Skip to main content
SpringerLink
Log in

Micellization and Adsorption Behaviors of New Reactive Polymerizable Surfactants Based on Modified Nonyl Phenol Ethoxylates

  • Original Article
  • Published:
Journal of Surfactants and Detergents

Abstract

The synthesis and characterization of a series of polymerizable surfactants based on alkyl phenol ethoxylate backbone and carboxylic or anhydride chain ends were investigated. Surface activities of these polymerizable surfactants were investigated to correlate their structure and their performances. The new bifunctional surfmers were prepared by reacting polyoxyethylene 4-nonyl-2-propylene-phenol nonionic reactive surfactants with maleic anhydride. The chemical structure of the prepared surfactants was characterized by 13C and 1H NMR analyses. The surface activities of the modified polymerizable surfactants were measured from the adsorption isotherm measurements which were determined from the relationship between the concentrations and surface tension of surfactants in aqueous medium at different temperatures. Critical micelle concentration (CMC) values were determined for water soluble surfactants. It was found that CMC decreases with the incorporation of the anhydride and acid groups in the chemical structure of polyoxyethylene 4-nonyl -2-propylene-phenol nonionic surfactant. surface-active parameters such as area per molecule at the interface (A min), surface excess concentration (Γmax) and the effectiveness of surface tension reduction (πCMC) were measured from the adsorption isotherms of the modified surfactants. Some thermodynamic data for the adsorption process were calculated and discussed. The data indicated that the new surfmers are more reactive than the simple polyoxyethylene 4-nonyl-2-propylene-phenol and more adsorbed at interfaces. We have performed a preliminary experiment to explore the emulsification efficiency of the newly synthesized reactive surfactants in equal volume oil–water emulsions. Different emulsion types and stabilities were obtained.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Piirma I (1992) Polymeric surfactants, surfactant science series. Marcel Dekker, New York, pp 42–60

    Google Scholar 

  2. Hentze HP, Kaler EW (2003) Polymerization of and within self-organized media. Curr Opin Colloid Interface Sci 8:164–178

    Article  CAS  Google Scholar 

  3. Meier W (1999) Nanostructure synthesis using surfactants and copolymers. Curr Opin Colloid Interface Sci 4:6–14

    Article  CAS  Google Scholar 

  4. Antonietti M, Hentze HP (1996) Synthesis of sponge-like polymer dispersions via polymerization of bicontinuous microemulsions. Colloid Polym Sci 274:696–702

    Article  CAS  Google Scholar 

  5. Xu W, Siow KS, Gao Z, Lee SY, Chow PY, Gan LM (1999) Microporous polymeric composite electrolytes from microemulsion polymerization. Langmuir 15:4812–4819

    Article  CAS  Google Scholar 

  6. Chow PY, Chew CH, Ong CC, Wang J, Xu G, Gan LM (1999) Ion-containing membranes from microemulsion polymerization. Langmuir 15:3202–3205

    Article  CAS  Google Scholar 

  7. Tan H, Nie J (2007) Photopolymerization and characteristics of polyurethane/organoclay nanocomposites. Macromol React Eng 1:384–390

    Article  CAS  Google Scholar 

  8. Ivanchev SS, Pavljuchenko VN, Byrdina NA (1987) Elementary reactions of the emulsions polymerization of styrene with the localization of radical formation acts at the interface. J Polym Sci A Polym Chem 25:47–62

    Article  CAS  Google Scholar 

  9. Tauer K, Zimmermann A (2000) New reactive polymeric stabilizers for emulsion polymerization. Macromol Rapid Commun 21:825–831

    Article  CAS  Google Scholar 

  10. Morrison BR, Casey BS, Lacik I, Leslie GL, Sangster DF, Gilbert RG, Napper DH (1992) Desorbed free radicals in emulsion polymerizations: effect of aqueous-phase spin trap. Macromolecules 25:4065–4072

    Article  Google Scholar 

  11. Hamaide T, Revillon A, Guyot A (1987) Radical transfer on styrenic macromonomers of polyoxyethylene, II: studies on model compounds. Eur Polym J 23:787–796

    Article  CAS  Google Scholar 

  12. Deen GR, Gan LH (2009) New piperazine-based polymerizable monoquaternary cationic surfactants: synthesis, polymerization, and swelling characteristics of gels. J Polym Sci, Part A: Polym Chem 47:2059–2072

    Article  CAS  Google Scholar 

  13. Vidal F, Guillot J, Guyot A (1995) Surfactants with transfer agent properties (transurfs) in styrene emulsion polymerization. Colloid Polym Sci 273:999

    Article  CAS  Google Scholar 

  14. Vidal F, Guillot J, Guyot A (1994) Steric stabilization of polystyrene colloids using thiol-ended polyethylene oxide. Polym Adv Technol 6:473–479

    Article  Google Scholar 

  15. Guyot A, Tauer K (1994) Reactive surfactants in emulsion polymerization. Adv Polym Sci 111:43–65

    Article  CAS  Google Scholar 

  16. Tauer K (1995) Reactive surfactants for emulsion polymerisation. Polym News 20:342–347

    CAS  Google Scholar 

  17. Lacroix-Desmazes P, Guyot A (1996) Reactive surfactants in heterophase polymerization. Polym Bull 37:183–189

    Article  CAS  Google Scholar 

  18. Takahashi K, Nagai K (1996) Preparation of reactive polymeric microspheres by seeded copolymerization using a polymerizable surfactant bearing an active ester group. Polymer 37:1257

    Article  CAS  Google Scholar 

  19. Al-Sabagh AM, Atta AM (1999) Water-based non-ionic polymeric surfactants as oil spill dispersants. J Chem Technol Biotechnol 74:1075–1081

    Article  CAS  Google Scholar 

  20. Makino S, Reynolds JA, Tanford C (1973) The binding of deoxycholate and Triton X-100 to proteins. J Biol Chem 248:4926

    CAS  Google Scholar 

  21. Almgren M, Lofroth J, Stam J (1986) Fluorescence decay kinetics in monodisperse confinements with exchange of probes and quenchers. J Phys Chem 90:4431–4437

    Article  CAS  Google Scholar 

  22. Kubeck E, Naylor CG (1990) Trace analysis of alkylphenol ethoxylates. J Am Oil Chem Soc 67:400–405

    Article  CAS  Google Scholar 

  23. Podo F, Ray A, Nemethy G (1973) Structure and hydration of nonionic detergent micelles. High resolution nuclear magnetic resonance study. J Am Chem Soc 95:6164–6171

    Article  CAS  Google Scholar 

  24. Schott H (1997) Effect of inorganic additives on solutions of nonionic surfactants. J Colloid Interface Sci 192:458–462

    Article  CAS  Google Scholar 

  25. Schott H (1998) Comparing the surface chemical properties and the effect of salts on the cloud point of a conventional nonionic surfactant, octoxynol 9, and of its oligomer. Tyloxapol J Colloid Interface Sci 205:496–502

    Article  CAS  Google Scholar 

  26. Leary B, Lyons CJ (1989) A novel composite polymer latex technology. Aust J Chem 42:2055–2070

    Article  CAS  Google Scholar 

  27. Schoonbrood HAS (1997) Reactive surfactants in heterophase polymerization. 9. Optimum surfmer behavior in emulsion polymerization. Macromolecules 30:6034–6041

    Article  CAS  Google Scholar 

  28. Lee DK, Choi J-Y, Lee ES, Ha C-S, Han M, Bae J-Y (2007) Synthesis and characterization of Triton X-based surfactants with carboxylic or amino groups in the oxyethylene chain end. J Appl Polym Sci 104:162–170

    Article  CAS  Google Scholar 

  29. Starostin N, Harvey S, Carlson G (2008) Aspects of latex particle size control for improved water blush resistance. Scanning 30:78–86

    Article  CAS  Google Scholar 

  30. Wada T, Inui K, Uragami TY (2006) Properties of organic–inorganic composite materials prepared from acrylic resin emulsions and colloidal silicas. J Appl Polym Sci 101:2051–2056

    Article  CAS  Google Scholar 

  31. Lai Z, Sudol ED, Dimonie VL, El-Aasser MS (2008) Kinetics of emulsion polymerization of styrene using the reactive surfactant Hitenol BC20. J Appl Polym Sci 109:2275–2282

    Article  CAS  Google Scholar 

  32. Shoaf GL (2010) Delivering solvent based polymers in eco-friendly water based systems. Chem Eng Technol 33:1788–1796

    Article  CAS  Google Scholar 

  33. Atta AM, El-Ghazawy RAM, Farag RK, Abdel-Azim AA (2006) Crosslinked reactive macromonomers based on polyisobutylene and octadecyl acrylate copolymers as crude oil sorbers. React Funct Polym 66:931–943

    Article  CAS  Google Scholar 

  34. Uzulina I, Zicmanis A, Graillat C, Claverie J, Guyot A (2001) Synthesis of polymer colloids using polymerizable surfactants. Macromol Chem Phys 202:3126–3135

    Article  CAS  Google Scholar 

  35. Atta AA (2007) Surface and thermodynamic parameters of polymeric surfactants from recycled poly (ethylene terephthalate). Polym Int 56:984–995

    Article  CAS  Google Scholar 

  36. Atta AA, Abdel-Rauf ME, Maysour NE, Abdul-Rahiem AM, Abdel-Azim AA (2006) Surfactants from recycled poly (ethylene terephthalate) waste as water based oil spill dispersants. J Polym Res 13:39–52

    Article  CAS  Google Scholar 

  37. Atta AM, Al-Shafy HI, Mohamed ZM (2011) Application of hydrophobically modified water-soluble polyacrylamide conjugated with poly(oxyethylene)-co-poly(oxypropylene), surfactant as emulsifier. Polym Adv Technol 22:1879–1887

    Article  CAS  Google Scholar 

  38. Nakagawa T, Shinoda K (1963) New aspects in colloidal surfactants. In: Shinoda K, Nakagawa T, Tamamuushi B, Esemura T (eds) Colloidal surfactants. Academic, New York, pp 129–145

  39. Xu XJ, Goh HL, Siow KS, Gan LM (2001) Synthesis of polymerizable anionic surfactants and their emulsion copolymerization with styrene. Langmuir 17:6077–6085

    Article  CAS  Google Scholar 

  40. Hamid SM, Sherrington DC (1987) Novel quaternary ammonium amphiphilic methacrylates: 1. Synthesis, melting and interfacial behaviour. Polymer 28:325–331

    Article  CAS  Google Scholar 

  41. Wertz DH (1980) Relationship between the gas-phase entropies of molecules and their entropies of solvation in water and 1-octanol. J Am Chem Soc 102:5316–5322

    Article  CAS  Google Scholar 

  42. Rosen MJ, Aronson S (1981) Standard free energies of adsorption of surfactants at the aqueous solution/air interface from surface tension data in the vicinity of the critical micelle concentration. Colloid Surf 3:201–208

    Article  CAS  Google Scholar 

  43. Binks BP (ed) (1998) Modern aspects of emulsion science. Royal Society of Chemistry, Cambridge, UK

    Google Scholar 

  44. Shinoda K, Saito H (1969) The stability of O/W type emulsions as functions of temperature and the HLB of emulsifiers: the emulsification by PIT-method. J Colloid Interface Sci 30:258–263

    Article  CAS  Google Scholar 

  45. Binks BP (1993) Relationship between microemulsion phase behavior and macroemulsion type in systems containing non-ionic surfactant. Langmuir 9:25–28

    Article  CAS  Google Scholar 

  46. Wennerström H, Soderman O, Olsson U, Lindman B (1997) Macroemulsions versus microemulsions. Colloids Surf A 123–124:13–26

    Article  Google Scholar 

Download references

Acknowledgments

This Project was supported by King Saud University, Deanship of Scientific Research, College of Science Research Center.

Author information

Authors and Affiliations

  1. Chemistry Department, College of Science, King Saud University, P.O.Box 2455, Riyadh, 11451, Kingdom of Saudi Arabia

    Ayman M. Atta, Amro K. F. Dyab & Hamad A. Al-Lohedan

  2. Egyptian Petroleum Research Institute, Petroleum Application Department, Nasr City, 11727, Cairo, Egypt

    Ayman M. Atta

  3. Chemistry Department, Faculty of Science, Minia University, 61519, Minia, Egypt

    Amro K. F. Dyab

Authors
  1. Ayman M. Atta
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Amro K. F. Dyab
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hamad A. Al-Lohedan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ayman M. Atta.

About this article

Cite this article

Atta, A.M., Dyab, A.K.F. & Al-Lohedan, H.A. Micellization and Adsorption Behaviors of New Reactive Polymerizable Surfactants Based on Modified Nonyl Phenol Ethoxylates. J Surfact Deterg 16, 343–355 (2013). https://doi.org/10.1007/s11743-012-1413-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11743-012-1413-5

Keywords

Search

Navigation