Skip to main content
Log in

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

  • Original Paper: Sol–gel and hybrid materials with surface modification for applications
  • Published:
Journal of Sol-Gel Science and Technology Aims and scope Submit manuscript


Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2–CHSi(OMe)3)n-RF; n = 2, 3; RF = fluoroalkyl group: RF-(VM)n-RF] was found to undergo the sol–gel reaction in the presence of micro-sized silica particles under alkaline conditions to afford the corresponding fluorinated oligomer/micro-sized silica composites [RF-(VM-SiO3/2)n-RF/μ-SiO2]. The obtained composites were applied to the surface modification of glass to reveal a superoleophilic/superhydrophobic characteristic on the modified surface. In contrast, fluoroalkyl end-capped vinyltrimethoxysilane oligomer/silica nanocomposites [RF-(VM-SiO3/2)n-RF/n-SiO2], which were prepared in the presence of nanometer-sized silica particles under similar sol–gel reactions, provided an oleophobic/superhydrophobic property on the surface. RF-(VM-SiO3/2)n-RF/μ-SiO2 composites were applied to the solid-phase extraction sorbent to isolate the transparent colorless oil from water-in-oil (W/O) emulsion. These composite powders were also applicable to the effective removal of traditional organic dyes, such as rhodamine B, acid red 289, and fluorescein from aqueous methanol solution. Of particular interest, it was demonstrated that RF-(VM-SiO3/2)n-RF/μ-SiO2 composites, of whose micro-sized silica gel is surface-functionalized with amino units, can exhibit a similar superoleophilic/superhydrophobic characteristic on the composite surface, giving the selective removal of fluorinated phenol-type aromatic compounds from aqueous methanol solutions, although the removal ability for the corresponding non-fluorinated ones was not observed at all under similar conditions.


  • Fluoroalkyl end-capped oligomer/micro-sized silica composites possessing a superoleophilic/superhydrophobic characteristic were prepared.

  • The obtained composites were applied to the separation of W/O emulsion to isolate the transparent colorless oil.

  • Effective removal of organic dyes from aqueous methanol solutions was observed by using these composites.

  • Selective removal of fluorinated organic compounds from aqueous methanol solutions was also observed.

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

Access this article

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

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

Similar content being viewed by others


  1. Schwarzenbach RP, Escher BI, Fenner K, Hofstetter TB, Johnson CA, von Gunten U, Wehrli B (2006) The challenge of micropollutants in aquatic systems. Science 313:1072–1077

    Article  CAS  Google Scholar 

  2. Alsbaiee A, Smith BJ, Xiao L, Ling Y, Helbling DE, Dichtel WR (2016) Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer. Nature 529(190):194

    Google Scholar 

  3. Muller K, Faeh C, Diederich F (2006) Fluorine in pharmaceuticals: looking beyond intuition. Science 317:1881–1887

    Article  Google Scholar 

  4. Isanbor C, O’Hagan D (2006) Fluorine in medicinal chemistry: A review of anti-cancer agents. J Fluor Chem 127:303–319

    Article  CAS  Google Scholar 

  5. Sawada H, Nakayama M (1991) Synthesis of fluorine-containing organosilicon oligomers. J Chem Soc Chem Commun 677–678.

  6. Ameduri B, Sawada H (eds.) (2016), Fluorinated polymers: Volume 1, “Synthesis, properties, processing and simulation”. Cambridge, RSC.

  7. Ameduri B, Sawada H (eds.) (2016), Fluorinated polymers: Volume 2, “Applications”. Cambridge, RSC.

  8. Sawada H (2007) Synthesis of self-assembled fluoroalkyl end-capped oligomeric aggregates—Applications of these aggregates to fluorinated oligomeric nanocomposites. Prog Polym Sci 32:509–533

    Article  CAS  Google Scholar 

  9. Sawada H (2007) Development of fluorinated polymeric functional materials using fluorinated organic peroxide as key material. Polym J 39:637–650

    Article  CAS  Google Scholar 

  10. Sawada H (1996) Fluorinated peroxides. Chem Rev 96:1779–1808

    Article  CAS  Google Scholar 

  11. Sawada H (2012) Preparation and applications of novel fluoroalkyl end-capped oligomeric nanocomposites. Polym Chem 3:46–65

    Article  CAS  Google Scholar 

  12. Sawada H (2003) Novel self-assembled molecular aggregates formed by fluoroalkyl end-capped oligomers and their application. J Fluor Chem 121:111–130

    Article  CAS  Google Scholar 

  13. Sawada H, Suzuki T, Takashima H, Takishita K (2008) 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

    Article  CAS  Google Scholar 

  14. Guo S, Yoshioka H, Kakehi H, Kato Y, Miura M, Isu N, Ameduri B, Sawada H (2012) Fluoroalkyl end-capped vinyltrimethoxysilane oligomer/anatase titanium oxide nanocomposites possessing photocatalytic activity even after calcination at 1000 °C. J Colloid Interface Sci 387:141–145

    Article  CAS  Google Scholar 

  15. Guo S, Ogasawara T, Saito T, Kakehi H, Kato Y, Miura M, Isu N, Sawada H (2013) 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

    Article  CAS  Google Scholar 

  16. Purcar V, Donescu D, Spataru IC, Ghiurea M, Caprarescu S, Petcu C, Nistor CL (2013) Surface modification of solgel hybrid films using fluorinated silica nanoparticles. Rev Roum Chim 58:37–42

    CAS  Google Scholar 

  17. Purcar V, Caprarescu S, Spataru CI, Ghiurea M, Raditoiu V, Donescu D, Petcu C, Somoghi R, Corobea MC (2013) Preparation of Hydrophobic and Antireflective Hybrid Films by Sol-Gel Process Using Perfluoroalkylsilane and Tetraethoxysilane. Rev Roum Chim 58:283–289

    CAS  Google Scholar 

  18. Goto Y, Takashima H, Takishita K, Sawada H (2011) 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

    Article  CAS  Google Scholar 

  19. Ling WX, Guo ZG (2013) Layered double hydroxide functionalized textile for effective oil/water separation and selective oil adsorption. RSC Adv 3:16469–16474

    Article  Google Scholar 

  20. Liu X, Ge L, Li W, Wang X, Li F (2015) Layered double hydroxide functionalized textile for effective oil/water separation and selective oil adsorption. ACS Appl Mater Interfaces 7(791):800

    Google Scholar 

  21. Feng XJ, Jiang L (2006) Design and creation of superwetting/antiwetting surfaces. Adv Mater 18:3063–3078

    Article  CAS  Google Scholar 

  22. Wu L, Zhang J, Li B, Wang A (2014) Mechanical- and oil-durable superhydrophobic polyester materials for selective oil absorption and oil/water separation. J Colloid Interface Sci 413:112–117

    Article  CAS  Google Scholar 

  23. Arbatan T, Zhang L, Fang X-Y, Shen W (2012) Cellulose nanofibers as binder for fabrication of superhydrophobic paper. Chem Eng J 210:74–79

    Article  CAS  Google Scholar 

  24. Yu JC, Jiang ZT, Liu HY, Yu L, Zhang I (2003) β-Cyclodextrin epichlorohydrin copolymer as a solid-phase extraction adsorbent for aromatic compounds in water samples. Anal Chim Acta 477:93–101

    Article  CAS  Google Scholar 

  25. Crini G, Bertini S, Torri G, Naggi A, Sforzini D, Vecchi C, Janus L, Lekchiri Y, Morcellet M (1998) Sorption of aromatic compounds in water using insoluble cyclodextrin polymers. J Appl Polym Sci 68:1973–1978

    Article  CAS  Google Scholar 

  26. Suzuki J, Takegahara Y, Oikawa Y, Aomi Y, Sawada H (2018) Preparation of fluoroalkyl end-capped oligomer/cyclodextrin polymer composites: development of fluorinated composite material having a higher adsorption ability toward organic molecules. J Encapsul Adsorpt Sci8:117–138

    CAS  Google Scholar 

  27. Farrukh A, Akram A, Ghaffar A, Tuncel E, Oluz Z, Duran H, Rehman HUR, Yameen B (2014) Surface-functionalized silica gel adsorbents for efficient remediation of cationic dyes. Pure Appl Chem 86:1177–1188

    Article  CAS  Google Scholar 

  28. Zhou L, Gao C, Xu W (2010) Magnetic dendritic materials for highly efficient adsorption of dyes and drugs. ACS Appl Mater Interfaces 2:1483–1491

    Article  CAS  Google Scholar 

  29. Crini G (2003) Studies on adsorption of dyes on beta-cyclodextrin polymer. Bioresour Technol 90:193–198

    Article  CAS  Google Scholar 

  30. Liu H, Yu H, Jin P, Jiang M, Zhu G, Duan Y, Yang Z, Qiu H (2020) Preparation of mesoporous silica materials functionalized with various amino-ligands and investigation of adsorption performances on aromatic acids. Chem Eng J 379(1–9):122405

    Article  CAS  Google Scholar 

  31. Regueiro J, Breidbach A, Wenzl T (2015) Derivatization of bisphenol a and its analogues with pyridine- 3-sulfonyl chloride: multivariate optimization and fragmentation patterns by liquid chromatography/Orbitrap mass spectrometry. Rapid Commun Mass Spectrom 29:1473–1484

    Article  CAS  Google Scholar 

  32. Zedda M, Tuerk J, Peil S, Schmidt T. C (2010) Determination of polymerÿelectrolyte membrane (PEM) degradation products in fuel cell water using electrosprayÿionization tandem mass spectrometry. Rapid Commun Mass Spectrom 24:3531–3538

    Article  CAS  Google Scholar 

Download references


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

Correspondence to Hideo Sawada.

Ethics declarations

Conflict of interest

The authors declare that they have no 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

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sawada, H., Chiba, M., Honma, G. et al. 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).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: