Abstract
To realize thermoplastic near-infrared-absorbing resin materials with weak absorbance in the visible region, the solubility of thermostable alkyl phosphate ester copper complexes in poly(alkyl methacrylate) has been investigated for their use as near-infrared-absorbing dyes. C4–C12 alkyl phosphate ester copper complexes were synthesized and mixed with n-butyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate at 0.10 mol/g copper ion in the monomer solution. The obtained solutions were polymerized to prepare 3 mm resin plates, and the plate transparency was evaluated by a haze meter. 2-Ethylhexyl methacrylate solutions of the 2-ethylhexyl phosphate copper complex and the isodecyl phosphate copper complex maintained their transparency even after polymerization, so these two copper complexes show good solubility in poly(2-ethylhexyl methacrylate). Both of the resin plates have >80% visible light transmittance and <50% solar direct transmittance. Thus, these resin materials are suitable as window materials that require heat-shielding properties and transparency.
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References
Ashie Y, Ito D, Fujimoto T. Investigation on spectral characteristics of adhesive film for glazings. AIJ J Technol Des. 2008;14:487–90.
Katono H. Technology and features of solar heat shielding functional material. JETI. 2005;53:93–5.
Katono H. High performance heat shielding material with high visible transmittance. Chemistry and Chemical Industry 2005;58:1339–41.
Katono H, Ujiie T. KUREHA heat ray absorbing materials. Convertech. 2006;34:31–3.
Katono H. Visible light transparency and heat shielding effect of selective near infrared ray absorber. Sho-Energy. 2005;57:39–41.
Funabiki K, Yagi K, Nomoto M, Kubota Y, Matui M. Improvement of the thermal stability of near-infrared-absorbing heptamethinecyanine dyes by anion-exchange from an iodide to fluorine-containing anions. J Fluor Chem. 2015;174:132–6.
Salvador MA, Almeida P, Reis LV, Santos PF. Near-infrared absorbing delocalized cationic azo dyes. Dyes Pigments. 2009;82:118–23.
Liu Y, Zhang Z, Chen X, Xu S, Cao S. Near-infrared absorbing dyes at 1064 nm: Soluble dithiolene nickel complexes with alkylated electron-donating groups as Peripheral substituents. Dyes Pigments. 2016;128:179–89.
Cameron LA, Ziller JW, Heyduk AF. Near-IR absorbing donor–acceptor ligand-to-ligand charge-transfer complexes of nickel (II). Chem Sci. 2016;7:1807–14.
Liu P, Gao F, Zho L, Chen Y, Chen Z. Tetrathienyl-functionalized red-and NIR-absorbing BODIPY dyes appending various peripheral substituents. Org Biomol Chem. 2017;15:1393–9.
Zorlu Y, Kumru U, Isci U, Divrik B, Jeanneau E, Albrieux F, Dede Y, Ahsen V, Dumoulin F. 1,4,8,11,15,18,22,25-Alkylsulfanyl phthalocyanines: effect of macrocycle distortion on spectroscopic and packing properties. Chem Commun. 2015;51:6580–3.
Bricks JL, Kachkovskii AD, Slominskii YL, Gerasov AO, Popv SV. Molecular design of near infrared polymethine dyes: a review. Dyes Pigments. 2015;121:238–55.
Chao L, Bao L, Wei W, Tegus O, Zhang Z. Effects of nanoparticle shape and size on optical properties of LaB6. Plasmonics. 2016;11:697–701.
Zeng X, Zhou Y, Ji S, Luo H, Yao H, Huang X, Jin P. The preparation of a high performance near-infrared shielding CsxWO3/SiO2 composite resin coating and research on its optical stability under ultraviolet illumination. J Mater Chem C. 2015;3:8050–60.
Hayashi N, Machida K, Otawara K, Hasegawa A, Kosaka N. Polymer-soluble thermostable phosphate-ester copper complexes for near-infrared absorbing dyes with weak absorbance in the visible region. Opt Mater. 2018;77:111–6.
Hayashi N, Hoshi H, Katono H. Dissolution of Phosphate-Copper Complex to Polymer and Application to Thermoplastic Resin as Near Infrared Ray Cut-Off Filter. Kobunshi Ronbunshu. 2004;61:310–14.
NIST Chemistry WebBook. https://webbook.nist.gov/cgi/cbook.cgi?ID=C298077&Units=SI&Mask=80#IR-Spec. Accessed 15 July 2019.
Katono H, Sakagami T, Shoji M, Ogihara T. Introduction of Cu (II) complex into transparent synthetic resin and optical function of the resin as a near‐infrared ray cut-off filter. J Appl Poly Sci. 1998;67:903–12.
Goto Y, Yamauchi T, Ohkoshi Y, Nagura M. Structure of Cu (II) Complexes Formed with Phosphate Ligands in Polymethylmethacrylate. Kobunshi Ronbunshu. 2000;57:45–52.
Steytler DC, Jenta TR, Robinson BH. Structure of reversed micelles formed by metal salts of bis (ethylhexyl) phosphoric acid. Langmuir. 1996;12:1483–9.
Neuman RD, Zhou NF, Wu J, Jones MA, Gaonkar AG, Park SJ, Agrawal ML. General Model for Aggregation of Metal-Extractant Complex in Acidic Organophosphorus solvent extraction system. Sep Sci Tech. 1990;25:1655–74.
Kitahara A, Kon-no K. Mechanism of solubilization of water in nonpolar solutions of oil—soluble surfactants. J Phys Chem. 1966;70:3394–8.
Kon-no K, Kitahara A. Solubility behavior of water in nonaqueous solutions of oil-soluble surfactants: Effect of molecular structure of surfactants and solvents. J Colloid Interface Sci. 1971;37:469–75.
Kon-no K, Ueno Y, Ishii Y, Kitahara A. Temperature dependence for solubilization of water in nonaqueous solution of dialkyl sulfosuccinate salt. Nihon Kagaku Zasshi. 1971;92:381–386.
Kitahara A. Properties of surfactant in organic media. Aburagaku. 1985;34:46–51.
Ozaki S. Phosphorus-containing flame retardant. Kobunshi. 1973;22:235–9.
Acknowledgements
This work was funded by the Kureha Corporation. We thank Dr Sasanuma of Chiba University for helpful advice on article writing.
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Hayashi, N., Koshiji, A. Solubility of thermostable alkyl phosphate ester copper complexes in poly(alkyl methacrylate) for near-infrared-absorbing dyes. Polym J 52, 245–253 (2020). https://doi.org/10.1038/s41428-019-0255-7
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DOI: https://doi.org/10.1038/s41428-019-0255-7


