. & Caporiccio, G. A new telogen for telechelic oligomers of chlorotrifluoroethylene. J. Chem. Soc. Chem. Comm. 18, 1323 (1991).
Manseri, A., Ameduri, B., Boutevin, B., Kotora, M., Hajek, M. & Caporiccio, G. Synthesis of telechelic dienes from fluorinated α,ω-diiodoalkanes. Part I. divinyl and diallyl derivatives from model I(C2F4)nI Compounds. J. Fluorine Chem. 73, 151–158 (1995).
Chambers, R. D., Greenhall, M. P., Wright, A. P. & Caporiccio, G. A new telogen for telechelic oligomers of chlorotrifluoroethylene. J. Fluorine Chem. 73, 87–94 (1995).
Li, A. R. & Chen, Q. Y. One-pot synthesis of dialkyldifluoromethane and alkyldifluoromethyl iodides from the reaction of difluorodiiodomethane with alkenes in sulfinatodehalogenation systems. J. Fluorine Chem. 82, 151–155 (1997).
Brace, N. O. Syntheses with perfluoroalkyl iodides. A review: Part III. Addition of RFI to norbornene esters, acids and anhydrides, alkenoic acids and esters, alkenylsuccinic anhydrides or diesters, and to vinyl monomers; lactonization and other reactions of adducts; hydroperfluoroalkylation by RFI; synthesis and reactions of I(CF2)nI homologues (n=1–3); perfluoroalkylation of arenes by RFI or [RFCO2]2; RF-I in the synthesis of RFSR and segmented RF(CH2)nSH; and, useful derivatives therefrom. J. Fluorine Chem. 108, 147–175 (2001).
Baum, K., Bedford, C. D. & Hunadi, R. J. Synthesis of fluorinated acetylenes. J. Org Chem. 47, 2251–2257 (1982).
Omote, K., Ohigashi, K. & Koga, K. Temperature dependence of elastic, dielectric, and piezoelectric properties of ‘single crystalline’ films of vinylidene fluoride-trifluoroethylene copolymer. J. Appl. Phys. 81, 2760–2769 (1997).
Durand, N., Ameduri, B. & Boutevin, B. Synthesis and characterization of functional fluorinated telomers. J. Polym. Sci.:Part A: Polym. Chem. (in press; doi:10.1002/pola.24420).
Acknowledgements
We thank all of the companies (Atofina, Solvay and Akzo Nobel) that contributed to this work by providing reactants, Professor Boutevin for fruitful discussion and G Coste for improvements of autoclave Laboratory facilities. This work was partially supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan and the Japan Science and Technology Agency, and by ARPE project funded by Région Languedoc Roussillon.
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Durand, N., Ameduri, B., Takashima, K. et al. Vinylidene fluoride telomers for piezoelectric devices. Polym J 43, 171–179 (2011). https://doi.org/10.1038/pj.2010.102
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DOI: https://doi.org/10.1038/pj.2010.102
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