Skip to main content

Advertisement

SpringerLink
Log in

Surface characterization of flat and rough films of perfluoromethacrylate-methylmethacrylate statistical copolymers synthesized in CO2-expanded monomers

  • Original Contribution
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

Statistical copolymers of perfluoroalkyl ethyl methacrylate (Zonyl-TM) and methylmethacrylate were synthesized in CO2-expanded monomer mixture at a low pressure of 10–13 MPa for the first time. M w of the copolymers was found to decrease with the increase of Zonyl-TM content. Flat films of these copolymers were obtained by dip coating from their chloroform solutions and were characterized using contact angle measurements, optical microscopy, and 3D profilometry. The increase in the Zonyl-TM content of the copolymers resulted in a decrease of the total surface free energy. Superhydrophobic and oleophobic rough copolymer films were also prepared by applying a phase-separation process where THF was used as the solvent and ethanol as the non-solvent. Surface roughness increased with the increase in the nonsolvent ratio resulting in an increase in the water contact angle from 103° to 151° and hexadecane contact angle from 49° to 73°.

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
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Du L, Kelly JY, Roberts GW, DeSimone JM (2009) Fluoropolymer synthesis in supercritical carbon dioxide. J Supercrit Fluids 47:447–457

    Article  CAS  Google Scholar 

  2. Liu JJ, Moore G, Pellerite GI (2010) (3M Innovative Properties Company) US Patent, March, 23 7,682,771

  3. Canelas DA, DeSimone JM (1997) Polymerizations in liquid and supercritical carbon dioxide. Adv Polym Sci 133:103–140

    Article  CAS  Google Scholar 

  4. Kendall JL, Canelas DA, Young JL, DeSimone JM (1999) Polymerizations in supercritical carbon dioxide. Chem Rev 99:543–563

    Article  CAS  Google Scholar 

  5. Beckman EJ (2004) Supercritical and near-critical CO2 in green chemical synthesis and processing. J Supercrit Fluids 28:121–191

    Article  CAS  Google Scholar 

  6. Kennedy KA, Roberts GW, DeSimone JM (2005) Heterogeneous polymerization of fluoroolefins in supercritical carbon dioxide. Adv Polym Sci 175:329–346

    Article  CAS  Google Scholar 

  7. Zetterlund PB, Aldabbagh F, Okubo M (2009) Controlled/living heterogeneous radical polymerization in supercritical carbon dioxide. J Polym Sci Part A Polym Chem 47:3711–3728

    Article  CAS  Google Scholar 

  8. Katano Y, Tomono H, Nakajima T (1994) Surface property of polymer films with fluoroalkyl side chains. Macromolecules 27:2342–2344

    Article  CAS  Google Scholar 

  9. Stone M, Nevell TG, Tsibouklis J (1998) Surface energy characteristics of poly(perfluoroacrylate) film structures. Mater Lett 37:102–105

    Article  CAS  Google Scholar 

  10. Nishino T, Meguro M, Nakamae K, Matsushita M, Ueda Y (1999) The lowest surface free energy based on -CF3 alignment. Langmuir 15:4321–4323

    Article  CAS  Google Scholar 

  11. van de Grampel RD, Ming W, Gildenpfennig A, van Gennip WJH, Laven J, Niemantsverdriet JW, Brongersma HH, de With G, van der Linde R (2004) The outermost atomic layer of thin films of fluorinated polymethacrylates. Langmuir 20:6344–6351

    Article  Google Scholar 

  12. Youssef A, Pabon M, Severac R, Gilbert RG (2009) The effect of copolymer composition on the surface properties of perfluoroalkylethyl acrylates. J Appl Polym Sci 114:4020–4029

    Article  CAS  Google Scholar 

  13. Castner DG, Grainger DW (2001) Fluorinated surfaces, coatings and films. American Chemical Society, Washington DC

    Book  Google Scholar 

  14. Wang Q, Zhang Q, Zhan X, Chen F (2010) Structure and surface properties of polyacrylates with short fluorocarbon side chain: role of the main chain and spacer group. J Polym Sci Part A Polym Chem 48:2584–2593

    Article  CAS  Google Scholar 

  15. Tsibouklis J, Graham P, Eaton PJ, Smith JR, Nevell TG, Smart JD, Ewen RJ (2000) Surface organization phenomena, surface energy determinations, and force of adhesion measurements. Macromolecules 33:8460–8465

    Article  CAS  Google Scholar 

  16. Guo J, Resnick P, Efimenko K, Genzer J, DeSimone JM (2008) Alternative fluoropolymers to avoid the challenges associated with perfluorooctanoic acid. Ind Eng Chem Res 47:502–508

    Article  CAS  Google Scholar 

  17. Thomas RR, Anton DR, Graham WF, Darmon MJ, Sauer BB, Stika KM, Swartzfager DG (1997) Preparation and surface properties of acrylic polymers containing fluorinated monomers. Macromolecules 30:2883–2890

    Article  CAS  Google Scholar 

  18. Park IJ, Lee SB, Choi CK (1997) Synthesis of fluorine-containing graft copolymers of poly(perfluoroalkyl ethyl methacrylate)-g-poly(methyl methacrylate) by the macromonomer technique and emulsion copolymerization method. Polymer 38:2523–2527

    Article  CAS  Google Scholar 

  19. Park IJ, Lee SB, Choi CK (1998) Surface properties of the fluorine-containing graft copolymer of poly((perfluoroalkyl)ethyl methacrylate)-g-poly(methyl methacrylate). Macromolecules 31:7555–7558

    Article  CAS  Google Scholar 

  20. Morita M, Ogisu H, Kubo M (1999) Surface properties of perfluoroalkylethyl acrylate/n-alkyl acrylate copolymers. J Appl Polym Sci 73:1741–1749

    Article  CAS  Google Scholar 

  21. Nishino T, Urushihara Y, Meguro M, Nakamae K (2005) Surface properties and structures of diblock copolymer and homopolymer with perfluoroalkyl side chains. J Colloid Interface Sci 283:533–538

    Article  CAS  Google Scholar 

  22. Gui TJ, Wei H, Zhao Y, Wang XL, Wang DJ, Xu DF (2006) Preparation and surface properties of acrylic copolymers containing fluorinated monomers. Chin J Polym Sci 24:575–578

    Article  CAS  Google Scholar 

  23. Saidi S, Guittard F, Guimon C, Geribaldi S (2006) Fluorinated acrylic polymers: surface properties and XPS investigations. J Appl Polym Sci 99:821–827

    Article  CAS  Google Scholar 

  24. Chang KC, Chen H, Huang CK, Huang SI (2007) Preparation of super-hydrophobic film with fluorinated-copolymer. J Appl Polym Sci 104:1646–1653

    Article  CAS  Google Scholar 

  25. Ye XY, Zuo B, Deng M, Hei Y, Ni H, Lu X, Wang X (2010) Surface segregation of fluorinated moieties on poly(methyl methacrylate-ran-2-perfluorooctylethyl methacrylate) films during film formation: entropic or enthalpic influences. J Colloid Interface Sci 349:205–214

    Article  CAS  Google Scholar 

  26. Yang T, Yao L, Peng H, Cheng S, Park IJ (2006) Characterization of a low-wettable surface based on perfluoroalkyl acrylate copolymers. J Fluor Chem 127:1105–1110

    Article  CAS  Google Scholar 

  27. Erbil HY (2006) Surface chemistry of solid and liquid interfaces. Blackwell, Oxford

    Google Scholar 

  28. Erbil HY, Demirel AL, Avci Y, Mert O (2003) Transformation of a simple plastic into a superhydrophobic surface. Science 299:1377–1380

    Article  CAS  Google Scholar 

  29. Xie BQ, Xu J, Feng L, Jiang L, Tang W, Lua X, Han CC (2004) Facile creation of a super-amphiphobic coating surface with bionic microstructure. Adv Mater 16:302–305

    Article  CAS  Google Scholar 

  30. Wei ZJ, Liu WL, Tian D, Xiao CL, Wang XQ (2010) Preparation of lotus-like superhydrophobic fluoropolymer films. Appl Surf Sci 256:3972–3976

    Article  CAS  Google Scholar 

  31. Cengiz U, Avci MZ, Erbil HY, Sarac AS (2012) Superhydrophobic terpolymer nanofibers containing perfluoroethyl alkyl methacrylate by electrospinning. Appl Surf Sci 258:5815–5821

    Article  CAS  Google Scholar 

  32. DeSimone JM, Guan Z, Elsbernd CS (1992) Synthesis of fluoropolymers in supercritical carbon dioxide. Science 257:945–947

    Article  CAS  Google Scholar 

  33. Kwon S, Bae W, Kim H (2004) The effect of CO2 in free-radical polymerization of 2,2,2-trifluoroethyl methacrylate. Korean J Chem Eng 4:910–914

    Article  Google Scholar 

  34. Wang Z, Yang YJ, Dong QZ, Hu CP (2008) Free radical polymerizations of some vinyl monomers in carbon dioxide fluid. J Appl Polym Sci 110:468–474

    Article  CAS  Google Scholar 

  35. Shin J, Lee YW, Kim H (2006) High-pressure phase behavior of carbon dioxide+heptadecafluorodecyl acrylate+poly(heptadecafluorodecyl acrylate) system. J Chem Eng Data 51:1571–1575

    Article  CAS  Google Scholar 

  36. Guo J, Andre P, Adam M, Panyukov S, Rubinstein M, DeSimone JM (2006) Solution properties of a fluorinated alkyl methacrylate polymer in carbon dioxide. Macromolecules 39:3427–3434

    Article  CAS  Google Scholar 

  37. Shin J, Bae W, Lee YW, Kim H (2007) Kinetics for free radical solution polymerization of heptadecafluorodecyl (meth)acrylate in supercritical carbon dioxide. Korean J Chem Eng 24:664–669

    Article  CAS  Google Scholar 

  38. Kim J, Efimenko K, Genzer J, Carbonell RG (2007) Surface properties of poly[2-(perfluorooctyl)ethyl acrylate] deposited from liquid CO2 high-pressure free meniscus coating. Macromolecules 40:588–597

    Article  CAS  Google Scholar 

  39. Shin J, Bae W, Kim H, Lee YW (2008) Phase behavior of binary and ternary carbon dioxide+heptadecafluorodecyl methacrylate+poly(heptadecafluorodecyl methacrylate) systems. J Chem Eng Data 53:1523–1527

    Article  CAS  Google Scholar 

  40. Hwang HS, Lee WK, Hong SS, Jin SH, Lim KT (2007) Dispersion polymerization of MMA in supercritical CO2 in the presence of poly(poly(ethylene glycol) methacrylate-co-1H,1H,2H,2H-perfluorooctylmethacrylate). J Supercrit Fluids 39:409–415

    Article  CAS  Google Scholar 

  41. Shin J, Oh KS, Bae W, Lee YW, Kim H (2008) Dispersion polymerization of methyl methacrylate using poly(HDFDMA-co-MMA) as a surfactant in supercritical carbon dioxide. Ind Eng Chem Res 47:5680–5685

    Article  CAS  Google Scholar 

  42. Kim BG, Shin J, Sohn EH, Chung JS, Bae W, Kim H, Lee JC (2010) Dispersion polymerization in supercritical carbon dioxide using comb-like fluorinated polymer surfactants having different backbone structures. J Supercrit Fluids 55:381–385

    Article  CAS  Google Scholar 

  43. Shiho H, DeSimone JM (2000) Radical polymerizations of a silicone-containing acrylic monomer in supercritical carbon dioxide. J Polym Sci Part A Polym Chem 38:3100–3105

    Article  CAS  Google Scholar 

  44. Hwang HS, Kim HJ, Jeong YT, Gal YS, Lim KT (2004) Synthesis and properties of semifluorinated copolymers of oligo(ethylene glycol) methacrylate and 1H,1H,2H,2H-perfluorooctyl methacrylate. Macromolecules 37:9821–9825

    Article  CAS  Google Scholar 

  45. Liu ZT, Chen JG, Liu ZW, Lu J (2008) New process for synthesizing fluorinated polymers in supercritical carbon dioxide. Macromolecules 41:6987–6992

    Article  CAS  Google Scholar 

  46. Liu J, Han B, Zhang R, Liu Z, Jiang T, Yang G (2003) Effect of antisolvent carbon dioxide on the polymerization of methyl methacrylate in different solvents. J Supercrit Fluids 25:91–97

    Article  CAS  Google Scholar 

  47. Zwolak G, Lioe L, Lucien FP (2005) Vapor–liquid equilibria of carbon dioxide+methyl methacrylate at 308, 313, 323, and 333K. Ind Eng Chem Res 44:1021–1026

    Article  CAS  Google Scholar 

  48. Zwolak G, Lucien FP (2008) Molecular weight evolution in the catalytic chain transfer polymerization of CO2-expanded methyl methacrylate. Macromolecules 41:5141–5147

    Article  CAS  Google Scholar 

  49. Pu DW, Lucien FP, Zetterlund PB (2010) Nitroxide-mediated radical polymerization of carbon dioxide-expanded methyl methacrylate. J Polym Sci Part A Polym Chem 48:5636–5641

    Article  CAS  Google Scholar 

  50. Cengiz U, Gengec NA, Kaya NU, Erbil HY, Sarac S (2011) Mechanical and thermal properties of perfluoroalkyl ethyl methacrylate–methyl methacrylate statistical copolymers synthesized in supercritical carbon dioxide. J Fluor Chem 132:348–355

    Article  CAS  Google Scholar 

  51. Dupont Zonyl-TM Data Sheet (2007) http://www2.dupont.com/Zonyl_Foraperle/en_US/assets/downloads/Zonyl_TM.pdf

  52. Dupont Zonyl Fluorochemical Intermediates (2008) http://www2.dupont.com/home/en-us/index.html

  53. Erbil HY, McHale G, Rowan SM, Newton MI (1999) Determination of the receding contact angle of sessile drops on polymer surfaces by evaporation. Langmuir 15:7378–7385

    Article  CAS  Google Scholar 

  54. van Oss CJ, Chaudhury MK, Good R (1988) Interfacial Lifshitz-van der Waals and polar interactions in macroscopic systems. Chem Rev 88:927–941

    Article  Google Scholar 

  55. Houwink RJ (1940) Prakt Chem/Chem-Ztg 157:156

    Google Scholar 

  56. Wagner HL (1987) The Mark-Houwink-Sakaruda relation for poly(methyl methacrylate). J Phys Chem Ref Data 16:165–173

    Article  CAS  Google Scholar 

  57. Lepilleur C, Beckman EJ (1997) Dispersion polymerization of methyl methacrylate in supercritical CO2. Macromolecules 30:745–756

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the Scientific and Technological Research Council of Turkey (TUBITAK) under the project “Development of Environmentally Benign Processes for the Fabrication of Self-Cleaning and Self-Healing Superhydrophobic Surfaces” (project no: MAG-104M360). The authors would like to thank Dr. Serpil Harbeck and Ph.D. student Ilker Un for obtaining GPC and NMR data and the Chemistry Department of Gebze Institute of Technology for the use of GPC and NMR facilities.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Gebze Institute of Technology, Cayirova, Gebze, 41400, Kocaeli, Turkey

    Ugur Cengiz, Nevin A. Gengec & H. Yildirim Erbil

Authors
  1. Ugur Cengiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nevin A. Gengec
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. H. Yildirim Erbil
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to H. Yildirim Erbil.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOCX 1320 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Cengiz, U., Gengec, N.A. & Erbil, H.Y. Surface characterization of flat and rough films of perfluoromethacrylate-methylmethacrylate statistical copolymers synthesized in CO2-expanded monomers. Colloid Polym Sci 291, 641–652 (2013). https://doi.org/10.1007/s00396-012-2766-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-012-2766-z

Keywords

Search

Navigation