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Oligomeric cationic Gemini surfactants: synthesis, surface activities and rheological properties as thickener

  • Ming Zhou

    Ming Zhou received his B.Sc., M.Sc. and Ph.D. from the Southwest Petroleum University in Chengdu of the PR China and worked at the School of New Energy and Materials at Southwest Petroleum University as a research chemist in 2002. He is a professor at the State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation. His research field is oil-field chemicals.

     EMAIL logo     , Xinyi Deng

    Xinyi Deng studied at the School of New Energy and Materials at Southwest Petroleum University as a doctoral student (2020 Grade). She is majoring in materials and chemicals.

         , Yiping Chen

    Yiping Chen studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2017 Grade). She is majoring in materials engineering.

         , Yaxiong Zhao

    Yaxiong Zhao studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2020 Grade). He is majoring in materials and chemicals.

         , Ruifeng Ni

    Ruifeng Ni studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2020 Grade). He is majoring in materials science and engineering.

         and Jiangyu Huang

    Jiangyu Huang studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2020 Grade). He is majoring in materials science and engineering.
Published/Copyright: September 22, 2022
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Tenside Surfactants Detergents
From the journal Tenside Surfactants Detergents Volume 59 Issue 6

Abstract

In this study, three oligomeric cationic Gemini surfactants (Ⅲ1, Ⅲ2, and Ⅲ3) were prepared from different major raw materials, including long-chain alkyl amine (dodecyl amine, tetradecyl amine or cetyl amine), formic acid, formaldehyde, diethyl amine hydrochloride and epichlorohydrin. The synthesis conditions for one of the three surfactants, bis-[2-hydroxy-3-(N,N-dimethyl-N-dodecyl)propyl]dipropylammonium chloride (Ⅲ1), were optimised by orthogonal experiments. The optimum synthesis conditions were: molar ratio of intermediate Ⅱ to intermediate Ⅰ1 = 1.0:2.2, reaction temperature = 85 °C and reaction time = 16 h. The structures of the three prepared compounds were characterised by FTIR and 1H NMR. Their thermal properties were evaluated by thermal gravimetric analysis (TGA). The Geminisurfactants prepared exhibited better surface active properties than conventional single chain cationic surfactants. With increasing carbon chain length from C12 to C16, both CMC and surface tension γCMC decreased, while the viscosity of the thickening solution prepared with the synthesised oligomeric cationic Gemini surfactants as the main component increased. The optimum thickening formula was: 2.0 wt% Ⅲ3 + 0.8 wt% sodium salicylate (NaSal) + 0.6 wt% KCl. The viscosity of the optimum thickening formulation was 190.4 mPa s. Gemini oligomeric cationic surfactants could be used as thickeners in the production of fracturing fluids, flooding agents and drilling fluids for oil and gas production in oil fields.

Keywords: fracturing fluids; oligomeric cationic Gemini surfactants; rheological properties; surface properties; thickener; wormlike micelle
Corresponding author: Dr. Ming Zhou, State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan 610500, China; School of New Energy and Materials, Southwest Petroleum University, Chengdu, Sichuan 610500, China, E-mail:

About the authors

Ming Zhou

Ming Zhou received his B.Sc., M.Sc. and Ph.D. from the Southwest Petroleum University in Chengdu of the PR China and worked at the School of New Energy and Materials at Southwest Petroleum University as a research chemist in 2002. He is a professor at the State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation. His research field is oil-field chemicals.

Xinyi Deng

Xinyi Deng studied at the School of New Energy and Materials at Southwest Petroleum University as a doctoral student (2020 Grade). She is majoring in materials and chemicals.

Yiping Chen

Yiping Chen studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2017 Grade). She is majoring in materials engineering.

Yaxiong Zhao

Yaxiong Zhao studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2020 Grade). He is majoring in materials and chemicals.

Ruifeng Ni

Ruifeng Ni studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2020 Grade). He is majoring in materials science and engineering.

Jiangyu Huang

Jiangyu Huang studied at the School of New Energy and Materials at Southwest Petroleum University as a graduate student (2020 Grade). He is majoring in materials science and engineering.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This research is supported by National Natural Science Foundation of China (Projects No. 51074133), Project of State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Projects No. PLN201807 and 201930), and Major Frontier Projects of Application Foundation in Sichuan Province (Projects No. 2019YJ0421).

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

1. Zhou, M., Li, S., Zhang, Z., Wang, C., Luo, G., Zhao, J. Progress in the synthesis of zwitterionic Gemini surfactants. J. Surfactants Deterg. 2017, 20, 1243–1254; https://doi.org/10.1007/s11743-017-2014-0.Search in Google Scholar

2. Kamal, M. S., Hussein, I. A., Sultan, A. S. Review on surfactant flooding: phase behavior, retention, IFT, and field applications. Energy Fuel. 2017, 31, 7701–7720; https://doi.org/10.1021/acs.energyfuels.7b00353.Search in Google Scholar

3. Zhou, M., Zhou, L., Guo, X. Synthesis of sulfobetaine-type zwitterionic Gemini surfactants (EAPMAC) and their oilfield application properties. J. Surfactants Deterg. 2019, 22, 23–32; https://doi.org/10.1002/jsde.12199.Search in Google Scholar

4. Satam, R., Sawant, M. Synthesis of amphoteric surfactants via esterification process. J. Dispersion Sci. Technol. 2006, 27, 407–411; https://doi.org/10.1080/01932690500359749.Search in Google Scholar

5. Cheng, X., Cheng, R., Ou, S., Li, Y. Synthesis and adsorption performance of dithiocarbamate-modified glycidyl methacrylate starch. Carbohydr. Polym. 2013, 96, 320–325; https://doi.org/10.1016/j.carbpol.2013.04.001.Search in Google Scholar PubMed

6. Wang, G., Zhou, M., Ding, S., Huang, Z., Zhang, Z., Li, S. Reaction principle of alcohol ether sulfonates by sulfonated alkylation method-A review. Tenside Surfactants Deterg. 2017, 54, 5–10; https://doi.org/10.3139/113.110472.Search in Google Scholar

7. Zhou, M., Li, S., Zhang, Z., Luo, G., Zhao, J. Synthesis of oligomer betaine surfactant (DDTPA) and rheological properties of wormlike micellar solution system. J. Taiwan Inst. Chem. Eng. 2016, 66, 1–11; https://doi.org/10.1016/j.jtice.2016.05.013.Search in Google Scholar

8. Hiroki, I., Yuya, T., Shintaro, K. Solubilization of progesterone and its derivatives into Gemini surfactant solutions. J. Oleo Sci. 2020, 69, 557–562; https://doi.org/10.5650/jos.ess20007.Search in Google Scholar PubMed

9. Bunton, C., Robinson, L., Schaak, J. Catalysis of nucleophilic substitutions by micelles of dicationic detergents. J. Org. Chem. 1971, 36, 2346–2350; https://doi.org/10.1021/jo00815a033.Search in Google Scholar

10. Zhou, M., Chen, Y., Zou, J., Bu, J. Recent advances in the synthesis of sulfonate Gemini surfactants. J. Surfactants Deterg. 2018, 21, 443–453; https://doi.org/10.1002/jsde.12046.Search in Google Scholar

11. Bhadani, A., Singh, S. Synthesis and properties of thioether spacer containing Gemini imidazolium surfactants. Langmuir 2011, 27, 14033–14044; https://doi.org/10.1021/la202201r.Search in Google Scholar PubMed

12. Okahara, M., Masuyama, A., Sumida, Y., Zhu, Y. Surface active properties of new types of amphipathic compounds with two hydrophilic ionic groups and two lipophilic alkyl chains. J. Japan Oil Chem. Soc. 1988, 37, 746–748; https://doi.org/10.5650/jos1956.37.746.Search in Google Scholar

13. Zhou, M., Bu, J., Wang, J., Guo, X., Huang, J., Huang, M. Study on three phase foam for Enhanced Oil Recovery in extra-low permeability reservoirs. Oil Gas Sci. Technol. 2018, 73, 55; https://doi.org/10.2516/ogst/2018059.Search in Google Scholar

14. Liu, J., Hu, M., Xie, Y., Xu, H. Study on a class of cationic Gemini surfactants. Tenside Surfactants Deterg. 2019, 56, 319–326; https://doi.org/10.3139/113.110628.Search in Google Scholar

15. Zhu, Y., Masuyama, A., Okahara, M. Preparation and surface-active properties of amphipathic compounds with two phosphate groups and two long-chain alkyl chains. J. Am. Oil Chem. Soc. 1991, 68, 268–271; https://doi.org/10.1007/BF02657622.Search in Google Scholar

16. Zhou, M., Nie, X., Zhou, L., Hou, L., Zhao, J., Yang, Y. Study of crosslinked copolymer nanospheres with temperature resistance, salinity resistance, and deep profile control. J. Appl. Polym. Sci. 2017, 134, 45131; https://doi.org/10.1002/app.45131.Search in Google Scholar

17. Menger, F. M., Littau, C. A. Gemini surfactants: a new class of self-assembling molecules. J. Am. Chem. Soc. 1993, 115, 10083–10090; https://doi.org/10.1021/ja00075a025.Search in Google Scholar

18. ShahzadKamal, M., ShakilHussain, S. M., Sultan, S. A. Development of novel amidosulfobetaine surfactant-polymer systems for EOR applications. J. Surfactants Deterg. 2016, 19, 989–997; https://doi.org/10.1007/s11743-016-1848-1.Search in Google Scholar

19. Parikh, K., Singh, S., Sanjeev, K. Self-assembly in an aqueous gemini surfactant containing sugar based (isosorbide) spacer. Arab. J. Chem. 2020, 13, 1848–1857; https://doi.org/10.1016/j.arabjc.2018.01.020.Search in Google Scholar

20. Zhou, M., Zhao, J., Hu, X. Synthesis of Bis [N, N′-(alkylamideethyl) ethyl] triethylenediamine bromide surfactants and their oilfield application investigation. J. Surfactants Deterg. 2012, 15, 309–315; https://doi.org/10.1007/s11743-011-1313-0.Search in Google Scholar

21. Menger, F. M., Keiper, J. S. Gemini surfactants. Angew. Chem. Int. Ed. 2000, 39, 1906–1920; https://doi.org/10.1002/1521-3773(20000602)39:11<1906::AID-ANIE1906>3.0.CO;2-Q.10.1002/1521-3773(20000602)39:11<1906::AID-ANIE1906>3.0.CO;2-QSearch in Google Scholar

22. Laska, U., Wilk, A., Maliszewska, I., Syper, L. Novel glucose-derived gemini surfactants with a 1, 1’-ethylenebisurea spacer: preparation, thermotropic behavior, and biological properties. J. Surfactants Deterg. 2007, 9, 115–124; https://doi.org/10.1007/s11743-006-0380-0.Search in Google Scholar

23. Xue, C., Zhu, H., Zhang, T., Cao, D., Hu, Z. Synthesis and properties of novel alkylbetaine zwitterionic Gemini surfactants derived from cyanuric chloride. Colloids Surf. A: Physicochem. Eng. Asp. 2011, 375, 141–146; https://doi.org/10.1016/j.colsurfa.2010.12.004.Search in Google Scholar

24. Xu, H., Hui, G., Peng, K., Chen, D. Synthesis and properties of a novel linear alkylated diphenylmethane sulfonate Gemini surfactant. J. Surfactants Deterg. 2013, 16, 57–61; https://doi.org/10.1007/s11743-012-1407-3.Search in Google Scholar

25. Zhou, M., Wang, G., Xu, Y., Zhang, Z., Li, S., Hu, B., Zhao, Y. Synthesis and performance evaluation of CO2/N2 switchable tertiary amine Gemini surfactant. J. Surfactants Deterg. 2017, 20, 1–7; https://doi.org/10.1007/s11743-017-2019-8.Search in Google Scholar

26. Liu, S., Sang, R., Hong, S., Cai, Y., Wang, H. A novel type of highly effective nonionic Gemini alkyl o-glucoside surfactants: a versatile strategy of design. Langmuir 2013, 29, 8511–8516; https://doi.org/10.1021/la401569n.Search in Google Scholar

27. Yoshimura, T., Ohno, A., Esumi, K. Equilibrium and dynamic surface tension properties of partially fluorinated quaternary ammonium salt Gemini surfactants. Langmuir 2006, 22, 4643–4648; https://doi.org/10.1021/la0534266.Search in Google Scholar

28. Xing, F., Gao, Y., Xu, Q., Li, X., Wang, L., Meng, J., Wang, P. The Effects of the organic groups attached at the silicone atoms of the organosilane-based Gemini nonionic surfactants on their surface activities. J. Surfactants Deterg. 2014, 17, 739–745; https://doi.org/10.1007/s11743-013-1545-2.Search in Google Scholar

29. Menger, F. M., Littau, C. Gemini-surfactants: synthesis and properties. J. Am. Chem. Soc. 1991, 113, 5467–5468; https://doi.org/10.1021/ja00004a077.Search in Google Scholar

30. Zana, R. Dimeric (Gemini) surfactants: effect of the spacer group on the association behavior in aqueous solution. J. Colloid Interface Sci. 2002, 248, 203–220; https://doi.org/10.1006/jcis.2001.8104.Search in Google Scholar

31. Knaebel, A., Oda, R., Mendes, E., Candau, S. Lamellar structures in aqueous solutions of a dimeric surfactant. Langmuir 2000, 16, 2489–2494; https://doi.org/10.1021/la990937h.Search in Google Scholar

32. He, Y. F., SalonenLecchi, A. A., Veber, M., Langevin, D. Adsorption of gemini surfactants at the air-water surface. Colloid Polym. Sci. 2016, 294, 483–490; https://doi.org/10.1007/s00396-015-3813-3.Search in Google Scholar

33. Pal, N., Saxena, N., Mandal, A. Studies on the physicochemical properties of synthesized tailor-made gemini surfactants for application in enhanced oil recovery. J. Mol. Liq. 2018, 258, 211–224; https://doi.org/10.1016/j.molliq.2018.03.037.Search in Google Scholar

34. Saavedra, L., Gomez, E. M. P., Oliveira, R. G. Aggregation behaviour and solubilization capability of mixed micellar systems formed by a gemini lipoamino acid and a non-ionic surfactant. Colloids Surf. A: Physicochem. Eng. Asp. 2017, 533, 41–47; https://doi.org/10.1016/j.colsurfa.2017.08.011.Search in Google Scholar

35. Huang, Z., ZhongWang, H. S., Xia, L., Zhao, G., Liu, G. Gemini trisiloxane surfactant: synthesis and flotation of aluminosilicate minerals. Miner. Eng. 2014, 56, 145–154; https://doi.org/10.1016/j.mineng.2013.11.006.Search in Google Scholar

36. Huang, T. P., Crews, J. B. Nanotechnology applications in viscoelastic surfactant stimulation fluids. SPE Prod. Oper. 2008, 23, 512–517; https://doi.org/10.2118/107728-PA.Search in Google Scholar

37. Chen, H., Han, L., Luo, P., Ye, Z. The ultralow interfacial tensions between crude oils and gemini surfactant solutions. J. Colloid Interface Sci. 2005, 285, 872–874; https://doi.org/10.1016/j.jcis.2004.11.066.Search in Google Scholar PubMed

38. Liu, Z., Ge, Y., Zhang, Q. Adsorption and micellization of gemini surfactantswith diethylammonium headgroups: effect of the spacer rigidity. J. Surfactants Deterg. 2017, 20, 765–775; https://doi.org/10.1007/s11743-017-1964-6.Search in Google Scholar

39. Zhong, X., GuoFeng, J. L., Xu, X., Zhu, D. Cationic gemini surfactant based on adamantane: synthesis, surface activity and aggregation properties. Colloids Surf. A: Physicochem. Eng. Asp. 2014, 441, 572–580; https://doi.org/10.1016/j.colsurfa.2013.10.016.Search in Google Scholar

40. Zhou, M., Zhong, X., Zhao, J., Wang, X. Synthesis and surface active properties of 1, 1, 1, 1-Tetra-(2-oxypropyl sulfonate-3-alkylether-propoxy) neopentanes. J. Surfactants Deterg. 2013, 16, 285–290; https://doi.org/10.1007/s11743-012-1420-6.Search in Google Scholar

41. Zhou, M., Zhao, J., Wang, X., Jing, J., Zhou, L. Synthesis and characterization of novel surfactants 1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy) propanes. J. Surfactants Deterg. 2013, 16, 665–672; https://doi.org/10.1007/s11743-013-1442-8.Search in Google Scholar

42. Zhao, J., Zhou, M., Wang, X., Yang, Y. Synthesis and surface active properties of dimeric gemini sulfonate surfactants. Tenside Surfactants Deterg. 2014, 51, 26–31; https://doi.org/10.3139/113.110282.Search in Google Scholar

43. Gu, Y., Zhou, M., Wang, X., Tu, H., Yang, Y., Zhao, Y. Preparation and performance evaluation sulfate-quaternary ammonium Gemini surfactant. J. Mol. Liq. 2021, 343, 117665; https://doi.org/10.1016/j.molliq.2021.117665.Search in Google Scholar

44. Zuo, Z., Zhou, M., Liao, M., Peng, P., Zhang, J. Preparation and performance evaluation of Gemini sulphobetaine surfactant bis{[(N-methyl-N-(3-alkoxy-2-hydroxy)propyl-N-(3-sulfonic) propyl] methylene. Tenside Surfactants Deterg. 2021, 58, 468–474; https://doi.org/10.1515/tsd-2021-2350.Search in Google Scholar

45. Pei, X., Zhao, J., Ye, Y., You, Y., Wei, X. Wormlike micelles and gels reinforced by hydrogen bonding in aqueous cationic gemini surfactant systems. Soft Matt. 2011, 7, 2953–2960; https://doi.org/10.1039/c0sm01071e.Search in Google Scholar

46. Tang, S., Zheng, Y., Yang, W. Experimental study of sulfonate gemini surfactants as thickeners for clean fracturing fluids. Energies 2018, 11, 3182; https://doi.org/10.3390/en11113182.Search in Google Scholar

47. Du, X., Li, L., Lu, Y., Yang, Z. Unusual viscosity behavior of a kind of anionic gemini surfactant. Colloids Surf. A: Physicochem. Eng. Asp. 2007, 308, 147–149; https://doi.org/10.1016/j.colsurfa.2007.05.020.Search in Google Scholar

48. Han, L., Chen, H., Luo, P. Viscosity behavior of cationic gemini surfactants with long alkyl chains. Surf. Sci. 2004, 564, 141–148; https://doi.org/10.1016/j.susc.2004.06.172.Search in Google Scholar

49. Mao, J., Yang, X., Chen, Y., Zhang, Z., Zhang, C., Yang, B., Zhao, J. Viscosity reduction mechanism in high temperature of a Gemini viscoelastic surfactant (VES) fracturing fluid and effect of counter-ion salt (KCl) on its heat resistance. J. Pet. Sci. Eng. 2018, 164, 189–195; https://doi.org/10.1016/j.petrol.2018.01.052.Search in Google Scholar

50. Zhu, H., Niu, H., Lou, P., Ding, H., Zhang, H. Synthesis and performance of Gemini surfactant-containing acidic clean fracturing fluid. Adv. Fine Petrochem. 2011, 12, 5–8.Search in Google Scholar

51. Yu, H., Shen, Y., Yang, X., Liu, G., Zhang, L. Interfacial activity and rheological behavior of N,N-bis(hexadecyldimethyl)-1,2-dibro-mide-ethanediyl ammonium salt. Acta Pet. Sin. 2014, 30, 542–547; https://doi.org/10.3969/j.issn.1001-8719.2014.03.02410.1007/s10114-014-3180-x.Search in Google Scholar

52. Tang, S., Zheng, Y., Yang, W., Wang, J., Fan, Y., Lu, J. Experimental study of sulfonate gemini surfactants as thickeners for clean fracturing fluids. Energies 2018, 11, 312; https://doi.org/10.3390/en11113182.Search in Google Scholar

53. Abang, G., Pin, Y., Ridzuan, N. Application of silica (SiO2) nanofluid and Gemini surfactants to improve the viscous behavior and surface tension of water-based drilling fluids. Egypt. J. Pet. 2021, 30, 37–42; https://doi.org/10.1016/j.ejpe.2021.10.002.Search in Google Scholar
Received: 2022-04-05
Accepted: 2022-06-24
Published Online: 2022-09-22
Published in Print: 2022-11-25

© 2022 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.1515/tsd-2022-2445
Keywords for this article
fracturing fluids; oligomeric cationic Gemini surfactants; rheological properties; surface properties; thickener; wormlike micelle

Articles in the same Issue

  1. Frontmatter
  2. Novel Cleaning Concepts
  3. Innovative foam-based cleaning concepts for historical objects
  4. Automatic Dishwashing
  5. Development of an imaging station and scoring model for automatic dishwashing evaluation
  6. Physical Chemistry
  7. Thermodynamics of complex chemical equilibria in surfactant mixtures
  8. Dispersion of copper phthalocyanine pigment nanoparticles by eco-friendly ethoxylated cardanol in aqueous solution
  9. Study on the compounding of sodium N-lauroyl glutamate and cationic cellulose
  10. Interaction of Direct Blue 86 with cationic surfactant micelles: spectroscopic, conductometric and thermodynamic aspects
  11. Novel Surfactants
  12. Oligomeric cationic Gemini surfactants: synthesis, surface activities and rheological properties as thickener
  13. Application
  14. Influence of Bacillus subtilis on the surface behavior and separation of talc and chlorite minerals
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