Skip to main content

Advertisement

SpringerLink
Log in

Reaction of fluorinated aliphatic alcohols with calcium chloride: formation of the fluorinated alcohol/calcium fluoride nanocomposites—thermal stability and application to the surface modification of these nanocomposites

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

A variety of fluorinated aliphatic alcohols such as 1H,1H,2H,2H-nonafluoro-1-hexanol (FA-4), 1H,1H,2H,2H-tridecafluoro-1-n-octanol (FA-6), 1H,1H,2H,2H-heptadecafluoro-1-decanol (FA-8), 1H,1H,2H,2H,6H,6H-nonadecafluoro-1-undecanol (DTFA), 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(heptafluoropropoxy) propoxy]-1-propanol (PO-3-OH), and 2,4,4,5,7,7,8,10,10,11,13,13,14,16,16,17,17,18,18,18-icosafluoro-2,5,8,11,14-pentakis(trifluoromethyl)-3,6,9,12,15-pentaoxaoctadecane-1-ol (PO-6-OH) were applied to the reaction with calcium chloride under alkaline conditions. In these fluorinated alcohols, only the DTFA can react with calcium chloride under alkaline conditions to provide the corresponding fluorinated alcohol/calcium fluoride nanocomposites. This reactivity is due to the relatively higher acidity of the inside methylene unit in the DTFA, whose acidic protons should react with the neighboring fluorines and successively with calcium chloride under alkaline conditions to afford the DTFA/calcium fluoride nanocomposites. Interestingly, the DTFA/CaF2 nanocomposites were found to exhibit a no weight loss characteristic even after calcination at 800°C. More interestingly, the DTFA/CaF2 nanocomposites after calcination at 800°C are applicable to the surface modification of poly(methyl methacrylate) (PMMA) to exhibit both good oleophobicity and lower refractive indices imparted by longer fluoroalkyl units in the composites on the modified PMMA film surfaces, as well as those before calcination of the DTFA/CaF2 nanocomposites.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  1. Ameduri, B, Boutevin, B, “Copolymerization of Fluorinated Monomers: Recent Developments and Future Trends.” J. Fluor. Chem., 104 53–62 (2000)

    Article  Google Scholar 

  2. Dolbier, WR, Jr, “Fluorine Chemistry at the Millennium.” J. Fluor. Chem., 126 157–163 (2005)

    Article  Google Scholar 

  3. Imae, T, “Fluorinated Polymers.” Curr. Opin. Colloid Interface Sci., 8 307–314 (2003)

    Article  Google Scholar 

  4. Johns, K, Stead, G, “Fluoroproducts—The Extremophiles.” J. Fluor. Chem., 104 5–18 (2000)

    Article  Google Scholar 

  5. Renfrew, MM, Lewis, EE, “Polytetrafluoroethylene. Heat Resistant, Chemically Inert Plastic.” Ind. Eng. Chem., 38 870–877 (1946)

    Article  Google Scholar 

  6. Matsumoto, K, Kubota, M, Matsuoka, H, Yamaoka, H, “Water-Soluble Fluorine-Containing Amphiphilic Block Copolymer: Synthesis and Aggregation Behavior in Aqueous Solution.” Macromolecules, 32 7122–7127 (1999)

    Article  Google Scholar 

  7. Boschet, F, Kostov, G, Ameduri, B, Jackson, A, Boutevin, B, “Synthesis of 3,3,3-Trifluoropropene Telomers and Their Modification into Fluorosurfactants.” Polym. Chem., 3 217–223 (2012)

    Article  Google Scholar 

  8. 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)

  9. 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. Fluor. Chem., 65 169–173 (1992)

    Article  Google Scholar 

  10. Sawada, H, “Fluorinated Peroxides.” Chem. Rev., 96 1779–1808 (1996)

    Article  Google Scholar 

  11. Sawada, H, “Chemistry of Fluoroalkanoyl Peroxides, 1980–1998.” J. Fluor. Chem., 105 219–220 (2000)

    Article  Google Scholar 

  12. 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)

    Article  Google Scholar 

  13. Sawada, H, “Development of Fluorinated Polymeric Functional Materials Using Fluorinated Organic Peroxide as Key Material.” Polym. J., 39 637–650 (2007)

    Article  Google Scholar 

  14. Sawada, H, “Preparation and Applications of Novel Fluoroalkyl End-Capped Oligomeric Nanocomposites.” Polym. Chem., 3 46–65 (2012)

    Article  Google Scholar 

  15. 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)

    Article  Google Scholar 

  16. Sawada, H, Narumi, T, Kiyohara, M, Baba, M, “Preparation of Fluoroalkyl End-Capped Cooligomers/Silica Nanoparticles: A New Approach to Fluorinated Nanoparticle Inhibitors of Human Immunodeficiency Virus Type 1 and Simian Immunodeficiency Virus (SIVmac).” J. Fluor. Chem., 128 1416–1420 (2007)

    Article  Google Scholar 

  17. Sawada, H, Tashima, T, Kakehi, H, Nishiyama, Y, Kikuchi, M, Miura, M, Sato, Y, Isu, N, “Fluoroalkyl End-Capped Oligomers Possessing Nonflammable and Flammable Characteristics in Silica Gel Matrices After Calcination at 800 °C Under Atmospheric Conditions.” Polym. J., 42 167–171 (2010)

    Article  Google Scholar 

  18. Sawada, H, Izumi, S, Sasazawa, K, Yoshida, M, “Coloring–Decoloring Behavior of Amphiphilic Fluoroalkyl End-Capped N-(1,1-dimethyl-3-oxobutyl)acrylamide—Acryloylmorpholine Cooligomer/Fluorescein Nanocomposites in Protic and Aprotic Solvents.” J. Colloid Interface Sci., 377 76–80 (2012)

    Article  Google Scholar 

  19. Mugisawa, M, Sawada, H, “Architecture of Linear Arrays of Fluorinated Cooligomeric Nanocomposites-Encapsulated Gold Nanoparticles: A New Approach to the Development of Gold Nanoparticles Possessing an Extremely Red-Shifted Absorption Characteristic.” Langmuir, 24 9215–9218 (2008)

    Article  Google Scholar 

  20. Guo, S, Ogasawara, T, Saito, T, Kakehi, H, Kato, Y, Miura, M, Isu, N, Sawada, H, “Preparation and Photocatalytic Activity of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Anatase Titanium Oxide Nanocomposite-Encapsulated Low Molecular Weight Aromatic Compounds.” Colloid Polym. Sci., 291 2947–2957 (2013)

    Article  Google Scholar 

  21. Sawada, H, Shikauchi, Y, Kakehi, H, Katoh, Y, Miura, M, “Preparation and Applications of Novel Fluoroalkyl End-Capped Oligomers/Calcium Carbonate Nanocomposites.” Colloid Polym. Sci., 285 499–506 (2007)

    Article  Google Scholar 

  22. Saito, T, Kakehi, H, Kato, Y, Miura, M, Isu, N, Sawada, H, “Fluoroalkyl End-Capped Oligomers Possessing Nonflammable Characteristic in Calcium Carbonate Nanocomposites.” Polym. Adv. Technol., 24 532–540 (2013)

    Article  Google Scholar 

  23. Blue, G-D, Green, JW, Bautista, RG, Margrave, JL, “The Sublimation Pressure of Calcium (II) Fluoride and the Dissociation Energy of Calcium (I) Fluoride.” J. Phys. Chem., 67 877–882 (1963)

    Article  Google Scholar 

  24. Saito, T, Nishida, M, Fukaya, H, Kakehi, H, Kato, Y, Miura, M, Isu, N, Sawada, H, “Low Molecular Weight Aromatic Compounds Possessing Nonflammable and Flammable Characteristics in Calcium Fluoride Nanocomposite Matrices After Calcination at 800°C.” Colloid Polym. Sci., 291 945–953 (2013)

    Article  Google Scholar 

  25. Gaussian, 03, Revision, D.02, Frisch, MJ, Trucks, GW, Schlegel, HB, Scuseria, GE, Robb, MA, Cheeseman, JR, Montgomery, Jr. JA, Vreven, T, Kudin, KN, Burant, JC, Millam, JM, Iyengar, SS, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, GA, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, JE, Hratchian, HP, Cross, JB, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, RE, Yazyev, O, Austin, AJ, Cammi, R, Pomelli, C, Ochterski, JW, Ayala, PY, Morokuma, K, Voth, GA, Salvador, P, Dannenberg, JJ, Zakrzewski, VG, Dapprich, S, Daniels, AD, Strain, MC, Farkas, O, Malick, DK, Rabuck, AD, Raghavachari, K, Foresman, JB, Ortiz, JV, Cui, Q, Baboul, AG, Clifford, S, Cioslowski, J, Stefanov, BB, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, RL, Fox, DJ, Keith, T, Al-Laham, MA, Peng, CY, Nanayakkara, A, Challacombe, M, Gill, PMW, Johnson, B, Chen, W, Wong, MW, Gonzalez, C, Pople, JA, Gaussian, Inc., Wallingford CT (2004).

  26. Crowe, R, Badyal, JPS, “Surface Modification of Poly(vinylidene difluoride) (PVDF) by LiOH.” J. Chem. Soc. Chem. Commun., 958–959 (1991)

  27. Kise, H, Ogata, H, “Phase Transfer Catalysis in Dehydrofluorination of Poly(vinylidene fluoride) by Aqueous Sodium Hydroxide Solutions.” J. Polym. Sci.: Polym. Chem. Ed., 21 3443–3451 (1983)

    Google Scholar 

  28. Ross, GJ, Watts, JF, Hill, MP, Morrissey, P, “Surface Modification of Poly(vinylidene fluoride) by Alkaline Treatment 1. The Degradation Mechanism.” Polymer, 41 1685–1696 (2000)

    Article  Google Scholar 

  29. Ross, GJ, Watts, JF, Hill, MP, Morrissey, P, “Surface Modification of Poly(vinylidene fluoride) by Alkaline Treatment Part 2. Process Modification by the Use of Phase Transfer Catalysts.” Polymer, 42 403–413 (2001)

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Frontier Materials Chemistry, Graduate School of Science and Technology, Hirosaki University, Hirosaki, 036-8561, Japan

    Tomoya Saito, Shohei Yamazaki & Hideo Sawada

  2. Faculty of Agriculture and Life Science, Hirosaki University, Hirosaki, 036-8561, Japan

    Yusei Tsushima

  3. Unimatec Co., Ltd., Kitaibaraki-shi, Ibaraki, 319-1593, Japan

    Katsuyuki Sato

Authors
  1. Tomoya Saito
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shohei Yamazaki
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yusei Tsushima
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Katsuyuki Sato
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hideo Sawada
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hideo Sawada.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Saito, T., Yamazaki, S., Tsushima, Y. et al. Reaction of fluorinated aliphatic alcohols with calcium chloride: formation of the fluorinated alcohol/calcium fluoride nanocomposites—thermal stability and application to the surface modification of these nanocomposites. J Coat Technol Res 13, 851–861 (2016). https://doi.org/10.1007/s11998-016-9797-1

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-016-9797-1

Keywords

Search

Navigation