Abstract
Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF; n = 2, 3; RF = CF(CF3)OC3F7] undergoes sol–gel reactions in the presence of hexagonal boron nitride (h-BN) nanoparticles under alkaline or acidic conditions at room temperature to afford the corresponding fluorinated oligomeric silica/h-BN nanocomposites in good isolated yields (~ 80%), respectively. The fluorinated oligomeric silica/h-BN nanocomposites thus obtained were found to exhibit a good dispersibility toward the traditional organic media including water. These two kinds of fluorinated nanocomposites were applied to the surface modification of poly(methyl methacrylate) (PMMA). The fluorinated nanocomposites prepared under alkaline conditions can give not only a good oleophobic characteristic imparted by longer fluoroalkyl groups in the composites but also the higher fluorescent emission related to the presence of h-BN on the only surface side of the modified PMMA film. In contrast, the fluorinated nanocomposites prepared under acidic conditions can provide a good oleophobic characteristic and a higher fluorescent emission on both the surface and even on the reverse side of the PMMA film. Such unique controlled surface modification ability will be discussed by 29Si solid-state NMR spectra of these two types of the nanocomposites.
Graphic abstract
Surface arrangement of the RF-(VM-SiO2)n-RF/h-BN nanocomposites, which were prepared under alkaline or acidic conditions, toward the PMMA film
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References
Zheng, Z, Cox, M, Li, B, “Surface Modification of Hexagonal Boron Nitride Nanomaterials: A Review.” J. Mater. Sci., 53 66–99 (2018)
Yin, J, Li, J, Hang, Y, Yu, J, Tai, G, Li, X, Zhang, Z, Guo, W, “Boron Nitride Nanostructures: Fabrication, Functionalization and Applications.” Small, 12 2942–2968 (2016)
Cakmakci, E, Kocyigit, C, Cakir, S, Durmus, A, Kahraman, MV, “Preparation and Characterization of Thermally Conductive Thermoplastic Polyurethane/h-BN Nanocomposites.” Polym. Compos., (2014). https://doi.org/10.1002/pc.22692
Kim, K, Kim, M, Hwang, Y, Kim, J, “Chemically Modified Boron Nitride-Epoxy Terminated Dimethylsiloxane Composite for Improving the Thermal Conductivity.” Ceram. Int., 1 2047–2056 (2014)
Qin, L, Li, G, Hou, J, Yu, X, Ding, H, Zhang, Q, Wang, N, Qu, X, “Preparation, Characterization, and Thermal Properties of Poly(methyl methacrylate)/Boron Nitride Composites by Bulk Polymerization.” Polym. Compos., (2015). https://doi.org/10.1002/pc.2308
Gao, Y, Gu, A, Jiao, Y, Yang, Y, Liang, G, Hu, J-T, Yao, W, Yuan, L, “High-Performance Hexagonal Boron Nitride/Bismaleimide Composites with High Thermal Conductivity, Low Coefficient of Thermal Expansion, and Low Dielectric Loss.” Polym. Adv. Technol., 23 919–928 (2012)
Zhang, J, Wang, X, Yu, C, Li, Q, Li, Z, Li, C, Lu, H, Zhang, Q, Zhao, J, Hu, M, Yao, Y, “A Facile Method to Prepare Flexible Boron Nitride/Poly(vinyl alcohol) Composites with Enhanced Thermal Conductivity.” Compos. Sci. Technol., 149 41–47 (2017)
Song, W-L, Wang, P, Cao, L, Anderson, A, Meziani, MJ, Farr, AJ, Sun, Y-P, “Polymer/Boron Nitride Nanocomposite Materials for Superior Thermal Transport Performance.” Angew. Chem., 124 6604–6607 (2012)
Yang, N, Xu, C, Hou, J, Yao, Y, Zhang, Q, Grami, ME, He, L, Wang, N, Qu, X, “Preparation and Properties of Thermally Conductive Polyimide/Boron Nitride Composites.” RSC Adv., 6 18279–18287 (2016)
Gu, J, Lv, Z, Wu, Y, Guo, Y, Tian, L, Qiu, H, Li, W, Zhang, Q, “Dielectric Thermally Conductive Boron Nitride/Polyimide Composites with Outstanding Thermal Stabilities via In Situ Polymerization-Electrospinning-Hot Press Method.” Compos. Part A, 94 209–216 (2017)
Li, T-L, Hsu, SL-C, “Preparation and Properties of Thermally Conductive Photosensitive Polyimide/Boron Nitride Nanocomposites.” J. Appl. Polym. Sci., 121 916–922 (2011)
Wu, Y, Xue, Y, Qin, S, Liu, D, Wang, X, Hu, X, Li, J, Wang, X, Bando, Y, Golberg, D, Chen, Y, Gogotsi, Y, Lei, W, “BN Nanosheet/Polymer Films with Highly Anisotropic Thermal Conductivity for Thermal Management Applications.” ACS Appl. Mater. Interfaces, 9 43163–43170 (2017)
Wang, J, Wu, Y, Xue, Y, Liu, D, Wang, X, Hu, X, Bando, Y, Lei, W, “Super-Compatible Functional Boron Nitride Nanosheets/Polymer Films with Excellent Mechanical Properties and Ultra-high Thermal Conductivity for Thermal Management.” J. Mater. Chem. C, 6 1363–1369 (2018)
Wu, Y, Guo, M, Liu, G, Xue, S, Xia, Y, Liu, D, Lei, W, “Surface Modification of Boron Nitride Nanosheets by Polyelectrolytes via Atom Transfer Radical Polymerization.” Mater. Res. Express, 5 045026 (2018). https://doi.org/10.1088/2053-1591/aab8ec
Guo, M, Wu, Y, Xue, S, Xia, Y, Zhang, R, Liu, D, Lei, W, Zhang, T, “Surface Modification of Boron Nitride Nanosheets with Polycationic Electrolytes Through ARGET ATRP for Enhancing Mechanical Properties of Cellulose Film.” Mater. Lett., 242 127–130 (2019)
Xue, S, Wu, Y, Guo, M, Xia, Y, Liu, D, Zhou, H, Lei, W, “Self-healable Poly(acrylic Acid-co-Maleic Acid)/Glycerol/Boron Nitride Nanosheet Composite Hydrogels at Low Temperature with Enhanced Mechanical Properties and Water Retention.” Soft Matter., 15 3680–3688 (2019)
Xue, S, Wu, Y, Wang, J, Guo, M, Liu, D, Lei, W, “Boron Nitride Nanosheets/PNIPAM Hydrogels with Improved Thermo-responsive Performance.” Materials, 11 1069 (2018). https://doi.org/10.3390/ma11071069
Ameduri, B, Sawada, H (eds.), Fluorinated Polymers: Volume 1, “Synthesis, Properties, Processing and Simulation”. RSC, Cambridge (2016)
Ameduri, B, Sawada, H (eds.), Fluorinated Polymers: Volume 2, “Applications”. RSC, Cambridge (2016)
Sawada, H, “Fluorinated Peroxides.” Chem. Rev., 96 1779–1808 (1996)
Sawada, H, “Synthesis of Self-assembled Fluoroalkyl End-Capped Oligomeric Aggregates—Applications of These Aggregates to Fluorinated Oligomeric Nanocomposites.” Prog. Polym. Sci., 32 509–533 (2007)
Sawada, H, “Preparation and Applications of Novel Fluoroalkyl End-Capped Oligomeric Nanocomposites.” Polym. Chem., 3 46–65 (2012)
Sawada, H, “Novel Self-assembled Molecular Aggregates Formed by Fluoroalkyl End-Capped Oligomers and Their Application.” J. Fluorine Chem., 121 111–130 (2003)
Sawada, H, Suzuki, T, Takashima, H, Takishita, K, “Preparation and Properties of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Nanoparticles—A New Approach to Facile Creation of a Completely Superhydrophobic Coating Surface with These Nanoparticles.” Colloid Polym. Sci., 286 1569 (2008)
Sawada, H, Nakayama, M, “Synthesis of Fluorine-Containing Organosilicon Oligomers.” J. Chem. Soc. Chem. Commun., 10 677–678 (1991)
Mugisawa, M, Kasai, R, Sawada, H, “Cross-Linked Fluoroalkyl End-Capped Co-oligomeric Nanoparticle-Encapsulated Fullerene—A New Approach to the Surface Modification of Traditional Organic Polymers with Fullerene-Containing Nanoparticles.” Langmuir, 25 415–421 (2009)
Sawada, H, Yanagida, K, Inaba, Y, Sugiya, M, Kawase, T, Tomita, T, “Synthesis and Antibacterial Activity of Novel Fluoroalkyl End-Capped Cooligomers Containing Dimethyl(octyl) Ammonium Segments.” Eur. Polym. J., 37 1433–1439 (2001)
Suzuki, J, Takegahara, Y, Oikawa, Y, Chiba, M, Yamada, S, Sugiya, M, Sawada, H, “Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica/Poly(tetrafluoroethylene) Nanocomposites Possessing a Superoleophilic/Superhydrophobic Characteristic: Application to the Separation of Oil and Water.” J. Sol Gel Sci. Technol., 81 611–622 (2017)
Museur, L, Anglos, D, Petitet, J-P, Michel, J-P, Kanaev, AV, “Photoluminescence of Hexagonal Boron Nitride: Effect of Surface Oxidation Under UV-Laser Irradiation.” J. Photoluminescence, 127 595–600 (2007)
Kubota, Y, Watanabe, K, Tsuda, O, Taniguchi, T, “Deep Ultraviolet Light-Emitting Hexagonal Boron Nitride Synthesized at Atmospheric Pressure.” Science, 317 932–934 (2007)
Watanabe, K, Taniguchi, T, Kaneda, H, “Direct-Bandgap Properties and Evidence for Ultraviolet Lasing of Hexagonal Boron Nitride Single Crystal.” Nat. Mater., 3 404–409 (2004)
Watanabe, K, Taniguchi, GT, Kaneda, H, “Direct-Bandgap Properties and Evidence for Ultraviolet Lasing of Hexagonal Boron Nitride Single Crystal.” Phys. Stat. Sol. (a), 201 2561–2565 (2004)
Saengkaew, J, Ogasawara, T, Yamashita, K, Kongparakul, S, Sawada, H, “Preparation of Fluoroalkyl End-Capped Oligomers/Hexagonal Boron Nitride Nanocomposites Possessing No Weight Loss Behavior in Nanocomposites Even After Calcination at 800°C.” Open J. Compos. Mater., 9 72–98 (2019)
Wei, L, Shi, D, Zhou, Z, Ye, P, Wang, J, Zhao, J, Liu, L, Chen, C, Zhang, Y, “Functionalized Self-assembled Monolayers on Mesoporous Silica Nanoparticles with High Surface Coverage.” Nanoscale Res. Lett., 7 (334) 1–8 (2012)
Comotti, A, Bracco, S, Valsesia, P, Ferretti, L, Sozzani, P, “2D Multinuclear NMR, Hyperpolarized Xenon and Gas Storage in Organosilica Nanochannels with Crystalline Order in the Walls.” J. Am. Chem. Soc., 129 8566–8576 (2007)
Nishida, M, Tanaka, T, Kanematsu, W, “Solid–State NMR Study on Changes of Phosphate and Proton Species in Metal Pyrophosphate Composite (MP2O7–MO2) Ceramics.” Magn. Reson. Chem., 55 570–578 (2017)
Ide, M, El-Roz, M, De Canck, E, Vicente, A, Planckaert, T, Bogaerts, T, Van Driessche, I, Lynen, F, Van Speybroeck, V, Thybault-Starzyk, F, Van Der Voort, P, “Quantification of Silanol Sites for the Most Common Mesoporous Ordered Silicas and Organosilicas: Total Versus Accessible Silanols.” Phys. Chem. Chem. Phys., 15 642–650 (2013)
Acknowledgments
Thanks are due to MARUKA Co., Ltd., Gifu, Japan, for supplying h-BN nanoparticles.
Funding
This work was partially supported by a Grant-in-Aid for Scientific Research 19K05027 from the Ministry of Education, Science, Sports, and Culture, Japan.
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Saengkaew, J., Ogasawara, T., Yamashita, K. et al. Controlled surface modification of poly(methyl methacrylate) film by fluoroalkyl end-capped vinyltrimethoxysilane oligomeric silica/hexagonal boron nitride nanocomposites. J Coat Technol Res 17, 643–655 (2020). https://doi.org/10.1007/s11998-019-00261-y
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DOI: https://doi.org/10.1007/s11998-019-00261-y