Skip to main content
SpringerLink
Log in

The preparation and aggregation behaviors of comb-like thermally-responsive fluoropolymer

  • ORIGINAL PAPER
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

Amphipathic comb-like fluoropolymer (P(OEGMA-co-FHA)) based on oligomer (ethylene glycol) methacrylate (OEGMA) and 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate (FHA) monomers was prepared by atom transfer radical polymerization, which was first characterized by Fourier-transform infrared spectroscopy and (9F,1H) nuclear magnetic resonance. And their aggregation behaviors at different temperatures were studied by transmittance,fluorescence spectroscopy,dynamic light scattering,transmission electron microscopy, small angle X-ray scattering and rheology. The results show that P (OEGMA-co-FHA) has thermal responsiveness, which leads to changes in aggregation behaviors with the increase of temperature. Low critical solution temperature (LCST) was 45 °C. The critical associating concentration (CAC) values are 1.85 and 1.61 g/L at room temperature and 35 °C respectively. Moreover, the particles of P (OEGMA-co-FHA) was about 20 nm at room temperature and aggregated to about 100 nm at 60 °C. The viscosity of P (OEGMA-co-FHA) increase and had stronger shear-thin behaviors.

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
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Fu GD, Xu LQ, Yao F, Zhang K, Wang XF, Zhu MF, Nie SZ (2009) Smart nanofibers from combined living radical polymerization,“click chemistry”, and electrospinning. ACS Appl Mater Interfaces 1(2):239–243

    Article  CAS  PubMed  Google Scholar 

  2. Cai T, Neoh KG, Kang ET, Teo SLM (2011) Surface-functionalized and surface-functionalizable poly (vinylidene fluoride) graft copolymer membranes via click chemistry and atom transfer radical polymerization. Langmuir 27(6):2936–2945

    Article  CAS  PubMed  Google Scholar 

  3. Ge Z, Wang D, Zhou Y, Liu H, Liu S (2009) Synthesis of organic/inorganic hybrid quatrefoil-shaped star-cyclic polymer containing a polyhedral oligomeric silsesquioxane core. Macromolecules 42(8):2903–2910

    Article  CAS  Google Scholar 

  4. Koji Honda, †., Masamichi Morita, †., Hideyuki Otsuka, †. ‡. A., & Atsushi Takahara, †. ‡. (2005). Molecular aggregation structure and surface properties of poly(fluoroalkyl acrylate) thin films. Kōbunshi Rombun Shū, 64(4), 55–62

  5. Guo TY, Tang D, Song M, Zhang B (2007) Copolymerizations of butyl methacrylate and fluorinated methacrylates via RAFT miniemulsion polymerization. J Polym Sci A Polym Chem 45(22):5067–5075

    Article  CAS  Google Scholar 

  6. Yasutake M, Andou Y, Hiki S, Nishida H, Endo T (2004) Physically controlled, free-radical polymerization of vaporized fluoromonomer on solid surfaces. J Polym Sci A Polym Chem 42(11):2621–2630

    Article  CAS  Google Scholar 

  7. Chen Y, Cheng S, Wang Y, Zhang C (2006) Chemical components and properties of core–shell acrylate latex containing fluorine in the shell and their films. J Appl Polym Sci 99(1):107–114

    Article  CAS  Google Scholar 

  8. Kujawa P, Segui F, Shaban S, Diab C, Okada Y, Tanaka F, Winnik FM (2006) Impact of end-group association and main-chain hydration on the thermosensitive properties of hydrophobically modified telechelic poly (N-isopropylacrylamides) in water. Macromolecules 39(1):341–348

    Article  CAS  Google Scholar 

  9. Krishnan R, Srinivasan KSV (2003) Controlled/“living” radical polymerization of glycidyl methacrylate at ambient temperature. Macromolecules 36(6):1769–1771

    Article  CAS  Google Scholar 

  10. Ghadban A, Albertin L (2013) Synthesis of glycopolymer architectures by reversible-deactivation radical polymerization. Polymers 5(2):431–526

    Article  CAS  Google Scholar 

  11. Maeda Y, Higuchi T, Ikeda I (2000) Change in hydration state during the coil− globule transition of aqueous solutions of poly (N-isopropylacrylamide) as evidenced by FTIR spectroscopy. Langmuir 16(19):7503–7509

    Article  CAS  Google Scholar 

  12. Sugihara S, Hashimoto K, Okabe S, Shibayama M, Kanaoka S, Aoshima S (2004) Stimuli-responsive diblock copolymers by living cationic polymerization: precision synthesis and highly sensitive physical gelation. Macromolecules 37(2):336–343

    Article  CAS  Google Scholar 

  13. Bernstein RE, Cruz CA, Paul DR, Barlow JW (1977) LCST behavior in polymer blends. Macromolecules 10(3):681–686

    Article  CAS  Google Scholar 

  14. Fitch S, Horton RL, Mueller BL (2012). US Patent Application No 13(/445):201

    Google Scholar 

  15. Maeda Y, Kubota T, Yamauchi H, Nakaji T, Kitano H (2007) Hydration changes of poly (2-(2-methoxyethoxy) ethyl methacrylate) during thermosensitive phase separation in water. Langmuir 23(22):11259–11265

    Article  CAS  PubMed  Google Scholar 

  16. Nomura K, Makino H, Nakaji-Hirabayashi T, Kitano H, Ohno K (2015) Temperature-responsive copolymer brush constructed on a silica microparticle by atom transfer radical polymerization. Colloid Polym Sci 293(3):851–859

    Article  CAS  Google Scholar 

  17. Wilhelm M, Zhao CL, Wang Y, Xu R, Winnik MA, Mura JL, Riess G, Croucher MD (1991) Poly (styrene-ethylene oxide) block copolymer micelle formation in water: a fluorescence probe study. Macromolecules 24(5):1033–1040

    Article  CAS  Google Scholar 

  18. Zhao CL, Winnik MA, Riess G, Croucher MD (1990) Fluorescence probe techniques used to study micelle formation in water-soluble block copolymers. Langmuir 6(2):514–516

    Article  CAS  Google Scholar 

  19. Xu P, Tang H, Li S, Ren J, Van Kirk E, Murdoch WJ et al (2004) Enhanced stability of core− surface cross-linked micelles fabricated from amphiphilic brush copolymers. Biomacromolecules 5(5):1736–1744

    Article  CAS  PubMed  Google Scholar 

  20. Tong L, Shen Z, Yang D, Chen S, Li Y, Hu J, Lu G, Huang X (2009) PTPFCBBMA-b-PEG-b-PTPFCBBMA amphiphilic triblock copolymer: synthesis and self-assembly behavior. Polymer 50(11):2341–2348

    Article  CAS  Google Scholar 

  21. París R, Quijada-Garrido I (2011) Synthesis and aggregation properties in water solution of comblike methacrylic polymers with oligo (propylene glycol)-block-oligo (ethylene glycol) as side chains. J Polym Sci A Polym Chem 49(8):1928–1932

    Article  CAS  Google Scholar 

  22. Abbel R, Schleuss TW, Frey H, Kilbinger AF (2005) Rod-length dependent aggregation in a series of oligo (p-benzamide)-block-poly (ethylene glycol) rod-coil copolymers. Macromol Chem Phys 206(20):2067–2074

    Article  CAS  Google Scholar 

  23. Trzebicka B, Szweda D, Rangelov S, Kowalczuk A, Mendrek B, Utrata-Wesołek A, Dworak A (2013) (co) polymers of oligo (ethylene glycol) methacrylates—temperature-induced aggregation in aqueous solution. J Polym Sci A Polym Chem 51(3):614–623

    Article  CAS  Google Scholar 

  24. Zhao B, Li D, Hua F, Green DR (2005) Synthesis of thermosensitive water-soluble polystyrenics with pendant methoxyoligo (ethylene glycol) groups by nitroxide-mediated radical polymerization. Macromolecules 38(23):9509–9517

    Article  CAS  Google Scholar 

  25. Morris EA, Weisenberger MC, Bradley SB, Abdallah MG, Mecham SJ, Pisipati P, McGrath JE (2014) Synthesis, spinning, and properties of very high molecular weight poly (acrylonitrile-co-methyl acrylate) for high performance precursors for carbon fiber. Polymer 55(25):6471–6482

    Article  CAS  Google Scholar 

  26. Devasia R, Reghunadhan Nair CP, Ninan KN (2008) Rheological behavior of dope solutions of poly (acrylonitrile-co-itaconic acid) in N, N-dimethylformamide: effect of polymer molar mass. J Macromol Sci A 45(3):248–254

    Article  CAS  Google Scholar 

  27. Zuppardi F, Chiacchio FR, Sammarco R, Malinconico M, D'Ayala GG, Cerruti P (2017) Fluorinated oligo(ethylene glycol) methacrylate-based copolymers: tuning of self assembly properties and relationship with rheological behavior. Polymer 112:169–179

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We would like to acknowledge financial support from the Natural Science Foundation of China (5160030644), the Scientific Research Fund of Shaanxi University of Science and Technology (2016QNBJ-15), and the Scientific Research Fund of Shaanxi Provincial Education Department(17JK0101).

Author information

Authors and Affiliations

  1. Key Laboratory of Auxiliary Chemistry & Technology for Chemical Industry, College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi’an, 710021, People’s Republic of China

    Xiaowu Yang, Xia Wang & Chen Wang

Authors
  1. Xiaowu Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xia Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chen Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Chen Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, X., Wang, X. & Wang, C. The preparation and aggregation behaviors of comb-like thermally-responsive fluoropolymer. J Polym Res 25, 156 (2018). https://doi.org/10.1007/s10965-018-1559-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-018-1559-6

Keywords

Search

Navigation