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Gelation of Konjac glucomannan crosslinked by organotitanium chelated with different ligands

  • Original Paper: Sol-gel, hybrids and solution chemistries
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Abstract

Konjac Glucomannan (KGM) gels can be formed in the presence of organotitanium as crosslinkers which were chelated by different organic compounds. Organotitanium cross-linking agent is a chelate formed by coordination between tetrabutyl titanate and different organic compounds. The gel network was formed through the crosslinking reaction between titanium ions dissociated from organotitanium crosslinkers and the cis-diol hydroxyl groups on the mannose units of polysaccharide chains. Effect of concentration and species of ligands on rheological properties of the complex gels was studied by dynamic viscoelastic measurements. The gelation kinetics of the gels were investigated and the critical gelation points of the gels were accurately determined according to the Winter-Chambon criterion. The effects of kinds and concentrations of ligands on the shear storage modulus (G’), the loss modulus (G”), and the sol-gel transition points were studied. The sol-gel transition time varies with different ligands in the organotitanium crosslinkers. The sol-gel transition time and temperature were obviously observed and in good agreement with Winter–Chambon criterion.

Highlights

  • Konjac Glucomannan gels can be formed by crosslinking with organotitanium.

  • The sol-gel time and temperature were determined by Winter–Chambon criterion.

  • The sol-gel time varies with different ligands of organotitanium crosslinkers.

  • The so-gel transition time and temperature were controllable.

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References

  1. McGlade CE (2012) A review of the uncertainties in estimates of global oil resources. Energy 47:262–270

    Article  Google Scholar 

  2. Legemah M, Guerin M, Sun H et al. (2014) Novel high-efficiency boron crosslinkers for low-polymer-loading fracturing fluids. SPE J 19:737–743

    Article  Google Scholar 

  3. Liu J, Wang S, Wang C et al. (2020) Influence of nanomaterial morphology of guar-gum fracturing fluid, physical and mechanical properties. Carbohydr Polym 234:115915

    Article  CAS  Google Scholar 

  4. Kato K, Matsuda K (1969) Studies on the chemical structure of konjac mannan. Part I. Isolation and characterization of oligosaccharides from the partial acid hydrolyzate of the mannan. Agriculture Biol Chem 33:1446–1453

    CAS  Google Scholar 

  5. Kishida N, Okimasu S, Kamata T (1978) Molecular weight and intrinsic viscosity of konjac glucomannan. Agric Biol Chem 42:1645–1650

    CAS  Google Scholar 

  6. Annable P, Williams PA, Nishinari K (2002) Interaction in xanthan-glucomannan mixtures and the influence of electrolyte. Macromolecules 27:4204–4211

    Article  Google Scholar 

  7. Williams PA, Clegg SM, Langdon MJ et al. (1993) Investigation of the gelation mechanism in k-carrageenan/konjac mannan mixtures using differential scanning calorimetry and electron spin resonance spectroscopy. Macromolecules 26:0024–9297

    Article  Google Scholar 

  8. Ridout MJ, Gunning AP, Morris VJ et al. (1998) Characterisation of the polysaccharide produced by Acetobacter xylinum strain CR1/4 by light scattering and atomic force microscopy. Int J Biol Macromolecules 23:287–293

    Article  CAS  Google Scholar 

  9. Gao S, Wu C, Nishinari K (2008) In situ pH-decrease-induced gelation of sodium alginate/carboxymethylated konjac glucomannan. J Appl Polym Sci 108:2825–2832

    Article  CAS  Google Scholar 

  10. Gao S, Guo J, Wu L et al. (2008) Gelation of konjac glucomannan crosslinked by organic borate. Carbohydr Polym 73:498–505

    Article  CAS  Google Scholar 

  11. Goel N, Shah SN, Yuan W et al. (2001) Suspension characteristics of borate-crosslinked gels: Rheology and atomic force microscopy measurements. J Appl Polym Sci 8229:78–2990

    Google Scholar 

  12. Li R, Zeng H, Zhou X (2013) Inorganic chemistry (21th ed.). Beijing: Chemical Industry Press

  13. Dai C, Zhao G, You Q et al. (2014) A study on environment‐friendly polymer gel for water shut-off treatments in low-temperature reservoirs. J Appl Polym Sci 131:1–7

    Google Scholar 

  14. Allain C, Salome L (1987) Sol-gel transition of hydrolyzed polyacrylamide –chromium (III): Rheological behavior versus cross-link concentration. Macromolecules 20:2957–2958

    Article  CAS  Google Scholar 

  15. Ahad E (1974) Differential scanning calorimetry of aqueous polymer solutions and gels. J Appl Polym Sci 18:1587–1602

    Article  CAS  Google Scholar 

  16. Li C (2011) Preparation of Organic Zirconium Composite Crosslinking Agent and Research on Crosslinking. Xi’an Shiyou University

  17. Gao S, Nishinari K, Guo J (2007) Thermoreversible konjac glucomannan gel crosslinked by borax. Carbohydr Polym 72:315–325

    Article  Google Scholar 

  18. Brannon H, Ault M (1991) New delayed borate-crosslinked fluid provides improved fracture conductivity in high-temperature applications. SPE 22838

  19. Li X, Liu H, Jiang A et al. (2012) Research and application of ultra-high temperature organic boron crosslinking agent. Oilfield Chemistry 29:80–82

    CAS  Google Scholar 

  20. Ma G, Shen Y, Wei Z (2013) An organic titanium crosslinking agent and its preparation method and use method. China Patent CN103113874A May 22

  21. Xu Y, Shen C, Gao S (2015) Preparation and characterization of chitosan gel beads crosslinked by organic titanium. J Polym Res 22:53

    Article  Google Scholar 

  22. Gao S, Nishinari K (2004) Effect of deacetylation rate on gelation kinetics of konjac glucomannan. Colloids Surf B: Biointerfaces 38:241–249

    Article  CAS  Google Scholar 

  23. Gao S, Nishinari K (2004) Effect of degree of acetylation on gelation behavior of konjac glucomannan. Biomacromolecules 5:175–185

    Article  CAS  Google Scholar 

  24. Xie W, Song Z, Liu Z (2016) Surface modification of PCC with guar gum using organic titanium ionic crosslinking agent and its application as papermaking filler. Carbohydr Polym 150:114–120

    Article  CAS  Google Scholar 

  25. Driscoll P, Bowen J, Mark A(1980) Oil Base Foam Fracturing Applied to The Niobrara Shale Formation. SPE 9335

  26. DuPont Inc, Versatile Tyzor Organic Titanates, Product brochure, Wilmington, Delaware

  27. Rondesvadt C (1976) Titanium Compounds (Organic), Kirk-Othmer Encyclopedia of Chemical Technology, Vo123, 3rd ed

  28. Kramer J, Prud’Homme R, Wiltzius P et al. (1988) Comparison of galactomannan crosslinking with organotitanates and borates[J]. Colloid Polym Sci 266:145–155

    Article  CAS  Google Scholar 

  29. Nishinari K, Zhang H, Ikeda S (2000) Hydrocolloid gels of polysaccharides and proteins. Curr Opin Colloid Interface Sci 5:195–201

    Article  CAS  Google Scholar 

  30. Nishinari K, Takahashi R (2003) Interaction in polysaccharide solutions and gels. Curr Opin Colloid Interface Sci 8:396–400

    Article  CAS  Google Scholar 

  31. M Doi (1980) Molecular rheology of concentrated polymer systems. I. J Polym Sci Polym Phys Ed 18:1005–1020

    Article  Google Scholar 

  32. Chambon F, Winter HH (1985) Stopping of crosslinking reaction in a PDMS polymer at the gel point. Polym Bull 13:499–50

    Article  CAS  Google Scholar 

  33. Koike A, Takada A, Nemoto N (1998) Structure and dynamics of ovalbumin gels: II. Gels induced by heat treatment at 80 °C. Polym Gels Netw 6:257–271

    Article  CAS  Google Scholar 

  34. Chambon F, Winter HH (1985) Stopping of crosslinking reaction in a PDMS polymer at the gel point. Polym Bull 13:499–50

    Article  CAS  Google Scholar 

  35. Hellio-Serughetti D, Djabourov M (2006) Gelatin hydrogels cross- linked with bis(vinylsulfonyl)methane (BVSM): 1. The chemical networks. Langmuir 22:8509–8515

    Article  CAS  Google Scholar 

  36. Te Nijenhuis K, Winter HH (1989) Mechanical properties at the gel point of crystallizing poly vinyl chloride solutions. Macromolecules 22:411–414

    Article  Google Scholar 

  37. Rodd AB, Dunstan DE, Ross-Murphy SB et al. (2001) Dependence of linear viscoelastic critical strain and stress values on extent of gelation for a thermally activated gelling system. Rheologica Acta 40:23–29

    Article  CAS  Google Scholar 

  38. Huang L, Takahashi R, Kobayashi S et al. (2002) Gelation behavior of native acetylated konjac glucomannan. Biomacromolecules 3:1296–130

    Article  CAS  Google Scholar 

  39. Shinzo Y, Toshisuke K (1990) Cross-linking agent manual (8 th ed.). Beijing: Chemical Industry Press

Download references

Acknowledgements

We gratefully acknowledge the financial support by the National Natural Science Foundation of China (50703031).

Author contribution

ZZ: Validation, Formal analysis, Investigation, Data Curation, Writing- Original Draft, Writing- Review & Editing. SG: Conceptualization, Resources, Writing - Review & Editing, Visualization, Project administration, Funding acquisition, Supervision. YL: Validation, Investigation. FW: Validation, Investigation. CS: Resources, Visualization, Project administration, Supervision.

Funding

National Natural Science Foundation of China (50703031).

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Authors and Affiliations

  1. Department of Polymer Materials and Engineering, School of Material Sciences and Engineering, Wuhan University of Technology, Luoshi Road 122#, Wuhan, 430070, China

    Zhixin Zhao, Shanjun Gao, Yunzhe Li, Fucheng Wu & Chunhui Shen

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  1. Zhixin Zhao
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  2. Shanjun Gao
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  3. Yunzhe Li
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  5. Chunhui Shen
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Correspondence to Shanjun Gao.

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Zhao, Z., Gao, S., Li, Y. et al. Gelation of Konjac glucomannan crosslinked by organotitanium chelated with different ligands. J Sol-Gel Sci Technol 98, 401–410 (2021). https://doi.org/10.1007/s10971-021-05517-x

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  • DOI: https://doi.org/10.1007/s10971-021-05517-x

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