Skip to main content
Log in

Synthesis and properties novel polyurethane-hexafluorobutyl methacrylate copolymers

  • Published:
Journal of Materials Science: Materials in Medicine Aims and scope Submit manuscript

Abstract

Novel physically crosslinked polyurethane-hexafluorobutyl methacrylate (PU-M) copolymers were prepared by the macroiniferter-controlled radical polymerization method. The chemical structures of the PU-M copolymers were characterized by FT-IR, 1H-NMR, GPC, DSC, and XPS. The self-assembly and surface properties of the PU-M copolymers have been investigated. The results revealed that PU-M copolymers have good hydrophobility, so the hydrophobility of polyurethane could be easily adjusted by controlling the content of the hydrophobic vinyl monomers. The mechanical evaluation shows that PU-M copolymers exhibit good mechanical properties. The effects of the fluorine content on the surface properties and self-assembly of the PU-M copolymers were investigated. The morphology of the PU-M copolymers’ self-assembly was observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), and the mechanism of self-assembly was investigated. Antimicrobial property of the chlorinated PU-M copolymers against both Escherichia coli and Bacillus subtilis bacteria was examined and showed increase compared to that of pure polyurethane.

Graphical Abstract

Novel PU-M copolymers were synthesized by the macroiniferter controlled radical polymerization method. The structure of polymers was characterized by 1H NMR and IR. Solvent-induced assembly of polymers was investigated by dissolving the polymer in THF:water (80:20, v/v), filtering and dropping onto a glass patch. After evaporation for 48 h under ambient conditions, the samples were observed by SEM. The PU-M copolymers were subjected to solvent-induced self-assembly in THF + water to construct variety of morphologies ranging from pores (150–650 nm) to spheres (90 nm to 1.2 μm). A mechanism is proposed according to solvent-induced self-assembly.

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

Access this article

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

Instant access to the full article PDF.

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

Similar content being viewed by others

References

  1. Vara DS, Punshon G, Sales KM, Salacinski HJ. Development of an RNA isolation procedure for the characterisation of human endothelial cell interactions with polyurethane cardiovascular bypass grafts. Biomaterials. 2005;26:3987–93.

    Article  CAS  Google Scholar 

  2. Yu XH, Okkema AZ, Cooper SL. Synthesis and physical properties of poly(fluoroalkylether)urethanes. J Appl Polym Sci. 1990;41:1777–95.

    Article  CAS  Google Scholar 

  3. Massa TM, Yang ML, Ho JC, Brash JL, Santerre JP. Fibrinogen surface distribution correlates to platelet adhesion pattern on fluorinated surface-modified polyetherurethane. Biomaterials. 2005;26:7367–76.

    Article  CAS  Google Scholar 

  4. Tan H, Guo M, Du R, Xie X, Li J. The effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes. Polymer. 2004;45:1647–57.

    Article  CAS  Google Scholar 

  5. Robert W, James A, Rick M, Ken S. In vivo biostability of polyether polyurethanes with fluoropolymer and polyethylene oxide surface modifying endgroups; resistance to metal ion oxidation. J Biomed Mater Res Part A. 2007;80:34–44.

    Google Scholar 

  6. Robert W, James A, Rick M, Ken S. In vivo biostability of shore 55D polyether polyurethanes with and without fluoropolymer surface modifying endgroups. J Biomed Mater Res Part A. 2006;79:836–45.

    Google Scholar 

  7. Tonelli C, Ajroldi G, Turturro A, Marigo A. Synthesis methods of fluorinated polyurethanes. Polymer. 2001;42:5589–98.

    Article  CAS  Google Scholar 

  8. Huang SL, Chao MS, Ruaan RC, Lai JY. Microphase separated structure and protein adsorption of polyurethanes with butadiene soft segment. Eur Polym J. 2000;36:285–94.

    Article  CAS  Google Scholar 

  9. Chen K, Kuo JF. Synthesis and properties of novel fluorinated aliphatic polyurethanes with fluoro chain extenders. Macromol Chem Phys. 2000;201:2676–86.

    Article  CAS  Google Scholar 

  10. Wang LF, Wei YH, Chen KY, Lin JC. Properties of phospholipid monolayer deposited on a fluorinated polyurethane. J Biomater Sci Polym Ed. 2004;15:957–69.

    Article  CAS  Google Scholar 

  11. Tonelli C, Trombtta T, Scicchitano M, Simeone G, Ajroldi G. New fluorinated thermoplastic elastomers. J Appl Polym Sci. 1996;59:311–27.

    Article  CAS  Google Scholar 

  12. Ho T, Wynne KJ. A new fluorinated polyurethane: polymerization, characterization, and mechanical properties. Macromolecules. 1992;25:3521–7.

    Article  CAS  Google Scholar 

  13. Takahara A, Jo NJ, Takamori K, Kajiyama T. In progress in biomedical polymers. 2nd ed. New York: Plenum Press; 1990.

    Google Scholar 

  14. Tang YW, Santerre JP, Labow RS, Taylor DG. Use of surface-modifying macromolecules to enhance the biostability of segmented polyurethanes. J Biomed Mater Res. 1997;35:371–81.

    Article  CAS  Google Scholar 

  15. Grodzinski J. Preparation of functionalized polymers using living and controlled polymerizations. React Funct Polym. 2001;49:1–54.

    Article  Google Scholar 

  16. Sundar S, Tharanikkarasu K, Dhathathreyan A, Radhakrishnan G. Aqueous dispersions of poly(urethane-co-vinyl-pyridine) synthesised from polyurethane macroiniferter. Colloid Polym Sci. 2002;280:915–21.

    Article  CAS  Google Scholar 

  17. Otsu T, Matsumoto A. Controlled synthesis of polymers using the iniferter technique: developments in living radical polymerization. Adv Polym Sci. 1998;136:75–137.

    Article  CAS  Google Scholar 

  18. Mahesh GN, Sivaraman A, Tharanikkarasu K, Radhakrishnan G. Synthesis and characterization of polyurethane–polyvinylbenzyl chloride multiblock copolymers and their cationomers using a polyurethane macroiniferter. J Polym Sci A Polym Chem. 1997;35:1237–44.

    Article  CAS  Google Scholar 

  19. Baek SH, Kim BS, Kim BK. Hydrogels based on polyurethane–polyacrylic acid multiblock copolymers via macroiniferter technique. Prog Org Coat. 2004;49:353–7.

    Article  CAS  Google Scholar 

  20. Saimani S, Tharanikkarasu K, Radhakrishnan G. Aqueous dispersions of polyurethane polyacrylic acid multiblock copolymers through living radical polymerization. J Appl Polym Sci. 2003;87:1109–15.

    Article  CAS  Google Scholar 

  21. Tharanikkarasu K, Radhakrishnan G. Tetraphenylethane iniferters: polyurethane-polystyrene multiblock copolymers through “living” radical polymerization. J Appl Polym Sci. 1997;66:1551–60.

    Article  CAS  Google Scholar 

  22. Yoon SC, Ratner BD. Surface and bulk structure of segmented poly(ether urethanes) with perfluoro chain extenders. Macromolecules. 1988;21:2392–400.

    Article  CAS  Google Scholar 

  23. Tanaka M, Mochiziki A, Ishii N, Motomura T, Hatakeyama T. Study of blood compatibility with poly(2-methoxyethyl acrylate). Biomacromolecules. 2002;3:36–41.

    Article  CAS  Google Scholar 

  24. Lin YH, Chou NK, Chang CH, Wang SS, Chu SH, Hsieh KH. Blood compatibility of fluorodiol-containing polyurethanes. J Polym Sci Part A Polym Chem. 2007;45:3231–42.

    Article  CAS  Google Scholar 

  25. Karthaus O, Maruyama N, Cieren X, Shimomura M, Hasegawa H. Water-assisted formation of micrometer-size honeycomb patterns of polymers. Langmuir. 2000;16:6071–6.

    Article  CAS  Google Scholar 

  26. Wang Y, Liu Z, Huang Y, Han B, Yang G. Micropatterned polymer surfaces induced by nonsolvent. Langmuir. 2006;22:1928–31.

    Article  CAS  Google Scholar 

  27. Soo PL, Eisenberg A. Preparation of block copolymer vesicles in solution. J Polym Sci Part B Polym Phys. 2004;42:923–38.

    Article  CAS  Google Scholar 

  28. Huang W, Luo C, Zhang J, Yu K, Han Y. Tethered diblock copolymer chains on platelets prepared by semicrystalline abc triblock copolymers in toluene with trace amounts of water. Macromolecules. 2007;40:8022–30.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This project was supported by National 863 Foundation of China (No. 2006 AA 02 Z4D4) and the China Postdoctoral Science Foundation (Nos. 20080430033 and 200902090). The Project was Supported by The Tribology Science Fund of State Key Laboratory of Tribology (SKLTKF10B08).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Guichang Jiang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Jiang, G., Tuo, X., Wang, D. et al. Synthesis and properties novel polyurethane-hexafluorobutyl methacrylate copolymers. J Mater Sci: Mater Med 23, 1867–1877 (2012). https://doi.org/10.1007/s10856-012-4670-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10856-012-4670-y

Keywords

Navigation