Abstract
To identify components with different spin–spin relaxation times, T2, in the solid-echo pulse proton nuclear magnetic resonance (1H-NMR) spectra of crude acrylonitrile (AN)–butadiene rubbers (NBRs) with five different AN contents, we tried to understand the inhomogeneity in the crude NBRs in terms of their microstructures and molecular mobilities. The results of small-angle X-ray scattering, differential scanning calorimetry and dynamic mechanical analysis showed that crude NBRs have a single-phase and homogeneous morphology on the nanoscale. The microstructure of the crude NBRs shows alternately copolymerized AN–butadiene (BU) and BU block sequences, as indicated by 1H-NMR spectra. The T2 of the crude NBRs revealed three components with different molecular mobilities, even in homogeneous samples. The content of the highest-mobility component with T2l is negligible. Judging from the AN content dependence of the 1H ratio of these components, the low-mobility component with T2s and high-mobility component with T2m were assigned to the alternately copolymerized AN–BU sequences and BU block sequences, respectively.
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References
Borgia, G. C., Fantazzini, P., Ferrando, A. & Maddinelli, G. Characterisation of crosslinked elastomeric materials by 1H NMR relaxation time distributions. Magn. Reson. Imaging 19, 405–409 (2001).
Whittaker, A. K., Bremner, T. & Zelaya, F. O. The effect of field inhomogeneities and molecular diffusion on the NMR transverse relaxation behaviour of polymer melts. Polymer 36, 2159–2164 (1995).
Garrido, L., Mark, J. E., Sun, C. C., Ackerman, J. L. & Chang, C. NMR characterization of elastomers reinforced with in situ precipitated silica. Macromolecules 24, 4067–4072 (1991).
O'Brien, J., Cashell, E., Wardell, G. E. & McBrierty, V. J. An NMR investigation of the interaction between carbon black and cis-polybutadiene. Macromolecules 9, 653–660 (1976).
Fukumori, K., Kurauchi, T. & Kamigaito, O. Pulsed NMR study of elastomeric block copolymer under deformation. J. Appl. Polym. Sci. 38, 1313–1334 (1989).
Uehara, H., Yamanobe, T. & Komoto, T. Relationship between solid-state molecular motion and morphology for ultrahigh molecular weight polyethylene crystallized under different conditions. Macromolecules 33, 4861–4870 (2000).
Fukumori, K., Norio Sato, N. & Kurauchi, T. Deformation behaviors of nitrile rubber vulcanizates as studied by pulsed NMR: effects of carbon black fillers. Nippon Gomu Kyoukaishi 61, 561–566 (1988).
Faghihi, F., Mohammadi, N. & Hazendonk, P. Effect of restricted phase segregation and resultant nanostructural heterogeneity on glass transition of nonuniform acrylic random copolymers. Macromolecules 44, 2154–2160 (2011).
Kipper, M. J., Hou, S. -S., Seifert, S., Thiyagarajan, P., Schmidt-Rohr, K. & Narasimhan, B. Nanoscale morphology of polyanhydride copolymers. Macromolecules 38, 8468–8472 (2005).
Kwak, S. -Y. & Kim, S. Y. Microphase structures of polymers containing structural heterogeneity as probed by n.m.r. spin–lattice relaxation analysis. Polymer 39, 4099–4105 (1998).
Anachkov, M. P., Stefanova, R. V. & Rakovsky, S. K. 1H NMR study of monomer sequence distributions in some commercial acrylonitrile–butadiene copolymers. Br. Polym. J. 21, 429–432 (1989).
Pai Verneker, V. R. & Shaha, B. On coloration of polyacrylonitrile: a nuclear magnetic resonance study. Macromolecules 19, 1851–1856 (1986).
Matsuda, H., Asakura, T. & Miki, T. Triad sequence analysis of poly(ethylene/butylene terephthalate) copolymer using 1H NMR. Macromolecules 35, 4664–4668 (2002).
Hiemenz, P.C & Lodge, T. P. Polymer Chemistry 2nd edn. Vol. 168, (CRC Press, New York, NY, USA, 2007).
Greenley, R.Z. in Polymer Handbook 4th edn (eds. Brandrup J., Immergut E. H., Grulke E. A., Abe A., Bloch D. R.) Ch. 2, 203 (Wiley, New York, NY, USA, 1999).
Wang, X. -S., Kim, H. -K., Fujita, Y., Sudo, A., Nishida, H. & Endo, T. Relaxation and reinforcing effects of polyrotaxane in an epoxy resin matrix. Macromolecules 39, 1046–1052 (2006).
Rigaku X-ray Research Laboratory. X-ray diffraction Handbook 115–116 (Rigaku, Japan, 2000).
Chandler, L. A. & Collins, E. A. Multiple glass transitions in butadiene–acrylonitrile copolymers. J. Appl. Polym. Sci. 13, 1585–1593 (1969).
Hashimoto, K. in Rubber Industrial Handbook (The Society of Rubber Science and Technology Ch. 2, 238 (The Society of Rubber Science and Technology, 1994).
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This research has been supported by the New Energy and Industrial Technology Development Organization (NEDO) ‘Fundamental Research Project on Advanced Hydrogen Science (2006–2012)’.
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Ono, H., Fujiwara, H. & Nishimura, S. Nanoscale heterogeneous structure of polyacrylonitrile-co-butadiene with different molecular mobilities analyzed by spin–spin relaxation time. Polym J 45, 1027–1032 (2013). https://doi.org/10.1038/pj.2013.37
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DOI: https://doi.org/10.1038/pj.2013.37