Abstract
A titanium phosphonate cluster with a formula of [Ti4(μ3-O)(OiPr)5(μ-OiPr)3(PhPO3)3]·thf was synthesized by the reaction of titanium tetraisopropoxide with phenylphosphonic acid in tetrahydrofuran and the following hydrolysis. The titanium cluster phosphonate was mixed with poly(dimethylsiloxane) (PDMS), poly(methylsilsesquioxane), poly(ethoxysilsesquioxane), poly(methyl methacrylate) (PMMA), poly(vinyl alcohol) (PVA), poly(4-vinylphenol), poly(styrene-co-allyl alcohol), or poly(bisphenol A-co-epichlorohydrin) to form a hybrid film. The mechanical strengths and strains of PDMS hybrids were very low. The tensile strengths and elongations of PMMA hybrids increased with the increase in the titanium cluster concentration. The tensile strengths and elongations of PVA hybrids were highest when the titanium cluster concentration was 10 wt%.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Chujo Y, Tanaka K (2015) New polymer materials based on element–blocks. Bull Chem Soc Jpn 88:633–643
Kanezashi M, Shioda T, Gunji T, Tsuru T (2012) Gas permeation properties of silica membranes with uniform pore sizes derived from polyhedral oligomeric silsesquioxane. AICHE J 58:1733–1743
Tanaka K, Yamane H, Mitamura K, Watase S, Matsukawa K, Chujo Y (2014) Transformation of sulfur to organic–inorganic hybrids employed by networks and their application for the modulation of refractive indices. J Polym Sci Part A Polym Chem 52:2588–2595
Cordes DB, Lickiss PD, Rataboul F (2010) Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chem Rev 110:2081–2173
Bradley DC, Mehrotra RC, Rothwell IP, Singh A (2001) Alkoxo and aryloxo derivatives of metals. Academic, San Diego
Schubert U (2004) Organofunctional metal oxide clusters as building blocks for inorganic-organic hybrid materials. J Sol-Gel Sci Techn 31:19–24
Rozes L, Steunou N, Fornasieri G, Sanchez C (2006) Titanium-oxo clusters, versatile nanobuilding blocks for the design of advanced hybrid materials. Monatsh Chem 137:501–528
Gross S (2011) Oxocluster-reinforced organic–inorganic hybrid materials: effect of transition metal oxoclusters on structural and functional properties. J Mater Chem 21:15853–15861
Schubert U (2011) Cluster-based inorganic–organic hybrid materials. Chem Soc Rev 40:575–582
Kickelbick G (2006) Hybrid materials. Wiley VCH, Weinheim
Guerrero G, Mutin PH, Vioux A (2000) Mixed nonhydrolytic/hydrolytic sol−gel routes to novel metal oxide/phosphonate hybrids. Chem Mater 12:1268–1272
Guerrero G, Mehring M, Mutin PH, Dahan F, Vioux A (1999) Syntheses and single-crystal structures of novel soluble phosphonate- and phosphinato-bridged titanium oxo alkoxides. J Chem Soc Dalton Trans:1537–1538
Mehring M, Guerrero G, Dahan F, Mutin PH, Vioux A (2000) Syntheses, characterizations, and single-crystal x-ray structures of soluble titanium alkoxide phosphonates. Inorg Chem 39:3325–3332
Czakler M, Artner C, Schubert U (2013) Influence of the phosphonate ligand on the structure of phosphonate-substituted titanium oxo clusters. Eur J Inorg Chem:5790–5796
Czakler M, Artner C, Schubert U (2014) Acetic acid mediated synthesis of phosphonate-substituted titanium Oxo clusters. Eur J Inorg Chem 2014:2038–2045
Czakler M, Artner C, Schubert U (2015) Titanium oxo/alkoxo clusters with both phosphonate and methacrylate ligands. Monatsh Chem 146:1249–1256
Kalita L, Kalita AC, Murugavel R (2014) Organotitanium phosphates with free P–OH groups: synthesis, spectroscopy and solid state structures. J Organomet Chem 751:555–562
Sheldrick GM (1996) SADABS, program for Siemens area detector absorption correction. University of Göttingen, Germany
Sheldrick GM (1997) SHELXS-97, program for crystal structure solution. University of Göttingen, Germany
Armarego WLF, Chai C (2012) Purification of laboratory chemicals, 7th edn. Elsevier, Oxford
Otsuka T, Chujo Y (2010) Poly(methyl methacrylate) (PMMA)-based hybrid materials with reactive zirconium oxide nanocrystals. Polym J 42:58–65
Julián B, Gervais C, Cordoncillo E, Escribano P, Babonneau F, Sanchez C (2003) Synthesis and characterization of transparent PDMS-metal-oxo based organic–inorganic nanocomposites. Chem Mater 15:3026–3034
Hayami R, Wada K, Sagawa T, Tsukada S, Watase S, Gunji T (2017) Preparation and properties of organic-inorganic hybrid polymer films using [Ti4(μ 3-O)(OiPr)5(μ-OiPr)3(O3PPh)3]·thf. Polym J 49:223–228
Guńko VM, Borysenko MV, Pissis P, Spanoudaki A, Shinyashiki N, Sulim IY, Kulik TV, Palyanytsya BB (2007) Polydimethylsiloxane at the interfaces of fumed silica and zirconia/fumed silica. Appl Surf Sci 253:7143–7156
Adachi K, Hirano T (2008) Good linear relationship between logarithms of Eigen’s water exchange constants for several divalent metal ions and activation energies of corresponding metal-catalyzed alkoxysilane hydrolysis in ethylene-propylene copolymer system. Eur Polym J 44:542–549
Svetich GW, Voge AA (1972) The crystal and molecular structure of sym-trans-di-μ-phenoxyhexaphenoxydiphenolatodititanium (IV). Acta Crystallogr B 28:1760
Glaser RH, Wilkes GL (1988) Structure property behavior of polydimethylsiloxane and poly(tetramethylene oxide) modified TEOS based sol-gel materials V. effect of titaniumisopropoxide incorporation. Polym Bull 19:51–57
Liu M, Sun J, Sun Y, Bock C, Chen Q (2009) Thickness-dependent mechanical properties of polydimethylsiloxane membranes. J Micromech Microeng 19:35028–35031. https://doi.org/10.1088/0960-1317/19/3/035028
Lee DC, Jang LW (1996) Preparation and characterization of PMMA–clay hybrid composite by emulsion polymerization. J Appl Polym Sci 61:1117–1122
Acknowledgments
This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “New Polymeric Materials Based on Element-Blocks (No.2401)” (JSPS KAKENHI Grant Number JP24102008). This work was supported by JSPS KAKENHI Grant Number JP16K17951.
Shinji Ogihara, Ryuta Kitamura, and Ryosuke Matsuzaki are greatly acknowledged for their technical assistance in the tensile strength measurement.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2019 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Gunji, T., Tsukada, S. (2019). Metalloxane Cage Compounds as an Element-Block. In: Chujo, Y. (eds) New Polymeric Materials Based on Element-Blocks. Springer, Singapore. https://doi.org/10.1007/978-981-13-2889-3_12
Download citation
DOI: https://doi.org/10.1007/978-981-13-2889-3_12
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-13-2888-6
Online ISBN: 978-981-13-2889-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)