Abstract
We developed a molecular filler based on polyhedral oligomeric silsesquioxane (POSS) containing halogenated aromatic substituents to increase the refractive indices (RIs) of polystyrene (PS). PS hybrid films with a series of POSS derivatives were prepared through the solution method, and RI measurements were performed. Accordingly, it was revealed that these halogenated POSS fillers can increase the RI of the films. In particular, the degree of increase was larger than those estimated by theoretical prediction, suggesting that the accumulation of polymer chains around the POSS filler plays a key role in the increasing effect. In addition, it was shown that critical losses of thermal and mechanical properties were barely observed by adding POSS fillers. Preparation without the conventional sol‒gel method for the single-molecule-type filler with high-RI polymer hybrids based on chain assembly can be demonstrated.
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References
Gon M, Tanaka K, Chujo Y. Creative synthesis of organic–inorganic molecular hybrid materials. Bull Chem Soc Jpn. 2017;90:463–74.
Tanaka K, Kozuka H, Ueda K, Jeon J-H, Chujo Y. POSS-based molecular fillers for simultaneously enhancing thermal and viscoelasticity of poly(methyl methacrylate) films. Mater Lett. 2017;203:62–7.
Ueda K, Tanaka K, Chujo Y. Fluoroalkyl POSS with dual functional groups as a molecular filler for lowering refractive indices and improving thermomechanical properties of PMMA. Polymers. 2018;10:1332.
Ueda K, Tanaka K, Chujo Y. Remarkably high miscibility of octa-substituted POSS with commodity conjugated polymers and molecular fillers for the improvement of homogeneities of polymer matrices. Polym J. 2016;48:1133–9.
Yuasa S, Sato Y, Imoto H, Naka K. Fabrication of composite films with poly(methyl methacrylate) and incompletely condensed cage-silsesquioxane fillers. J Appl Polym Sci. 2018;135:46033.
Tkachenko IM, Kobzar YL, Tkachenko VF, Stryutsky AV, Matkovska LK, Shevchenko VV et al. Novel branched nanostructures based on polyhedral oligomeric silsesquioxanes and azobenzene dyes containing different spacers and isolation groups. J Mater Chem C. 2018;6:4065–76.
Ledin PA, Tkachenko IM, Xu W, Choi I, Shevchenko VV, Tsukruk VV. Star-shaped molecules with polyhedral oligomeric silsesquioxane core and azobenzene dye arms. Langmuir. 2014;30:8856–65.
Araki H, Naka K. Syntheses and properties of star- and dumbbell-shaped POSS derivatives containing isobutyl groups. Polym J. 2012;44:340–6.
Ledin PA, Russell M, Geldmeier JA, Tkachenko IM, Mahmoud MA, Shevchenko V et al. Light-responsive plasmonic arrays consisting of silver nanocubes and a photoisomerizable matrix. ACS Appl Mater Interfaces. 2015;7:4902–12.
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. 2009;42:3489–92.
Imoto H, Ishida A, Hashimoto M, Mizoue Y, Yusa S, Naka K. Soluble network polymers based on trifunctional open-cage silsesquioxanes. Chem Lett. 2019;48:1266–69.
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 Part A: Polym Chem. 2013;51:3583–89.
Ueda K, Tanaka K, Chujo Y. Synthesis of POSS derivatives having dual types of Alkyl substituents via in situ sol−gel reactions and their application as a molecular filler for low-refractive and highly-durable materials. Bull Chem Soc Jpn. 2017;90:205–9.
Ueda K, Tanaka K, Chujo Y. Optical, electrical and thermal properties of organic−inorganic hybrids with conjugated polymers based on POSS having heterogeneous substituents. Polymers. 2019;11:44.
Kato K, Gon M, Tanaka K, Chujo Y. Stretchable conductive hybrid films consisting of cubic silsesquioxane-capped polyurethane and poly(3-hexylthiophene). Polymers. 2019;11:1195.
Gon M, Kato K, Tanaka K, Chujo Y. Elastic and mechanofluorochromic hybrid films with POSS-capped polyurethane and polyfluorene. Mater Chem Front. 2019;3:1174–80.
Gon M, Tanaka K, Chujo Y. Recent progress in the development of advanced element-block materials. Polym J. 2018;50:109–26.
Chujo Y, Tanaka K. New polymeric materials based on element-blocks. Bull Chem Soc Jpn. 2015;88:633–43.
Gon M, Sato K, Tanaka K, Chujo Y. Controllable intramolecular interaction of 3D arranged π-conjugated luminophores based on a POSS scaffold, leading to highly thermostable and emissive materials. RSC Adv. 2016;6:78652–60.
Suenaga K, Tanaka K, Chujo Y. Heat-resistant mechanoluminescent chromism of the hybrid molecule based on boron ketoiminate-modified octa-substituted polyhedral oligomeric silsesquioxane. Chem Eur J. 2017;23:1409–14.
Nakamura R, Narikiyo H, Gon M, Tanaka K, Chujo Y. An optical sensor for discriminating the chemical compositions and sizes of plastic particles in water based on water-soluble networks consisting of polyhedral oligomeric silsesquioxane presenting dual-color luminescence. Mater Chem Front. 2019;3:2690–5.
Narikiyo H, Gon M, Tanaka K, Chujo Y. Control of intramolecular excimer emission in luminophore-integrated ionic POSSs possessing flexible side-chains. Mater Chem Front. 2018;2:1449–55.
Minns RA, Gaudiana RA. Design and synthesis of high refractive index polymers II. J Macromol Sci. 1992;29:19–30.
Kudo H, Inoue H, Inagaki T, Nishikubo T. Synthesis and refractive-index properties of star-shaped polysulfides radiating from calixarenes. Macromolecules. 2009;42:1051–7.
Kudo H, Inoue H, Nishikubo T, Anada T. Syntheses and refractive-indices properties of novel octa-arms star-shaped polysulfides radiating from p-t-butylcalix[8]arene core. Polym J. 2006;38:289–97.
Kudo H, Sato K, Nishikubo T. Controlled insertion reaction of thiirane into carbamothioate: novel synthesis of well-defined polysulfide. Macromolecules. 2010;43:9655–9.
Kudo H, Aoki H, Nishikubo T. Temperature dependence of refractive index of films of well-defined linear and star-shaped polystyrenes. Chem Lett. 2008;37:282–3.
Tanaka K, Yamane H, Mitamura K, Watase S, Matsukawa K, Chujo Y. Transformation of sulfur to organic−inorganic hybrids employed by POSS networks and their application for the modulation of refractive indices. J Polym Sci Part A: Polym Chem. 2014;52:2588–95.
Tanaka K, Adachi S, Chujo Y. Side-chain effect of octa-substituted POSS fillers on refraction in polymer composites. J Polym Sci Part A: Polym Chem 2010;48:5712–7.
Evert A, James A, Hawkins T, Foy P, Stolen R, Dragic P et al. Longitudinally-graded optical fibers. Opt Express. 2012;20:17393–401.
Hutsel MR, Gaylord TK. Concurrent three-dimensional characterization of the refractive-index and residual-stress distributions in optical fibers. Appl Opt. 2012;51:5442–52.
Hu Z, Xia J, Liang Y, Wen J, Miao E, Chen J et al. Tunable random polymer fiber laser. Opt Exp. 2017;25:18422.
Groh W, Zimmermann A. What is the lowest refractive index of an organic polymer? Macromolecules. 1991;24:6660–3.
Tanio N, Irie M. Estimate of light scattering loss of amorphous polymer glass from its molecular structure. Jpn J Appl Phys Part I. 1997;36:743–8.
Yuasa S, Imoto H, Naka K. Synthesis and properties of hyperbranched polymers by polymerization of an AB3-type incompletely condensed cage silsesquioxane (IC-POSS) monomer. Polym J. 2018;50:879–87.
Araki H, Naka K. Syntheses of dumbbell-shaped trifluoropropyl-substituted POSS derivatives linked by simple aliphatic chains and their optical transparent thermoplastic films. Macromolecules. 2011;44:6039–45.
Tanaka K, Adachi S, Chujo Y. Structure-property relationship of octa-substituted POSS in thermal and mechanical reinforcements of conventional. Polym J Polym Sci Part A: Polym Chem. 2009;47:5690–7.
Salamah MS, Aktawan A. Product distribution of pyrolysis of polystyrene foam waste using catalyst of natural zeolite and nickel/silica. IOP Confer Ser Earth Environ Sci. 2018;175:012012.
Acknowledgements
This work was partially supported by the Nakatani Foundation for Advancement of Measuring Technologies in biomedical engineering (for KT) and a Grant-in-Aid for Scientific Research (B) (JP17H03067) and (A) (JP17H01220), for Scientific Research on Innovative Areas “New Polymeric Materials Based on Element-Blocks (No. 2401)” (JP24102013) and for Challenging Research (Pioneering) (JP18H05356).
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Ueda, K., Tanaka, K. & Chujo, Y. Molecular fillers for increasing the refractive index of polystyrene hybrids by chain assembly at polyhedral oligomeric silsesquioxane. Polym J 52, 523–528 (2020). https://doi.org/10.1038/s41428-019-0302-4
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DOI: https://doi.org/10.1038/s41428-019-0302-4