Skip to main content
SpringerLink
Log in

Self-assembly of comb-like amphiphilic copolymers in aqueous solution

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

Comb-like amphiphilic copolymers (polysoaps) have been studied by small-angle neutron scattering and light scattering techniques. The copolymer was synthesized by randomly grafting pendant quaternized alkylamine moieties (surfactant-like unit) to a polystyrene (hydrophobic) chain. In aqueous solution, the polymers self-assembled into platelet aggregates at low concentrations. When the electrostatic repulsions are screened by increasing the polymer concentration or by the addition of salt, hydrophobic interactions lead to a faster aggregation of platelets and leads to a phase separation. As the polymer concentration increases, the platelets extend by the edges to yield a final smectic organization of large sized lamellae. As a consequence visco-elastic solutions or hydrogels were formed at higher concentrations.

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
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  1. Holder SJ, Sommerdijk NAJM (2011) New micellar morphologies from amphiphilic block copolymers: disks, toroids and bicontinuous micelles. Polym Chem 2:1018–1028. doi:10.1039/C0PY00379D

    Article  CAS  Google Scholar 

  2. Cheng G, Melnichenko YB, Wignall GD, Hua F, Hong K, Mays JW (2008) Small angle neutron scattering study of conformation of oligo(ethylene glycol)-grafted polystyrene in dilute solutions: effect of the backbone length. Macromolecules 41:9831–9836. doi:10.1021/ma801370q

    Article  CAS  Google Scholar 

  3. Xu W, Choi I, Plamper FA, Synatschke CV, Müller AHE, Melnichenko YB, Tsukruk VV (2014) Thermo-induced limited aggregation of responsive star polyelectrolytes. Macromolecules 47:2112–2121. doi:10.1021/ma500153w

    Article  CAS  Google Scholar 

  4. Chassenieux C, Nicolai T, Benyahia L (2011) Rheology of associative polymer solutions. Curr Opin Colloid Interface Sci 16:18–26. doi:10.1016/j.cocis.2010.07.007

    Article  CAS  Google Scholar 

  5. Glotzer SC, Solomon MJ (2007) Anisotropy of building blocks and their assembly into complex structures. Nat Mater 6:557–562. doi:10.1038/nmat1949

    Article  Google Scholar 

  6. Laschewsky A (1995) Molecular concepts, self-organization and properties of polysoaps. Adv Polym Sci 124:1–86. doi:10.1007/BFb0025228

    Article  CAS  Google Scholar 

  7. Hamid SM, Sherrington DC (1987) Novel quaternary ammonium amphiphilic (meth)acrylates. 1. Synthesis, melting and interfacial behaviour. Polymer 28:325–331. doi:10.1016/0032-3861(87)90426-5

    Article  CAS  Google Scholar 

  8. Guyot A, Tauer K (1985) Reactive surfactants in emulsion polymerization. Adv Poly Sci 111:43–65. doi:10.1007/BFb0024126

    Article  Google Scholar 

  9. Barbieri BW, Strauss UP (1985) Effect of alkyl group size on the cooperativity in conformational transitions of hydrophobic polyacids. Macromolecules 18:411–414. doi:10.1021/ma00145a019

    Article  CAS  Google Scholar 

  10. FitzGerald PA, Warr GG (2012) Structure of polymerizable surfactant micelles: insights from neutron scattering. Adv Colloid Interface Sci 179–182:14–21. doi:10.1016/j.cis.2012.06.003

    Article  Google Scholar 

  11. Cochin D, Candau F, Zana R (1993) Photopolymerization of micelle-forming monomers. 1. Characterization of the systems before and after polymerization. Macromolecules 26:5755–5764. doi:10.1021/ma00073a033

    Article  CAS  Google Scholar 

  12. Cochin D, Candau F, Zana R, Talmon Y (1992) Direct imaging of microstructures formed in aqueous solutions of polyamphiphiles. Macromolecules 25:4220–4223. doi:10.1021/ma00042a028

    Article  CAS  Google Scholar 

  13. Cochin D, Zana R, Candau F (1993) Photopolymerization of micelle-forming monomers. 2. Kinetic study and mechanism. Macromolecules 26:5765–5771. doi:10.1021/ma00073a034

    Article  CAS  Google Scholar 

  14. Moussa W (2016) Structure of a self-assembled network made of polymeric worm-like micelles. Polym Bull 73:2689–2705. doi:10.1007/s00289-016-1615-5

    Article  CAS  Google Scholar 

  15. Dutertre F, Gaillard C, Chassenieux C, Nicolai T (2015) Branched wormlike micelles formed by self-assembled comblike amphiphilic copolyelectrolytes. Macromolecules 48:7604–7612. doi:10.1021/acs.macromol.5b01503

    Article  CAS  Google Scholar 

  16. Chassenieux C, Fundin J, Ducouret G, Iliopoulos I (2000) Amphiphilic copolymers of styrene with a surfactant-like comonomer: gel formation in aqueous solution. J Mol Struct 554:99–108. doi:10.1016/S0022-2860(00)00563-9

    Article  CAS  Google Scholar 

  17. Limouzin-Morel C, Dutertre F, Moussa W, Gaillard C, Iliopoulos I, Bendejacq D, Nicolai T, Chassenieux C (2013) One and two dimensional self-assembly of comb-like amphiphilic copolyelectrolytes in aqueous solution. Soft Matter 9:8931–8937. doi:10.1039/c3sm51895g

    Article  CAS  Google Scholar 

  18. Nallet F, Laversanne R, Roux D (1993) Modelling X-ray or neutron scattering spectra of lyotropic lamellar phases: interplay between form and structure factors. J Phys II 3:487–502. doi:10.1051/jp2:1993146

    CAS  Google Scholar 

  19. Raghavan SR, Fritz G, Kaler EW (2002) Wormlike micelles formed by synergistic self-assembly in mixtures of anionic and cationic surfactants. Langmuir 18:3797–3803. doi:10.1021/la0115583

    Article  CAS  Google Scholar 

  20. Zhao Y, Haward SJ, Shen AQ (2015) Rheological characterizations of wormlike micellar solutions containing cationic surfactant and anionic hydrotropic salt. J Rheol 59:1229–1259. doi:10.1122/1.4928454

    Article  CAS  Google Scholar 

  21. Dazzazi A, Coppel Y, In M, Chassenieux C, Mascalchi P, Salomé L, Bouhaouss A, Kahn ML, Gauffre F (2013) Oligomeric and polymeric surfactants for the transfer of luminescent ZnO nanocrystals to water. J Mater Chem C 1:2158–2165. doi:10.1039/C3TC00877K

    Article  CAS  Google Scholar 

  22. Save M, Manguian M, Chassenieux C, Charleux B (2005) Synthesis by RAFT of amphiphilic block and comblike cationic copolymers and their use in emulsion polymerization for the electrosteric stabilization of latexes. Macromolecules 38:280–289. doi:10.1021/ma048487+

    Article  CAS  Google Scholar 

  23. Dif A, Henry E, Artzner F, Baudy-Floc’h M, Schmutz M, Dahan M, Marchi-Artzner V (2008) Interaction between water-soluble peptidic CdSe/ZnS nanocrystals and membranes: formation of hybrid vesicles and condensed lamellar phases. J Am Chem Soc 130:8289–8296. doi:10.1021/ja711378g

    Article  CAS  Google Scholar 

  24. Yeh SW, Wie KH, Sun YS, Jeng US, Liang KS (2005) CdS nanoparticles induce a morphological transformation of poly(styrene-b-4-vinylpyridine) from hexagonally packed cylinders to a lamellar structure. Macromolecules 38:6559–6565. doi:10.1021/ma047653a

    Article  CAS  Google Scholar 

  25. Thompson RB, Ginzburg VV, Matsen MW, Balazs AC (2001) Predicting the mesophases of copolymer-nanoparticle composites. Science 292:2469–2472. doi:10.1126/science.1060585

    Article  CAS  Google Scholar 

  26. Lee JY, Thompson RB, Jasnow D, Balazs AC (2002) Effect of nanoscopic particles on the mesophase structure of diblock copolymers. Macromolecules 35:4855–4858. doi:10.1021/ma0200266

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The financial support of Région Pays de la Loire is acknowledged. LLB is thanked for providing access to the SANS experiments. I also thank Pr. C. Chassenieux and Dr. O. Colombani for supervising this work.

Author information

Authors and Affiliations

  1. Département Polymères, Colloïdes, Interfaces, PRES LUNAM, Université du Maine, IMMM UMR CNRS 6283, Avenue O. Messiaen, 72085, Lemans Cedex 9, France

    Wissam Moussa

Authors
  1. Wissam Moussa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Wissam Moussa.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 344 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Moussa, W. Self-assembly of comb-like amphiphilic copolymers in aqueous solution. Polym. Bull. 74, 1405–1419 (2017). https://doi.org/10.1007/s00289-017-1910-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-017-1910-9

Keywords

Search

Navigation