Abstract
We studied the structure of polybutadiene rubber (BR) crosslinked with zinc diacrylate (ZDA) by using small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) to elucidate the regions of high crosslink density in the matrix rubber. The SAXS profiles of the swollen rubber materials with toluene were described well by a model that considers the hierarchical structure of the ZDA aggregates. By contrast, the SANS profiles of the swollen rubber materials with deuterated toluene were not well described by the same model, suggesting an influence of the high crosslink density region in the matrix rubber. We then considered the contributions of the high crosslink density segments of the BR (HC-BR) and the hierarchical structure of the ZDA aggregates, and succeeded in describing the SANS curves fairly well. This paper is the first report on high crosslink density segments in BR crosslinked with ZDA. We also performed tensile measurements on the sample and compared the results with those from the SAXS/SANS measurements, revealing that the size and the number density of the HC-BR and ZDA aggregates are related to the mechanical properties of the rubber material.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Nagata, N., Sato, T., Fujii, T. & Saito, Y. Structure and mechanical properties of hydrogenated NBR/Zinc di-methacrylate vulcanizates. J. Appl. Polym. Sci. 53, 103–120 (1994).
Yuan, X., Zhang, Y., Peng, Z. & Zhang, Y. In situ preparation of magnesium methacrylate to reinforce NBR. J. Appl. Polym. Sci. 84, 1403–1408 (2002).
Wei, Z., Lu, Y., Yan, S., Meng, Y. & Zhang, L. Dramatic influence of curing temperature on micro-nano structure transform of HNBR filled with zinc dimethacrylate. J. Appl. Polym. Sci. 124, 288–295 (2012).
Wei, Z., Lu, Y., Meng, Y. & Zhang, L. Improved understanding of in-situ polymerization of zinc dimethacrylate: the solid bulk polymerization. Polymer 53, 1409–1417 (2012).
Chu, B. J., Wu, D. Q., Lundberg, R. D. & Macknight, W. J. Small-angle X-ray scattering (SAXS) studies of sulfonated polystyrene ionomers. 1. Anomalous SAXS. Macromolecules 26, 994–999 (1993).
Tsujita, Y., Yasuda, M., Takei, M., Kinoshita, T., Takizawa, A. & Yoshimizu, H. Structure of ionic aggregates of ionomers. 1. Variation in the structure of ionic aggregates with different acid content and degree of neutralization of ethylene and styrene ionomers. Macromolecules 34, 2220–2224 (2001).
Al-Hussein, M., Lohmeijer, B. G. G., Schubert, U. S. & de Jeu, W. H. Melt morphology of polystyrene-poly(ethylene oxide) metallo-supramolecular diblock copolymer. Macromolecules 36, 9281–9284 (2003).
Zhou, C. N., Chan, D. C. & Winey, I. K. Reconciling STEM and X-ray scattering data to determine the nanoscale ionic aggregate morphology in sulfonated polystyrene ionomers. Macromolecules 41, 6134–6140 (2008).
Seitz, E. M., Chan, D. C., Opper, L. K., Baughman, W. T., Wagener, B. K. & Winey, I. K. Nanoscale morphology in precisely sequenced poly(ethylene-co-acrylic acid) zinc ionomers. J. Am. Chem. Soc. 132, 8165–8174 (2010).
Luo, H., Klüppel, M. & Schneider, H. Study of filled SBR elastomers using NMR and mechanical measurements. Macromolecules 37, 8000–8009 (2004).
Steren, C. A. & Monti, G. A. Contribution of the methine group to the transverse 1H NMR relaxation in vulcanized natural rubbers. Macromolecules 37, 5624–5629 (2004).
Hayashi, S. & Komori, Y. Determination of residual dipolar interaction from transverse 1H NMR relaxation in elastomers. Solid State Nucl. Magn. Reson. 36, 167–171 (2009).
Shiga, K., Murakami, R., Shigemitsu, T., Kimura, H. & Kitago, T. Golf ball material and golf ball patent appl. no. 207716(JP) (2011).
Takenaka, M., Nishituji, S., Amino, N., Ishikawa, Y., Yamaguchi, D. & Koizumi, S. Structure analyses of swollen rubber-filler systems by using contrast variation SANS. Macromolecules 42, 308–311 (2009).
Ikeda, Y., Higashitani, N., Hijikata, K., Kukubo, Y., Morita, Y., Shibayama, M., Osaka, N., Suzuki, T., Endo, H. & Kohjiya, S. Vulcanization: new focus on a traditional technology by small-angle neutron scattering. Macromolecules 42, 2741–2748 (2009).
Suzuki, T., Osaka, N., Endo, H., Shibayama, M., Ikeda, Y., Asai, H., Higashitani, N., Kokubo, Y. & Kohjiya, S. Nonuniformity in cross-linked natural rubber as revealed by contrast-variation small-angle neutron scattering. Macromolecules 43, 1556–1563 (2010).
Russell, T. P., Lin, J. S., Spooner, S. & Wignall, G. D. Intercalibration of small-angle X-ray and neutron scattering data. J. Appl. Cryst. 21, 629–638 (1988).
Kishimoto, H., Shinohara, Y., Amemiya, Y., Inoue, K., Suzuki, Y., Takeuchi, A., Uesugi, K. & Yagi, N. Structural analysis of filler in rubber composite under stretch with time-resolved two-dimensional ultra-small-angle X-ray scattering. Rubber Chem. Technol. 81, 541–551 (2008).
Beaucage, G. Approximations leading to a unified exponential/power-law approach to small-angle scattering. J. Appl. Cryst. 28, 717–728 (1995).
Beaucage, G. Small-angle scattering from polymeric mass fractals of arbitrary mass-fractal dimension. J. Appl. Cryst. 29, 134–146 (1996).
Beaucage, G., Kammler, H. K. & Pratsinis, S. E. Particle size distributions from small-angle scattering using global scattering functions. J. Appl. Cryst. 37, 523–535 (2004).
Endo, H., Mihalescu, M., Monkenbusch, M., Allgaier, J., Gompper, G., Richter, D., Jakos, B., Sottmann, T., Strey, R. & Grillo, I. Effect of amphiphilic block copolymers on the structure and phase behavior of oil-water-surfactant mixtures. J. Chem. Phys. 115, 580–600 (2001).
Acknowledgements
We thank Dr Yamaguchi of the Japan Atomic Energy Agency for his kind support in the SANS measurements at Japan Research Reactor-3 SANS-J-II (Proposal No. 2010B-A37), Dr Hiroyasu Masunaga of the Japan Synchrotron Radiation Research Institute for his kind support in the SAXS measurements at SPring-8 BL03XU (Proposal No. 2010B7264), Dr Noboru Ohta of the Japan Synchrotron Radiation Research Institute for his kind support in the SAXS measurements at SPring-8 BL40B2 (Proposal No. 2010A1746) and Dr Masugu Sato of the Japan Synchrotron Radiation Research Institute for his kind support in the USAXS measurements at SPring-8 BL19B2 (Proposal No. 2010B1932).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Mashita, R., Kishimoto, H., Inoue, R. et al. Small-angle X-ray and neutron scattering analyses of highly crosslinked rubber with unsaturated carboxylic acid. Polym J 45, 57–63 (2013). https://doi.org/10.1038/pj.2012.200
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2012.200