Abstract
Tripodal amphiphilic molecules toward organic–inorganic hybrid emulsions were successfully synthesized based on incompletely condensed polyhedral oligomeric silsesquioxanes (POSSs). The three silanol groups provide an excellent scaffold for the construction of three-dimensional amphiphilic molecules, thus well-defined tripodal amphiphilic POSS derivatives were readily synthesized. Thermal analyses revealed that an incompletely condensed POSS exhibited lower crystallinity without loss of thermal stability in comparison with a completely condensed POSS, whereas readily forms aggregates because of its high crystallinity. The newly synthesized tripodal amphiphilic POSSs possessed good solubility in water and effectively stabilized oil-in-water emulsions, while a conventional mono-substituted amphiphilic POSS did not work as an emulsifier because of its lack of water solubility. The prepared organic–inorganic hybrid emulsions were stable against coalescence, and no demulsification occurred over 1 month.
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
Usuki, A., Kojima, Y., Kawasumi, M., Okada, A., Fukushima, Y., Kurauchi, T. & Kamigaito, O. Synthesis of nylon 6-clay hybrid. J. Mater. Res. 8, 1179–1184 (1993).
Jousseaume, B., Lahcini, M., Rascle, M.-C., Ribot, F. & Sanchez, C. General routes to functional organotin trichlorides and trialkoxides involving the tricyclohexylstannyl group. Organometallics 14, 685–689 (1995).
Tamaki, R., Tanaka, Y., Asuncion, M. Z., Choi, J. & Laine, R. M. Octa(aminophenyl)silsesquioxane as a nanoconstruction site. J. Am. Chem. Soc. 123, 12416–12417 (2001).
Kageyama, K., Tamazawa, J. & Aida, T. Extrusion polymerization: catalyzed synthesis of crystalline linear polyethylene nanofibers within a mesoporous silica. Science 285, 2113–2115 (1999).
Naka, K., Yamaguchi, M. & Chujo, Y. Synthesis of poly(oxyethylene)-grafted palladium clusters. Chem. Mater. 11, 849–851 (1999).
Ramsden, W. Separation of solids in the surface-layers of solutions and ‘‘suspensions’’ (observations on surface-membranes, bubbles, emulsions, and mechanical coagulation). Proc. R. Soc. Lond. 72, 156–164 (1903).
Pickering, S. U. Emulsions. J. Chem. Soc. 91, 2001–2021 (1907).
Binks, B. P. & Horozov, T. S. Colloidal Particles at Liquid Interfaces (Cambridge University Press New York, USA, 2006).
Aveyard, R., Binks, B. P. & Clint, J. H. Emulsions stabilised solely by colloidal particles. Adv. Colloid Interface Sci. 100–102, 503–546 (2003).
Moore, W. C. Emulsification of water and of ammonium chloride solutions by means of lamp black. J. Am. Chem. Soc. 41, 940–946 (1919).
Lin, Y., Skaff, H., Emrick, T., Dinsmore, A. D. & Russell, T. P. Nanoparticle assembly and transport at liquid-liquid interfaces. Science 299, 226–229 (2003).
Wang, D., Duan, H. & Möhwald, H. The water/oil interface: the emerging horizon for self-assembly of nanoparticles. Soft Mater. 1, 412–416 (2005).
Takahara, Y. K., Ikeda, S., Ishino, S., Tachi, K., Ikeue, K., Sakata, T., Hasegawa, T., Mori, H., Matsumura, M. & Ohtani, B. Asymmetrically modified silica particles: a simple particulate surfactant for stabilization of oil droplets in water. J. Am. Chem. Soc. 127, 6271–6275 (2005).
Fujii, S., Okada, M. & Furuzono, T. Hydroxyapatite nanoparticles as stimulus-responsive particulate emulsifiers and building block for porous materials. J. Colloid Interface Sci. 315, 287–297 (2007).
Fujii, S., Okada, M., Sawa, H., Furuzono, T. & Nakamura, Y. Hydroxyapatite nanoparticles as particulate emulsifier: fabrication of hydroxyapatite-coated biodegradable microspheres. Langmuir 25, 9759–9766 (2009).
Fujii, S., Yokoyama, Y., Miyanari, Y., Shiono, T., Ito, M., Yusa, S. & Nakamura, Y. Micrometer-sized gold−silica Janus particles as particulate emulsifiers. Langmuir 29, 5457–5465 (2013).
Laine, R. M. Nanobuilding blocks based on the [OSiO1.5]x (x=6, 8, 10) octasilsesquioxanes. J. Mater. Chem. 15, 3725–3744 (2005).
Cordes, D. B., Lickiss, P. D. & Rataboul, F. Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chem. Rev. 110, 2081–2173 (2010).
Kuo, S. W. & Chang, F. C. POSS related polymer nanocomposites. Prog. Polym. Sci 36, 1649–1696 (2011).
Tanaka, K. & Chujo, Y. Advanced functional materials based on polyhedral oligomeric silsesquioxane (POSS). J. Mater. Chem. 22, 1733–1746 (2012).
Zhang, W.-B., Yu, W., Wang, C.-L., Sun, H.-J., Hsieh, I.-F., Li, Y., Dong, X.-H., Yue, K., Horn, R. V. & Cheng, S. Z. D. Molecular nanoparticles are unique elements for macromolecular science: from “nanoatoms” to giant molecules. Macromolecules 47, 1221–1239 (2014).
Tanaka, K., Adachi, S. & Chujo, Y. Structure-property relationship of octa-substituted POSS in thermal and mechanical reinforcements of conventional polymers. J. Polym. Sci. A Polym. Chem. 47, 5690–5697 (2009).
Tanaka, K., Adachi, S. & Chujo, Y. Side-chain effect of octa-substituted POSS fillers on refraction in polymer composites. J. Polym. Sci. A Polym. Chem. 48, 5712–5717 (2010).
Jeon, J.-H., Tanaka, K. & Chujo, Y. Rational design of POSS fillers for simultaneous improvements of thermomechanical properties and lowering refractive indices of polymer films. J. Polym. Sci. A Polym. Chem. 51, 3583–3589 (2013).
Fina, A., Monticelli, O. & Camino, G. POSS-based hybrids by melt/reactive blending. J. Mater. Chem. 20, 9297–9305 (2010).
Pramoda, K. P., Koh, C. B., Hazrat, H. & He, C. B. Performance enhancement of polylactide by nanoblending with POSS and graphene oxide. Polym. Compos 35, 118–126 (2014).
Blanco, I., Bottino, F. A., Cicala, G., Latteri, A. & Recca, A. Synthesis and characterization of differently substituted phenyl hepta isobutyl-polyhedral oligomeric silsesquioxane/polystyrene nanocomposites. Polym. Compos 35, 151–157 (2014).
Hayakawa, T., Seino, M., Goseki, R., Hirai, T., Kikuchi, R., Kakimoto, M., Tokita, M., Yokoyama, H. & Horiuchi, S. Fabrication of hierarchically ordered hybrid structures over multiple length scales via direct etching of self-organized polyhedral oligomeric silsesquioxane (POSS) functionalized block copolymer films. Polym. J. 38, 567–576 (2006).
Hirai, T., Leolukman, M., Hayakawa, T., Kakimoto, M. & Gopalan, P. Hierarchical nanostructures of organosilicate nanosheets within self-organized block copolymer films. Macromolecules 41, 4558–4560 (2008).
Hirai, T., Leolukman, M., Jin, S., Goseki, R., Ishida, Y., Kakimoto, M., Hayakawa, T., Ree, M. & Gopalan, P. Hierarchical self-assembled structures from POSS-containing block copolymers synthesized by living anionic polymerization. Macromolecules 42, 8835–8843 (2009).
Ishida, Y., Hirai, T., Goseki, R., Tokita, M., Kakimoto, M. & Hayakawa, T. Synthesis and self-assembly of thermotropic block copolymer with long alkyl tethered cage silsesquioxane in the side chain. J. Polym. Sci. A Polym. Chem. 49, 2653–2664 (2011).
Sun, D., Zhou, Z., Chen, G.-X. & Li, Q. Regulated dielectric loss of polymer composites from coating carbon nanotubes with a cross-linked silsesquioxane shell through free-radical polymerization. ACS Appl. Mater. Interfaces 6, 18635–18643 (2014).
Franczyk, A., He, H., Burdyńska, J., Hui, C. M., Matyjaszewski, K. & Marciniec, B. Synthesis of high molecular weight polymethacrylates with polyhedral oligomeric silsesquioxane moieties by atom transfer radical polymerization. ACS Macro Lett. 3, 799–802 (2014).
Wu, S., Hayakawa, T., Kikuchi, R., Grunzinger, S. J. & Kakimoto, M. Synthesis and characterization of semiaromatic polyimides containing POSS in main chain derived from double-decker-shaped silsesquioxane. Macromolecules 40, 5698–5705 (2007).
Wu, S., Hayakawa, T., Kakimoto, M. & Oikawa, H. Synthesis and characterization of organosoluble aromatic polyimides containing POSS in main chain derived from double-decker-shaped silsesquioxane. Macromolecules 41, 3481–3487 (2008).
Hoque, M. A., Kakihana, Y., Shinke, S. & Kawakami, Y. Polysiloxanes with periodically distributed isomeric double-decker silsesquioxane in the main chain. Macromolecules 42, 3309–3315 (2009).
Maegawa, T., Irie, Y., Fueno, H., Tanaka, K. & Naka, K. Synthesis and polymerization of a para-disubstituted T8-caged hexaisobutyl-POSS monomer. Chem. Lett. 43, 1532–1534 (2014).
Tamaki, R., Choi, J. & Laine, R. M. A polyimide nanocomposite from octa(aminophenyl)silsesquioxane. Chem. Mater. 15, 793–797 (2003).
Asuncion, M. Z. & Laine, R. M. Silsesquioxane barrier materials. Macromolecules 40, 555–562 (2007).
Tanaka, K., Inafuku, K., Adachi, S. & Chujo, Y. Tuning of properties of POSS-condensed water-soluble network polymers by modulating the crosslinking ratio between POSS. Macromolecules 42, 3489–3492 (2009).
Tanaka, K., Ohashi, W., Kitamura, N. & Chujo, Y. Glutathione-responsive molecular release using water-soluble POSS network polymers. Bull. Chem. Soc. Jpn. 84, 612–616 (2011).
Miyasaka, M., Fujiwara, Y., Kudo, H. & Nishikubo, T. Synthesis and characterization of hyperbranched polymer consisting of silsesquioxane derivatives. Polym. J. 42, 799–803 (2010).
Wu, J., Wu, Z. L., Yang, H. & Zheng, Q. Crosslinking of low density polyethylene with octavinyl polyhedral oligomeric silsesquioxane as the crosslinker. RSC Adv. 4, 44030–44038 (2014).
Li, Y., Dong, X.-H., Guo, K., Wang, Z., Chen, Z., Wesdemiotis, C., Quirk, R. P., Zhang, W.-B. & Cheng, S. Z. D. Synthesis of shape amphiphiles based on POSS tethered with two symmetric/asymmetric polymer tails via sequential “grafting-from” and thiol–ene “click” chemistry. ACS Macro Lett. 1, 834–839 (2012).
Yue, K., Liu, C., Guo, K., Yu, X., Huang, M., Li, Y., Wesdemiotis, C., Cheng, S. Z. D. & Zhang, W.-B. Sequential “click” approach to polyhedral oligomeric silsesquioxane-based shape amphiphiles. Macromolecules 45, 8126–8134 (2012).
Liu, H., Hsu, C.-H., Lin, Z., Shan, W., Wang, J., Jiang, J., Huang, M., Lotz, B., Yu, X., Zhang, W.-B., Yue, K. & Cheng, S. Z. D. Two-dimensional nanocrystals of molecular Janus particles. J. Am. Chem. Soc. 136, 10691–10699 (2014).
Feng, X., Zhu, S., Yue, K., Su, H., Guo, K., Wesdemiotis, C., Zhang, W.-B., Cheng, S. Z. D. & Li, Y. T10 polyhedral oligomeric silsesquioxane-based shape amphiphiles with diverse head functionalities via “click” chemistry. ACS Macro Lett. 3, 900–905 (2014).
Liu, D., Yu, B., Jiang, X. & Yin, J. Responsive hybrid microcapsules by the one-step interfacial thiol–ene photopolymerization. Langmuir 29, 5307–5314 (2013).
Liu, D., Jiang, X. & Yin, J. One-step interfacial thiol-ene photopolymerization for metal nanoparticle-decorated microcapsules (MNP@MCs). Langmuir 30, 7213–7220 (2014).
Ogi, K., Miyauchi, S. & Naka, K. Amphiphilic POSS-core dendrons for optically transparent thermoplastic films with tunable wettability. Polym. J. 47, 259–266 (2015).
Di Iulio, C., Jones, M. D., Mahon, M. F. & Apperley, D. C. Zinc(II) silsesquioxane complexes and their application for the ring-opening polymerization of rac-lactide. Inorg. Chem. 49, 10232–10234 (2010).
Zhou, J., Zhao, Y., Yu, K., Zhou, X. & Xie, X. Synthesis, thermal stability and photoresponsive behaviors of azobenzene-tethered polyhedral oligomeric silsesquioxanes. New J. Chem. 35, 2781–2792 (2011).
Yamahiro, M., Oikawa, H., Yoshida, K., Ito, K., Yamamoto, Y., Tanaka, M., Ootake, N., Watanabe, K., Ohno, K., Tsujii, Y. & Fukuda, T. Silicon compound useful as polymerization initiators PCT Int. Appl. WO 2004026883: A1 20040401
Ionescu, G., van der Vlugt, J. I., Abbenhuis, H. C. L. & Vogt, D. Synthesis and applications of chiral phosphite ligands derived from incompletely condensed silsesquioxane backbones. Tetrahedron 16, 3970–3975 (2005).
Bian, Y. & Mijović, J. Effect of side-chain architecture on dielectric relaxation in polyhedral oligomeric silsesquioxane/polypropylene oxide nanocomposites. Polymer 50, 1541–1547 (2009).
Lu, C.-H., Tsai, C.-H., Chang, F.-C., Jeong, K.-U. & Kuo, S.-W. Self-assembly behavior and photoluminescence property of bispyrenyl-POSS nanoparticle hybrid. J. Colloid Interface Sci. 358, 93–101 (2011).
Speier, J. L., Webster, J. A. & Barnes, G. H. The addition of silicon hydrides to olefinic double bonds. part II. The use of group VIII metal catalysts. J. Am. Chem. Soc. 79, 974–979 (1957).
Itami, K., Mitsudo, K., Nishino, A. & Yoshida, J. Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane. J. Org. Chem. 67, 2645–2652 (2002).
Araki, H. & Naka, K. Syntheses of dumbbell-shaped trifluoropropyl-substituted poss derivatives linked by simple aliphatic chains and their optical transparent thermoplastic films. Macromolecules 44, 6039–6045 (2011).
Acknowledgements
This study is part of a Grant-in-Aid for Scientific Research on Innovative Areas ‘New Polymeric Materials Based on Element-Blocks (no. 2401)’ (no. 24102003) of The Ministry of Education, Culture, Sports, Science and Technology of Japan.
Author information
Authors and Affiliations
Corresponding author
Additional information
Supplementary Information accompanies the paper on Polymer Journal website .
Supplementary information
Rights and permissions
About this article
Cite this article
Imoto, H., Nakao, Y., Nishizawa, N. et al. Tripodal polyhedral oligomeric silsesquioxanes as a novel class of three-dimensional emulsifiers. Polym J 47, 609–615 (2015). https://doi.org/10.1038/pj.2015.38
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2015.38
This article is cited by
-
Tripod-shaped POSS compounds as single-component silsesquioxane hybrids
Polymer Journal (2024)
-
Preparation of molecularly well-defined silicone resins based on trifluoropropyl-substituted trisilanol and their thermal, mechanical, and UV-resistance properties
Polymer Journal (2024)
-
Double-cyclopolymerization using trifunctional incompletely condensed cage silsesquioxane with methacryloyl groups
Polymer Journal (2023)
-
Development of macromolecules and supramolecules based on silicon and arsenic chemistries
Polymer Journal (2018)
-
Self-association behavior of amphiphilic molecules based on incompletely condensed cage silsesquioxanes and poly(ethylene glycol)s
Polymer Journal (2018)
