Abstract
Two fluoroalkyl end-capped vinyltrimethoxysilane oligomers [RF-(CH2CHSi(OMe)3)n-RF; RF = fluoroalkyl group] can be synthesized by reaction of fluoroalkanoyl peroxides [RF-C(=O)O-O(O=)C-RF] with vinyltrimethoxysilane under mild conditions. Fluorinated oligomers thus obtained have been applied to the sol-gel reactions in the presence of a wide range of guest molecules (Guest) under non-catalytic, alkaline or acidic conditions to provide the corresponding fluorinated oligomers/Guest composites. Some of these fluorinated composites were found to exhibit a superoleophilic/superhydrophobic characteristic on their surface, applying to not only the separation of oil and water but also the selective removal of fluorinated aromatic compounds in aqueous solutions. These findings will be reviewed in this article.
Graphical abstract
Similar content being viewed by others
References
Sawada, H, “Fluorinated Peroxide.” Chem. Rev., 96 1779–1808 (1996)
Sawada, H, Nakayama, M, Kikuchi, O, Yokoyama, Y, “MNDO MO Theoretical Study of Electronic Structure and Homolytic Dissociation of Perfluoroalkanoyl Peroxides.” J. Fluorine Chem., 50 393–410 (1990)
Sawada, H, “Fluoropolymers (Preparation by Aromatic Fluoroalkylation).” In: Salamone, JC, (ed.) Polymeric Materials Encyclopedia—Synthesis, Properties and Applications, Vol. 4, p. 2507. CRC Press Inc., Florida (1996)
Sawada, H, “Chemistry of Fluoroalkanoyl Peroxides, 1980–1998.” J. Fluorine Chem., 105 219–220 (2000)
Sawada, H, Kurachi, M, Maekawa, T, Kawase, T, Hayakawa, Y, Takishita, K, Tanedani, T, “Synthesis and Properties of Novel Perfluorocyclohexylated Compounds with Bis(perfluorocyclohexane carbonyl) Peroxide.” J. Appl. Polym. Sci., 72 1101–1108 (1999)
Sawada, H, Kurachi, M, Takishita, K, Tanedani, T, Terasawa, T, Hayakawa, Y, Kawase, T, “Synthesis and Applications of Bis(perfluorodecalin-1-carbonyl) Peroxide.” Eur. Polym. J., 37 1409–1415 (2001)
Sawada, H, Gong, Y-F, Minoshima, Y, Matsumoto, T, Nakayama, M, Kosugi, M, Migita, T, “Synthesis and Surfactant Properties of Fluoroalkylated Oligomers Containing Carboxy Groups.” J. Chem. Soc. Chem. Commun., 537–538 (1992)
Sawada, H, Minoshima, Y, Nakajima, H, “Reactions of Acrylic Acid with Fluoroalkanoyl Peroxides—the Formation of Acrylic Acid Oligomers Containing Two Fluoroalkylated End-Groups.” J. Fluorine Chem., 65 169–173 (1993)
Ameduri, B, Boutevin, B, Well—Architectured Fluoropolymers: Synthesis, Properties and Applications, pp. 231–348. Elsevier, Amsterdam (2004)
Imae, T, “Fluorinated Polymers.” Curr. Opin. Colloid Interface Sci., 8 307–314 (2003)
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, “Novel Self-Assembled Molecular Aggregates Formed by Fluoroalkyl End-Capped Oligomers and Their Application.” J. Fluorine Chem., 121 111–130 (2003)
Ameduri, B, Sawada, H (eds) Fluorinated Polymers: Vol. 1, Synthesis, Properties, Processing and Simulation. RSC, Cambridge (2016)
Ameduri, B, Sawada, H (eds) Fluorinated Polymers: Vol. 2, Applications. RSC, Cambridge (2016)
Berret, J-F, Calvet, D, Collet, A, Viguier, M, “Fluorocarbon Associative Polymers.” Curr. Opin. Colloid Interface Sci., 8 296–306 (2003)
Imae, T, Tabuchi, H, Funayama, K, Sato, A, Nakamura, T, Amaya, N, “Self-Assemblies of Block Copolymer of 2-Perfluorooctylethyl Methacrylate and Methyl Methacrylate.” Colloids Surf. A: Physicochem. Eng. Asp., 167 73–81 (2000)
Lebreton, P, Ameduri, B, Boutevin, B, Corpart, JM, “Use of Original ω-Perfluorinated Dithioesters for the Synthesis of Well-Controlled Polymers by Reversible Addition-Fragmentation Chain Transfer (RAFT).” Macromol. Chem. Phys., 203 522–537 (2002)
Monteiro, MJ, Adamy, MM, Leeuwen, BJ, Van Herk, AM, Destarac, M, “A ‘Living’ Radical ab Initio Emulsion Polymerization of Styrene Using a Fluorinated Xanthate Agent.” Macromolecules, 38 1538–1541 (2005)
Feiring, AE, Wonchoba, ER, Davdson, F, Percec, V, Barboiu, B, “Fluorocarbon-Ended Polymers: Metal Catalyzed Radical and Living Radical Polymerizations Initiated by Perfluoroalkylsulfonyl Halides.” J. Polym. Sci. Part A Polym. Chem., 38 3313–3335 (2000)
Destarac, M, Matyjaszewski, K, Silverman, E, Ameduri, B, Boutevin, B, “Atom Transfer Radical Polymerization Initiated with Vinylidene Fluoride Telomers.” Macromolecules, 33 4613–4615 (2000)
Shi, Z, Holdcroft, S, “Synthesis and Proton Conductivity of Partially Sulfonated Poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) Block Copolymers.” Macromolecules, 38 4193–4201 (2005)
Jankova, K, Hvilsted, S, “Novel Fluorinated Block Copolymer Architectures Fuelled by Atom Transfer Radical Polymerization.” J. Fluorine Chem., 126 241–250 (2005)
Laruelle, G, Nicol, E, Ameduri, B, Tassin, J-F, Ajellal, N, “Synthesis of Poly(vinylidene fluoride)-b-Poly(styrene sulfonate) Block Copolymers by Controlled Radical Polymerizations.” J. Polym. Chem. Sci. Part A Polym. Chem., 49 3960–3969 (2011)
Patil, Y, Ameduri, B, “First RAFT/MADIX Radical Copolymerization of tert-Butyl 2-Trifluoromethacrylate with Vinylidene Fluoride Controlled by Xanthate.” Polym. Chem., 4 2783–2799 (2013)
Sawada, H, Ikeno, K, Kawase, T, “Synthesis of Amphiphilic Fluoroalkoxyl End-Capped Cooligomers Containing Oxime-Blocked Isocyanato Segments: Architecture and Applications of New Self-Assembled Fluorinated Molecular Aggregates.” Macromolecules, 35 4306–4313 (2002)
Sawada, H, Itoh, N, Kawase, T, Mitani, M, Nakajima, H, Nishida, M, Moriya, Y, “Synthesis and Surfactant Properties of Novel Amphiphilic Fluorinated Silicon Oligomers Containing Carboxy Groups.” Langmuir, 10 994–995 (1994)
Sawada, H, Tanba, K, Itoh, N, Hosoi, C, Oue, M, Baba, M, Kawase, T, Mitani, M, Nakajima, H, “Synthesis and Surfactant Properties of Novel Acrylic Acid Co-oligomers Containing Fluoroalkylated End-Groups: A New Approach to Polymeric Inhibitors of Human Immunodeficiency Virus Type-1.” J. Fluorine Chem., 77 51–64 (1996)
Nakagawa, J, Kamogawa, K, Sakai, H, Kawase, Y, Sawada, H, Manosroi, J, Manosroi, A, Abe, M, “Surface Chemical and Solution Properties of Fluorinated Silicon Oligomers with Carboxylic Acid Groups.” Langmuir, 14 2055–2060 (1998)
Nakagawa, J, Kamogawa, K, Momozawa, N, Sakai, H, Kawase, T, Sawada, H, Sano, Y, Abe, M, “Molecular Assemblies of Fluorinated Silicon Oligomers with Carboxylic Acid Groups: Effects of Chemical Oligomer Structure on Assembly Shape.” Langmuir, 14 2061–2067 (1998)
Sawada, H, Katayama, S, Ariyoshi, Y, Kawase, T, Hayakawa, Y, Tomita, T, Baba, M, “Fluorinated Functional Materials Possessing Biological Activities: Gel Formation of Novel Fluoroalkylated End-Capped 2-Acrylamido-2-methylpropanesulfonic Acid Polymers Under Non-crosslinked Conditions.” J. Mater. Chem., 8 1517–1524 (1998)
Sawada, H, Kawase, T, “Synthesis of Fluoroalkyl End-Capped Oligomers with Fluoroalkanoyl Peroxides-Architecture of Self-Assembled Aggregates of These Oligomers.” Kobunshi Ronbunshu, 58 147–160 (2001)
Sawada, H, Kawase, T, “Properties of Self-Assembled Aggregates of Fluoroalkyl End-Capped Oligomers.” Koubunshi Ronbunshu, 58 255–266 (2001)
Sawada, H, “Preparation and Applications of Novel Fluoroalkyl End-Capped Oligomeric Nanocomposites.” Polym. Chem., 3 46–65 (2012)
Sawada, H, Nakayama, M, “Synthesis of Fluorine-Containing Organosilicon Oligomers.” J. Chem. Soc. Chem. Commun., 677–678 (1991)
Sawada, H, “Preparation and Applications of Fluoroalkyl End-Capped Oligomeric Composites.” Acc. Mater. Surf. Res., 4 97–114 (2019)
Sawada, H, “Preparation and Applications of Fluoroalkyl End-Capped Oligomeric Composites.” In: Amuduri, B, Fomin, S (eds.) Opportunities for Fluoropolymers, pp. 189–207. Elsevier, Amsterdam (2020)
Sawada, H, “Preparation and Application of Fluoirnated Polymeric Composites by Using of Aggregation Imparted by Fluorine.” C & I Commun., 45 29–32 (2020)
Schwarzenbach, RP, Escher, BI, Fenner, K, Hofstetter, KTB, Johnson, CA, Gunten, UV, Wehrli, B, “The Challenge of Micropollutants in Aquatic Systems.” Science, 313 1072–1077 (2006)
Alsbaiee, A, Smith, BJ, Xiao, L, Ling, Y, Helbling, DE, Dichtel, WR, “Rapid Removal of Organic Micropollutants from Water by a Porous β-Cyclodextrin Polymer.” Nature, 529 190–196 (2016)
Allan, SE, Smith, BW, Anderson, KA, “Impact of the Deepwater Horizon Oil Spill on Bioavailable Polycyclic Aromatic Hydrocarbons in Gulf of Mexico Coastal Waters.” Environ. Sci. Technol., 46 2033–2039 (2012)
Chu, Z, Feng, Y, Seeger, S, “Oil/Water Separation with Selective Superantiwetting/Superwetting Surface Materials.” Angew. Chem. Int. Ed., 54 2328–2338 (2015)
Kintish, E, “An Audacious Decision in Crisis Gets Cautious Praise.” Science, 329 735–736 (2010)
Gupta, RK, Dunderdale, GJ, England, MW, Hozumi, A, “Oil/Water Separation Techniques: A Review of Recent Progresses and Future Directions.” J. Mater. Chem. A, 5 16025–16058 (2017)
Muller, K, Faeh, C, Diederich, F, “Fluorine in Pharmaceuticals: Looking Beyond Intuition.” Science, 317 1881–1886 (2006)
Isanbor, C, O’Hagan, D, “Fluorine in Medicinal Chemistry: A Review of Anti-cancer Agents.” J. Fluorine Chem., 127 303–319 (2006)
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 1569–1574 (2008)
Li, J, Wan, H, Ye, Y, Zhou, H, Chen, J, “One-Step Process to Fabrication of Transparent Superhydrophobic SiO2 Paper.” Appl. Sur. Sci., 261 470–476 (2012)
Si, Y, Guo, Z, “Superwetting Materials of Oil Water Emulsion Separation.” Chem. Lett., 44 874–883 (2015)
Sawada, H, Arakawa, K, Aomi, Y, “Wettability Control between Oleophobic /Superhydrophilic and Superoleophilic/Superhydrophobic Characteristics on the Modified Surface Treated with Fluoroalkyl End-capped Oligomers/Micro-sized Polystyrene Particle Composites.” Open J. Composite Mater. (in press)
Oikawa, Y, Saito, T, Yamada, S, Sugiya, M, Sawada, H, “Preparation and Surface Property of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Talc Composite-Encapsulated Organic Compounds: Application for the Separation of Oil and Water.” ACS Appl. Mater. Interfaces, 7 13782–13793 (2015)
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)
Goto, Y, Takashima, H, Takishita, K, Sawada, H, “Creation of Coating Surfaces Possessing Superhydrophobic and Superoleophobic Characteristics with Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Nanocomposites Having Biphenylene Segments.” J. Colloid Interface Sci., 362 375–381 (2011)
Katayama, S, Fujii, S, Saito, T, Yamazaki, S, Sawada, H, “Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica Nanocomposites Containing Gluconamide Units Possessing Highly Oleophobic/Superhydrophobic, Highly Oleophobic/Superhydrophilic, and Superoleophilic/Superhydrophobic Characteristics on the Modified Surfaces.” Polymers, 9 292 (2017)
Habibi, Y, Lucia, LA, Rojas, OJ, “Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications.” Chem. Rev., 110 3479–3500 (2010)
Arbatan, T, Zhang, L, Fang, X-Y, Shen, W, “Cellulose Nanofibers as Binder for Fabrication of Superhydrophobic Paper.” Chem. Eng. J., 210 74–79 (2012)
Sawada, H, Suto, Y, Saito, T, Oikawa, Y, Yamashita, K, Yamada, S, Sugiya, M, Suzuki, J, “Preparation of RF-(VM-SiO2)n-RF/AM-Cellu Nanocomposites, and Use Thereof for the Modification of Glass and Filter Paper Surfaces: Creation of a Glass Thermoresponsive Switching Behavior and an Efficient Separation Paper Membrane.” Polymers, 9 92 (2017)
Herrington, TM, Midmore, BR, “Adsorption of Ions at the Cellulose/Aqueous Electrolyte Interface. Part 2.—Determination of the Surface Area of Cellulose Fibres.” J. Chem. Soc. Faraday Trans., 80 1539–1552 (1984)
Navarro, RR, Sumi, K, Fujii, N, Matsumura, M, “Mercury Removal from Wastewater Using Porous Cellulose Carrier Modified with Polyethyleneimine.” Water Res., 30 2488–2494 (1996)
Inukai, Y, Tanaka, Y, Matsuda, T, Mihara, N, Yamada, K, Nambu, N, Itoh, O, Doi, T, Kaida, Y, Yasuda, S, “Removal of Boron(III) by N-Methylglucamine-Type Cellulose Derivatives with Higher Adsorption Rate.” Anal. Chim. Acta, 511 261–265 (2004)
Sawada, H, Yamamoto, S, Tono, K, Yamashita, K, “Preparation and Applications of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica/Chemically Modified Cellulose Fibers Composites.” Polym. Polym. Compos. (2021). https://doi.org/10.1177/0967391121992923
Teisala, H, Tuominen, M, Kunnsipalo, J, “Superhydrophobic Coatings on Cellulose-Based Materials: Fabrication, Properties, and Applications.” Adv. Mater. Interfaces, 1 1300026 (2014)
Nogi, M, Iwamoto, S, Nakagaito, AN, Yano, H, “Optically Transparent Nanofiber Paper.” Adv. Mater., 21 1595–1598 (2009)
Sawada, H, Endo, Y, Oikawa, Y, “Preparation and Applications of Wettability-Controlled Fluoroalkyl End-Capped Oligomer/Cellulose Nanofiber Composites.” J. Compos. Mater., 55 609–623 (2020)
Sawada, H, Chiba, M, Honma, G, Yamashita, K, Suzuki, J, “Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Micro-Sized Silica Composites Possessing Superoleophilic/Superhydrophobic Characteristic: Application to Selective Removal of Aromatic Compounds from Aqueous Methanol Solution by Using These Composites.” J. Sol-Gel Sci. Technol., 96 636–648 (2020)
Men, X, Ge, B, Li, P, Zhu, X, Shi, X, Zhang, Z, “Facile Fabrication of Superhydrophobic Sand: Potential Advantages for Practical Application in Oil-water Separation.” J. Taiwan Inst. Chem. Eng., 60 651–655 (2016)
Jianlin, L, Xiaofei, Z, Hongwei, Z, Fuping, W, Bigui, W, Qing, C, “Superhydrophobic Coating on Quartz Sand Filter Media for Oily Wastewater Filtration.” Colloids Surfaces A, 553 509–514 (2018)
Yan, Y, Zeng, X, Yang, K, Zhou, P, Xu, S, Pi, P, Li, H, Fang, J, Wang, S, Wen, X, “Janus Sand Filter with Excellent Demulsification Ability in Separation of Surfactant-Stabilized Oil/Water Emulsions: An Experimental and Molecular Dynamics Simulation Study.” J. Hazard. Mater., 418 126346 (2021)
Liu, P, Niu, L, Tao, X, Li, X, Zhang, Z, “Facile Preparation of Superhydrophobic Quarz Sands with Micro-Nano-Molecule Hierarchical Structure for Controlling the Permeability of Oil and Water Phase.” Colloid Surf. A, 569 1–9 (2019)
Wang, B, Chen, C, Li, Z, Wu, J, Liu, X, Wang, J, “One-Step Fabrication Superhydrophobic Sand Filter for Capillary-Driven Separation of Water-in-Oil Emulsions.” Chin. J. Chem. Eng., 33 70–75 (2021)
Li, J, Xu, C, Guo, C, Tian, H, Zha, F, Guo, L, “Underoil Superhydrophilic Desert Sand Layer for Efficient Gravity-Directed Water-in-Oil Emulsions Separation with High Flux.” J. Mater. Chem. A, 6 223–230 (2018)
Yong, J, Chen, F, Yang, Q, Bian, H, Du, G, Shan, C, Huo, J, Fang, Y, Hou, X, “Oil-Water Separation: A Gift from the Desert.” Adv. Mater. Interfaces, 3 1500650 (2016)
Yang, S, Li, M, Fang, G, Xue, M, Lu, Y, “Flexible Cement-Sand Coated Cotton Fabrics with Superhydrophilic and Underwater Superoleophobic Wettability for the Separation of Water/Oil Mixtures and Oil-in-Water Emulsions.” Colloids Surf. A, 608 125611 (2021)
Crini, G, “Recent Developments in Polysaccharide-Based Materials Used as Adsorbents in Wastewater Treatment.” Prog. Polym. Sci., 30 38–70 (2005)
Moine, L, Amiel, C, Brown, W, Guerin, P, “Associations Between a Hydrophobically Modified, Degradable, Poly(malic acid) and a β-Cyclodextrin Polymer in Solution.” Polym. Int., 50 663–676 (2001)
Crini, G, Bertini, S, Torri, G, Naggi, A, Sforzini, D, Vecchi, C, Janus, L, Lekchiri, Y, Morcellet, M, “Sorption of Aromatic Compounds in Water Using Insoluble Cyclodextrin Polymers.” J. Appl. Polym. Sci., 68 1973–1978 (1998)
Suzuki, J, Takegahara, Y, Oikawa, Y, Aomi, Y, Sawada, H, “Preparation of Fluoroalkyl End-Capped Oligomer/Cyclodextrin Polymer Composites: Development of Fluorinated Composite Material Having a Higher Adsorption Ability toward Organic Molecules.” J. Encapsulation Ads. Sci., 8 117–138 (2018)
Huber, DL, “Synthesis, Properties, and Applications of Iron Nanoparticles.” Small, 1 482–501 (2005)
Perez, JM, Simeone, FJ, Tsourkas, A, Josephson, L, Weissleder, R, “Peroxidase Substrate Nanosensors for MR Imaging.” Nano Lett., 4 119–122 (2004)
Yamashita, K, Okada, S, Sawada, H, “Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomeric Silica/Magnetite Composites—Application to Separation of Oil and Water.” Colloids Surf. A Physicochem. Eng. Asp., 581 123668 (2019)
Yamashita, K, Sasahara, S, Sawada, H, “Preparation of Monolithic Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Methyltrimethoxysilane/Magnetite Composites: Application to Selective Removal of Fluorinated Aromatic Compounds from Aqueous Methanol Solution Under Magnetic Field.” Compos. Part C Open Access, 1 100003 (2020)
Inoue, M, Sumii, Y, Shibata, N, “Contribution of Organofluorine Compounds to Pharmaceuticals.” ACS Omega, 5 10633–10640 (2020)
Ogawa, Y, Tokunaga, E, Kobayashi, O, Hirai, K, Shibata, N, “Current Contributions of Organofluorine Compounds to the Agrochemical Industry.” iScience, 23 101467 (2020)
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.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The author declares no competing conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Sawada, H. Preparation and applications of two fluoroalkyl end-capped vinyltrimethoxysilane oligomeric composites possessing superoleophilic/superhydrophobic characteristic: a review. J Coat Technol Res 19, 741–756 (2022). https://doi.org/10.1007/s11998-021-00598-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11998-021-00598-3