Controlled synthesis and self-assembly of amphiphilic copolymers based on 2,2,3,3,4,4,5,5-octafluoropentyl acrylate and acrylic acid

  • Alexandra GrigorevaEmail author
  • Egor Polozov
  • Sergey Zaitsev
Original Contribution


The reversible addition–fragmentation chain transfer (RAFT) polymerization of 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (OFPA) in the presence of different concentrations of S,S-dibenzyl carbonotrithioate as chain transfer agent (CTA) was investigated. The estimate of Ctr was defined using the size-exclusion chromatography measurements. Copolymers of acrylic acid and OFPA with different microstructure were synthesized by three methods: block copolymerization, copolymerization of acrylic acid and OFPA, and chemical modification of copolymer of tert-butyl acrylate and OFPA. Copolymerization of abovementioned monomer pairs was studied. The reactivity ratios were calculated by using the Fineman–Ross and Kelen–Tudos models, as well as the method of least squares. Aggregation behavior of the obtained amphiphilic copolymers at the air/water interface was defined by the Langmuir monolayer technique. Monomolecular films of amphiphilic copolymers were studied using atomic force microscopy. The effect of the chain microstructure, the acrylic acid content in the copolymer, and subphase pH on the isotherm curves were shown.

Graphical abstract


RAFT polymerization Fluorinated poly(meth)acrylate Amphiphiles Copolymers Self-assembly 



We are grateful to Maksim A. Baten’kin (G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences) for help in performing studies by the AFM method.

Funding information

This work was supported by the Russian Foundation for Basic Research (Project No. 19-03-00843 and No. 17-03-00131a).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

396_2019_4559_MOESM1_ESM.docx (1 mb)
ESM 1 (DOCX 1036 kb)


  1. 1.
    Koiry BP, Singh NK, Chakraborty A, Natha RK (2018) Non-ionic fluorinated amphiphilic block copolymer via RAFT polymerization and their application as surfactant in emulsion polymerization. Materials Today: Proceedings 5:2040–2048. Google Scholar
  2. 2.
    Choi D, Yeom EH, Park M, Kim JK, Kim BC (2004) Preparation and properties of methyl methacrylate and fluoroacrylate copolymers for plastic optical fiber cladding. J Appl Polym Sci 93:2082–2089. CrossRefGoogle Scholar
  3. 3.
    Kabanov AV, Batrakova EV, Alakhov VY (2002) Pluronic block copolymers as novel polymer therapeutics for drug and gene delivery. J Control Release 82:189–212. CrossRefGoogle Scholar
  4. 4.
    Kataoka K, Harada A, Nagasaki Y (2001) Block copolymer micelles for drug delivery: design, characterization and biological significance. Adv Drug Deliv Rev 47:113–131. CrossRefGoogle Scholar
  5. 5.
    York AW, Kirkland ES, McCormick CL (2008) Advances in the synthesis of amphiphilic block copolymers via RAFT polymerization: stimuli-responsive drug and gene delivery. Adv Drug Deliv Rev 60:1018–1036. CrossRefGoogle Scholar
  6. 6.
    Rösler A, Vandermeulen GWM, Klok H (2012) Advanced drug delivery devices via self-assembly of amphiphilic block copolymers. Adv Drug Deliv Rev 64:270–279. CrossRefGoogle Scholar
  7. 7.
    Ahmed M, Narain R (2013) Progress of RAFT based polymers in gene delivery. Prog Polym Sci 38:767–790. CrossRefGoogle Scholar
  8. 8.
    Ringsdorf H, Schmidt G, Schneider J (1987) Oriented ultrathin membranes from monomeric and polymeric amphiphiles: monolayers, liposomes and multilayers. Thin Solid Films 152:207–222. CrossRefGoogle Scholar
  9. 9.
    Fukuda K, Shibasaki Y, Nakahara H (1988) Polymerizabilities of amphiphilic monomers with controlled arrangements in Langmuir-Blodgett films. Thin Solid Films 160:43–52.
  10. 10.
    Moad G, Rizzardo E, Thang SH (2006) Living radical polymerization by the RAFT process—a first update. Aust J Chem 59:669–692. CrossRefGoogle Scholar
  11. 11.
    Bruno A (2010) Controlled radical (Co)polymerization of fluoromonomers. Macromolecules 43:10163–10184. CrossRefGoogle Scholar
  12. 12.
    Koiry BP, Moukwa M, Singh NK (2013) Reversible addition–fragmentation chain transfer (RAFT) polymerization of 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA). J Fluor Chem 153:137–142. CrossRefGoogle Scholar
  13. 13.
    Koiry BP, Klok H, Singh NK (2014) Copolymerization of 2,2,3,3,4,4,4-heptafluorobutyl acrylate with butyl acrylate via RAFT polymerization. J Fluor Chem 165:109–115. CrossRefGoogle Scholar
  14. 14.
    Nuhn L, Overhoff L, Sperner M, Kaltenberg K, Zentel R (2014) RAFT-polymerized poly(hexafluoroisopropylmethacrylate)s as precursors for functional water-soluble polymers. Polym Chem 5:2484–2495. CrossRefGoogle Scholar
  15. 15.
    Zaitsev SD, Semchikov YD, Vasil’eva EV, Kurushina LV (2012) Controlled radical (co)polymerization of (meth)acrylic esters under reversible chain transfer conditions. Polymer Science Series B 54:605–614CrossRefGoogle Scholar
  16. 16.
    Serkhacheva NS, Smirnov OL, Tolkachev AV, Prokopov NI, Plutalova AV, Chernikova EV, Kozhunova EY, Khokhlovde AR (2017) Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous–organic, and aqueous media via RAFT polymerization. RSC Adv 7:24522–24536. CrossRefGoogle Scholar
  17. 17.
    Serkhacheva NS, Plutalova AV, Kozhunova EY, Prokopov NI, Chernikova EV (2018) Amphiphilic triblock copolymers based on acrylic acid and alkyl acrylates synthesized via RAFT polymerization-induced self-assembly and RAFT miniemulsion polymerization. Polymer Science, Series B 60:204–217. CrossRefGoogle Scholar
  18. 18.
    Guo T, Tang D, Song M, Zhang B (2007) Copolymerizations of butyl methacrylate and fluorinated methacrylates via RAFT miniemulsion polymerization. J Polym Sci A Polym Chem 45:5067–5075. CrossRefGoogle Scholar
  19. 19.
    Zhang Q, Wang Q, Luo Z, Zhan X, Chen F (2009) Conventional and RAFT miniemulsion copolymerizations of butyl methacrylate with fluoromethacrylate and monomer reactivity ratios. Polym Eng Sci 49:1818–1824. CrossRefGoogle Scholar
  20. 20.
    Zhang Q, Zhan X, Chen F, Shi Y, Wang Q (2007) Block copolymers of dodecafluoroheptyl methacrylate and butyl methacrylate by RAFT miniemulsion polymerization. J Polym Sci A Polym Chem 45:1585–1594. CrossRefGoogle Scholar
  21. 21.
    Ma Z, Lacroix-Desmazes P (2004) Synthesis of hydrophilic/CO2-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) block copolymers via controlled/living radical polymerizations and their properties in liquid and supercritical CO2. J Polym Sci A Polym Chem 42:2405–2415. CrossRefGoogle Scholar
  22. 22.
    Eberhardt M, Theґato P (2005) RAFT polymerization of pentafluorophenyl methacrylate: preparation of reactive linear diblock copolymers. Macromol Rapid Commun 26:1488–1493. CrossRefGoogle Scholar
  23. 23.
    Guyot B, Ameduri B, Boutevin B, Melas M, Viguie M, Colle A (1998) Kinetics of homopolymerization of fluorinated acrylates, influence of the spacer between the fluorinated chain and the ester group. Macromol Chem Phys 199:1879–1885.<1879::AID-MACP1879>3.0.CO;2-D CrossRefGoogle Scholar
  24. 24.
    Liu B, Yuan CG, Hu CP (2001) Synthesis and characterization of a well-defined graft copolymer containing fluorine grafts by “living”/controlled radical polymerization. Macromol Chem Phys 202:2504–2508.<2504::AID-MACP2504>3.0.CO;2-M CrossRefGoogle Scholar
  25. 25.
    Shampa RS, Ruilong C, Virgil P (2014) SET-LRP of semifluorinated acrylates and methacrylates. Polym Chem 5:5479–5491. CrossRefGoogle Scholar
  26. 26.
    Sprouse D, Jiang Y, Laaser JE, Lodge TP, Reineke TM (2016) Tuning cationic block copolymer micelle size by pH and ionic strength. Biomacromolecules 17:2849–2859. CrossRefGoogle Scholar
  27. 27.
    Wang Y, Wen G, Pispas S, Yang S, Youa K (2018) Effects of subphase pH, temperature and ionic strength on the aggregation behavior of PnBA-b-PAA at the air/water interface. J Colloid Interface Sci 512:862–870. CrossRefGoogle Scholar
  28. 28.
    Guennouni Z, Cousin F, Fauré MC, Perrin P, Limagne D, Konovalov O, Goldmann M (2016) Self-organization of polystyrene-b-polyacrylic acid (PS-b-PAA) monolayer at the air/water interface: a process driven by the release of the solvent spreading. Langmuir 32:1971–1980. CrossRefGoogle Scholar
  29. 29.
    Guennouni Z, Goldmann M, Fauré MC, Fontaine P, Perrin P, Limagne D, Cousin F (2017) Coupled effects of spreading solvent molecules and electrostatic repulsions on the behavior of PS-b-PAA monolayers at the air-water interface. Langmuir 33:12525–12534. CrossRefGoogle Scholar
  30. 30.
    Joncheray TJ, Bernard SA, Matmour R, Lepoittevin B, El-Khouri RJ, Taton D, Gnanou Y, Duran RS (2007) Polystyrene-b-poly(tert-butyl acrylate) and polystyrene-b-poly(acrylic acid) dendrimer-like copolymers: two-dimensional self-assembly at the air-water Interface. Langmuir 23:2531–2538. CrossRefGoogle Scholar
  31. 31.
    Xie D, Rezende CA, Liu G, Pispas S, Zhang G, Lee LT (2009) Effect of hydrogen-bonding complexation on the interfacial behavior of poly(isoprene)-b-poly(ethylene oxide) and poly(isoprene)-b-poly(acrylic acid) Langmuir monolayers. J Phys Chem B 113:739–744. CrossRefGoogle Scholar
  32. 32.
    Turshatov AA, Semchikov YD, Zaitsev SD, Smirnova LA (1998) Langmuir monolayers of styrene copolymers with acrylic and methacrylic acids. Vysokomolekularnye Soedineniya SerB 40:1238–1241Google Scholar
  33. 33.
    Turshatov AA, Pastukhov MO, Semchikov YD (1999) Langmuir monolayers of statistical copolymers with hydrophilic and hydrophobic units. Vysokomolekularnye Soedineniya SerA 41:841–845Google Scholar
  34. 34.
    Vishnevetskii DV, Plutalova AV, Yulusov VV, Zotova OS, Chernikova EV, Zaitsev SD (2015) Controlled radical copolymerization of styrene with acrylic acid and tert-butyl acrylate under conditions of reversible addition-fragmentation chain transfer: control of the chain microstructure. Polymer Science Series B 57:197–206. CrossRefGoogle Scholar
  35. 35.
    Chernikova EV, Zaitsev SD, Plutalova AV, Mineeva KO, Zotova OS, Vishnevetsky DV (2018) Control over the relative reactivities of monomers in RAFT copolymerization of styrene and acrylic acid. RSC Advanced 8:14300–14310. CrossRefGoogle Scholar
  36. 36.
    Chernikova EV, Terpugova PS, Garina ES, Golubev VB (2007) Controlled radical polymerization of styrene and n-butyl acrylate mediated by trithiocarbonates. Polymer Science Series A 49:108–119. CrossRefGoogle Scholar
  37. 37.
    Barner-Kowollik C (2008) Handbook of RAFT Polymerization. In: Barner-Kowollik C (ed) WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimGoogle Scholar
  38. 38.
    Zhou J, Zhang L, Ma J (2013) Fluorinated polyacrylate emulsifier-free emulsion mediated by poly(acrylic acid)-b-poly(hexafluorobutyl acrylate) trithiocarbonate via ab initio RAFT emulsion polymerization. Chem Eng J 223:8–17. CrossRefGoogle Scholar
  39. 39.
    Chernikova EV, Terpugova PS, Baskakov AA, Plutalova AV, Garina ES, Sivtsov EV (2010) Pseudoliving radical polymerization of methyl methacrylate in the presence of S,S′-bis(methyl-2-isobutyrate) trithiocarbonate. Polymer Science, Ser B 52:119–128. CrossRefGoogle Scholar
  40. 40.
    Fineman M, Ross SD (1950) Linear method for determining monomer reactivity ratios in copolymerization. J Polym Sci 5:259–262. CrossRefGoogle Scholar
  41. 41.
    Kelen T, Tudos F, Turcsanyi B (1980) Confidence intervals for copolymerization reactivity ratios determined by the Kelen-Tudos method. Polym Bull 2:71–76.
  42. 42.
    Bichuch NA, Malyshev AS, Kronman AG, Pastukhov MO, Semchikov YD, Zaitsev SD (2003) Determination of relative reactivities of monomers from their instantaneous concentrations in the feed. Polymer Science, Ser. B 45:851–855Google Scholar
  43. 43.
    Borisova O, Billon L, Zaremski M, Grassl B, Bakaeva Z, Lapp A, Stepanek P, Borisov O (2012) Synthesis and pH- and salinity-controlled self-assembly of novel amphiphilic block-gradient copolymers of styrene and acrylic acid. Soft Matter 8(29):7649–7659. CrossRefGoogle Scholar
  44. 44.
    Borisova O, Zaremski M, Borisov O, Billon L (2013) The well defined bootstrap effect in the macroinitiator mediated pseudo living radical copolymerization of styrene and acrylic acid. Polymer Science Series B 55(11–12):573–576CrossRefGoogle Scholar
  45. 45.
    Pai TSC, Barner-Kowollik C, Davis TP, Stenzel MH (2004) Synthesis of amphiphilic block copolymers based on poly(dimethylsiloxane) via fragmentation chain transfer (RAFT) polymerization. Polymer 45:4383–4389. CrossRefGoogle Scholar
  46. 46.
    Kerber R (1966) Änderung der copolymerisationsparameter im system styrol/acrylsäure durch lösungsmitteleffekte. Makromol Chem 96:30–40. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Alexandra Grigoreva
    • 1
    Email author
  • Egor Polozov
    • 1
  • Sergey Zaitsev
    • 1
  1. 1.Lobachevsky State University of Nizhni NovgorodNizhni NovgorodRussia

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