Skip to main content
SpringerLink
Log in

Synthesis and Characterization of Novel Surfactants Based on 2-Hydroxy-4-(Methylthio)Butanoic Acid: 1. Anionic Surfactants

  • Original Article
  • Published:
Journal of Surfactants and Detergents

Abstract

2-Hydroxy-4-(methylthio)butanoic acid (HMTBA) is a commonly used animal feed additive available in large quantities. In this study, anionic surfactants were synthesized utilizing HMTBA as a starting material. Specifically, a straight-chain fatty acid containing 12 or 16 carbon atoms was attached to the hydroxyl group via esterification. After neutralization of the carboxylic acid with sodium, the molecules behave as anionic surfactants. Oxidation of the sulfur atom can be performed to further increase water solubility. The molecules exhibit critical micelle concentrations (CMCs), and lower the surface tension to 35–45 mN/m at the CMC. The derivatives have low Krafft points (<4 °C) and good wetting performance. The hardness tolerance of the ester made from dodecanoic acid is ~2.5–4 orders of magnitude higher than an analogous carboxylate surfactant, namely sodium dodecanoate. Foam created according to the Ross-Miles foam test is substantial, but dissipates quickly as compared to other anionic surfactants.

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

Similar content being viewed by others

Abbreviations

HMTBA:

2-Hydroxy-4-(methylthio)butanoic acid

AES:

Alkyl ether sulfate

SDS:

Sodium dodecyl sulfate

SDBS:

Sodium dodecylbenzene sulfonate

CMC:

Critical micelle concentration

γ CMC :

Surface tension at the CMC

Γm :

Maximum surface excess concentration/maximum adsorption density

C20:

Surfactant concentration that lowers the surface tension by 20 mN/m

a min :

Minimum area per molecule at the interface

References

  1. Tsoler U (1999) Handbook of detergents. M. Dekker, New York

    Google Scholar 

  2. Smulders E, von Rybinski W, Sung E, Rähse W, Steber J, Wiebel F, Nordskog A (2000) Laundry detergents. Wiley, Germany

    Google Scholar 

  3. Atwood JL, Steed JW (2004) Encyclopedia of supramolecular chemistry. Marcel Dekker, New York

    Google Scholar 

  4. El-Sukkary MMA, Soliman EA, Ismail DA, El Rayes SM, Saad MA (2011) Synthesis and properties of some N-acylethylenediamine triacetic acid chelating surfactants. Tenside Surfactants Deterg 48:82–86

    Article  CAS  Google Scholar 

  5. Fujiwara M, Miyake M, Abe Y (1993) Colloidal properties of alpha-sulfonated fatty acid methyl esters and their applicability in hard water. Colloid Polym Sci 271:780–785

    Article  CAS  Google Scholar 

  6. Hong J-J, Yang S-M, Choi Y-K, Lee C-H (1995) Precipitation of tricarboxylic acid biosurfactant derived from spiculisporic acid with metal ions in aqueous solution. J Colloid Interface Sci 173:92–103

    Article  CAS  Google Scholar 

  7. Laurent JCTRBS, Connor DS, Cripe TA, Dupont JS, Scheibel JJ, Stidham RE, Vinson PK, Willman KW (2000) Mid-chain branched surfactants. US Patent 6,020,303

  8. Laurent JCTRBS, Connor DS, Cripe TA, Dupont JS, Vinson PK, Willman KW (2000) Mid-chain branched alkyl sulfate surfactants. US patent 6,060,443

  9. Laurent JCTRBS, Connor DS, Cripe TA, Vinson PK, Willman KW (1999) Mid-chain branched alkoxylated sulfate surfactants. US Patent 6,008,181

  10. Scheibel J (2004) The evolution of anionic surfactant technology to meet the requirements of the laundry detergent industry. J Surfactants Deterg 7:319–328

    Article  CAS  Google Scholar 

  11. Shi J, Kloepper-Sams P, Giolando S, Federle T, Versteeg D, Belanger S (2000) Biodegradable high solubility alkyl sulfate surfactants: environmental safety profiles, in 5th World Surfactant Congress. Federchimica, Milan, pp 1525–1531

    Google Scholar 

  12. Stirton AJ, Bistline RG, Maurer EW, Weil JK, Ault WC (1962) Sodium salts of alkyl esters of alpha-sulfo fatty acids–wetting, lime soap dispersion, and related properties. J Am Oil Chem Soc 39:128–139

    Article  CAS  Google Scholar 

  13. van Duynhoven J, Leika A, van der Hoeven R (2005) Quantitative assessment of alkyl chain branching in alcohol-based surfactants by nuclear magnetic resonance. J Surfactants Deterg 8:73–82

    Article  Google Scholar 

  14. Xing F, Niu J, Liu X, Wang X (2014) Effect of a spacer group on surface activity, salinity and hardness tolerance, mimic oil washing efficiency of monododecyl diaryl disulfonate. J Surfactants Deterg 17:95–100

    Article  CAS  Google Scholar 

  15. Yu D, Wang Y, Zhang J, Tian M, Han Y, Wang Y (2012) Effects of calcium ions on solubility and aggregation behavior of an anionic sulfonate gemini surfactant in aqueous solutions. J Colloid Interface Sci 381:83–88

    Article  CAS  Google Scholar 

  16. Dawe B, Oswald T (1991) Reduced adsorption and separation of blended surfactants on sand and clay. J Can Pet Technol 30:133–137

    Article  CAS  Google Scholar 

  17. Lad K, Bahadur A, Pandya K, Bahadur P (1995) Clouding and aggregation behavior of ethylene-oxide propylene-oxide ethylene-oxide block-copolymers in aqueous-media in the presence of sodium dodecyl-sulfate. Indian J Chem Sec a-Inorg Bio-Inorg Physical Theor Anal Chem 34:938–945

    Google Scholar 

  18. Rodriguez CH, Scamehorn JF (1999) Modification of Krafft temperature or solubility of surfactants using surfactant mixtures. J Surfactants Deterg 2:17–28

    CAS  Google Scholar 

  19. Sharma R, Desai A, Bahadur P (2003) Hardness tolerance of anionic surfactants in the presence of nonionic surfactants. Tenside Surfactants Deterg 40:31–34

    CAS  Google Scholar 

  20. Satsuki T, Nagoh Y, Yoshimura H (1998) Effect of calcium ions on detergency—part 2: interactions between a surfactant, a calcium-sequestering builder and calcium ions. Tenside Surfactants Deterg 35:112–118

    CAS  Google Scholar 

  21. Yu YX, Zhao J, Bayly AE (2008) Development of surfactants and builders in detergent formulations. Chin J Chem Eng 16:517–527

    Article  CAS  Google Scholar 

  22. Tanthakit P, Nakrachata-Amorn A, Scamehorn JF, Sabatini DA, Tongcumpou C, Chavadej S (2009) Microemulsion formation and detergency with oily soil: V. Effects of water hardness and builder. J Surfactants Deterg 12:173–183

    Article  CAS  Google Scholar 

  23. Sweeney W, Anderson R (1989) Biodegradability of alkylbenzene sulfonates. J Am Oil Chem Soc 66:1844–1849

    Article  CAS  Google Scholar 

  24. Anonymous (1965) Testing for surfactant biodegradability industrial and engineering chemistry 57: 45–6

  25. Dibner JJ, Knight CD (1984) Conversion of 2-hydroxy-4-(methylthio)butanoic acid to l-methionine in the chick—a stereospecific pathway. J Nutr 114:1716–1723

    CAS  Google Scholar 

  26. Schott H, Han SK (1976) Effect of inorganic additives on solutions of nonionic surfactants 4: Krafft points. J Pharm Sci 65:979–981

    Article  CAS  Google Scholar 

  27. International ASTM (2007) Standard test method for foaming properties of surface-active agents. West Conshohocken, Pennsylvania

    Google Scholar 

  28. International ASTM (2010) Standard test method for evaluation of wetting agents by the Skein test. West Conshohocken, Pennsylvania

    Google Scholar 

  29. Guzman A, Bueno A, Carbognani L (2009) Molecular weight determination of asphaltenes from Colombian crudes by size exclusion chromatography (SEC) and vapor pressure osmometry (VPO). Pet Sci Technol 27:801–816

    Article  CAS  Google Scholar 

  30. Dahanayake M, Cohen AW, Rosen MJ (1986) Relationship of structure to properties of surfactants. 13. Surface and thermodynamic properties of some oxyethylenated sulfates and sulfonates. J Phys Chem 90:2413–2418

    Article  CAS  Google Scholar 

  31. Glukhareva NA, Pletnev MY (1995) Krafft points of some mixtures based on individual sodium soaps. Colloid J 57:253–255

    CAS  Google Scholar 

  32. Elworthy PH, Mysels KJ (1966) Surface tension of sodium dodecylsulfate solutions and phase separation model of micelle formation. J Colloid Interface Sci 21:331–347

    Article  CAS  Google Scholar 

  33. Acevedo S, Gutierrez LB, Negrin G, Pereira JC, Mendez B, Delolme F, Dessalces G, Broseta D (2005) Molecular weight of petroleum asphaltenes: a comparison between mass spectrometry and vapor pressure osmometry. Energy Fuels 19:1548–1560

    Article  CAS  Google Scholar 

  34. van Voorst Vader F (1960) Adsorption of detergents at the liquid-liquid interface. Part 1. Trans Faraday Soc 56:1067–1077

    Article  Google Scholar 

  35. DeLisi R, Inglese A, Milioto S, Pellerito A (1997) Demixing of mixed micelles Thermodynamics of sodium perfluorooctanoate sodium dodecanoate mixtures in water. Langmuir 13:192–202

    Article  CAS  Google Scholar 

  36. Ingram T, Jones MN (1969) Membrane Potential Studies on Surfactant Solutions. Trans Faraday Soc 65:297–304

    Article  CAS  Google Scholar 

  37. Akhter MS (1997) Effect of acetamide on the critical micelle concentration of aqueous solutions of some surfactants. Colloids Surf A Physicochem Eng Asp 121:103–109

    Article  CAS  Google Scholar 

  38. Kralchevsky PA, Danov KD, Pishmanova CI, Kralchevska SD, Christov NC, Ananthapadmanabhan KP, Lips A (2007) Effect of the precipitation of neutral-soap, acid-soap, and alkanoic acid crystallites on the bulk pH and surface tension of soap solutions. Langmuir 23:3538–3553

    Article  CAS  Google Scholar 

  39. Jackson LP, Townsend C, Grady BP (2013) Mixtures of nonionic surfactants made from renewable resources with alkyl sulfates and sodium n-alkanecarboxylates: comparison of mixing behavior using Rubingh’s treatment. J Surfactants Deterg 16:893–902

    Article  CAS  Google Scholar 

  40. Wen X, Franses EI (2000) Effect of protonation on the solution and phase behavior of aqueous sodium myristate. J Colloid Interface Sci 231:42–51

    Article  CAS  Google Scholar 

  41. Campbell AN, Lakshmin GR (1965) Conductances and surface tensions of aqueous solutions of sodium decanoate sodium laurate and sodium myristate at 25° and 35°. Can J Chem 43:1729–1737

    Article  CAS  Google Scholar 

  42. Tanaka S, Kawasaki H, Maeda H (2005) Complex formation in alkyldimethylamine oxide/sodium palmitate/water mixtures. J Colloid Interface Sci 283:238–244

    Article  CAS  Google Scholar 

  43. Blanco E, González-Pérez A, Ruso JM, Pedrido R, Prieto G, Sarmiento F (2005) A comparative study of the physicochemical properties of perfluorinated and hydrogenated amphiphiles. J Colloid Interface Sci 288:247–260

    Article  CAS  Google Scholar 

  44. Weil JK, Smith FD, Bistline RG, Stirton AJ (1963) Long chain alkanesulfonates and 1-hydroxy-2-alkanesulfonates—structure and property relations. J Am Oil Chem Soc 40:538–541

    Article  CAS  Google Scholar 

  45. Stellner KL, Scamehorn JF (1989) Hardness tolerance of anionic surfactant solutions. 1. Anionic surfactant with added mono-valent electrolyte. Langmuir 5:70–77

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute for Applied Surfactant Research and School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, OK, 73019, USA

    Guangzhe Yu, Scott A. Long, Kyle A. Karinshak, Brian P. Grady, Jeff H. Harwell & Graciela B. Arhancet

  2. Novus International Inc., 20 Research Park Drive, St. Charles, MO, 63304, USA

    Scott A. Long & Graciela B. Arhancet

Authors
  1. Guangzhe Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Scott A. Long
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kyle A. Karinshak
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Brian P. Grady
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jeff H. Harwell
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Graciela B. Arhancet
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Brian P. Grady or Graciela B. Arhancet.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 70 kb)

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yu, G., Long, S.A., Karinshak, K.A. et al. Synthesis and Characterization of Novel Surfactants Based on 2-Hydroxy-4-(Methylthio)Butanoic Acid: 1. Anionic Surfactants. J Surfact Deterg 18, 895–903 (2015). https://doi.org/10.1007/s11743-015-1690-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11743-015-1690-x

Keywords

Search

Navigation