Enhancement of the glass transition temperature of poly(methyl methacrylate) by salt

Abstract

We investigated the effects of two metal salts, lithium trifluoromethanesulfonate (LiCF3SO3) and lithium bromide (LiBr), on the glass transition temperature (Tg) of poly(methyl methacrylate) (PMMA). Both LiCF3SO3 and LiBr greatly enhanced the Tg of PMMA under dry conditions. However, once the sample films were exposed to humidity, the PMMA containing LiCF3SO3 absorbed a large amount of water, which acts as a plasticizer. As a result, the Tg shifted to a lower temperature, which limits the utility of this polymer in industrial applications. In contrast, the Tg of PMMA containing LiBr was minimally affected by the absorption of water. This phenomenon can be explained by the ion–dipole interactions with the small number of dissociated lithium cations.

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References

  1. 1.

    Cowie JMG. Some general features of T g-M relations for oligomers and amorphous polymers. Eur Polym J. 1975;11:297–300.

    Article  CAS  Google Scholar 

  2. 2.

    Tadlaoui K, Pietrasanta Y, Michel A, Verney V. Influence of molecular weight on the glass transition temperature and the melt rheological behaviour of methyl methacrylate telomers. Polymer. 1991;32:2234–7.

    Article  CAS  Google Scholar 

  3. 3.

    Wooley KL, Hawker CJ, Pochan JM, Frechet JMJ. Physical properties of dendritic macromolecules: a study of glass transition temperature. Macromolecules. 1993;26:1514–9.

    Article  CAS  Google Scholar 

  4. 4.

    Forrest JA, Dalnoki-Veress K, Dutcher JR. Interface and chain confinement effects on the glass transition temperature of thin polymer films. Phys Rev E. 1997;56:5705–16.

    Article  CAS  Google Scholar 

  5. 5.

    Painter PC, Graf JF, Coleman MM. Effect of hydrogen bonding on the enthalpy of mixing and the composition dependence of the glass transition temperature in polymer blends. Macromolecules. 1991;24:5630–8.

    Article  CAS  Google Scholar 

  6. 6.

    Lodge TP, McLeish TCB. Self-concentrations and effective glass transition temperatures in polymer blends. Macromolecules. 2000;33:5278–84.

    Article  CAS  Google Scholar 

  7. 7.

    Shefer A, Gottlieb M. Effect of crosslinks on the glass transition temperature of end-linked elastomers. Macromolecules. 1992;25:4036–42.

    Article  CAS  Google Scholar 

  8. 8.

    Liu H, Zheng S. Polyurethane networks nanoreinforced by polyhedral oligomeric silsesquioxane. Macromol Rapid Commun. 2005;26:196–200.

    Article  CAS  Google Scholar 

  9. 9.

    Fairbanks BD, Scott TF, Kloxin CJ, Anseth KS, Bowman CN. Thiol−Yne photopolymerizations: novel mechanism, kinetics, and step-growth formation of highly cross-linked networks. Macromolecules. 2009;42:211–7.

    Article  CAS  PubMed  Google Scholar 

  10. 10.

    Juang TY, Liu JK, Chang CC, Shau SM, Tsai MH, Dai SA, et al. A reactive modifier that enhances the thermal mechanical properties of epoxy resin through the formation of multiple hydrogen-bonded network. J Polym Res. 2011;18:1169–76.

    Article  CAS  Google Scholar 

  11. 11.

    Shangguan Y, Yang J, Zheng Q. Rheology of nitrile rubber with hybrid crosslinked network composed of covalent bonding and hydrogen bonding. RSC Adv. 2017;7:15978–85.

    Article  CAS  Google Scholar 

  12. 12.

    Donat BP, Viallat A, Blachot JF, Lombard C. Electromechanical polymer gels combining rubber elasticity with electronic conduction. Adv Matter. 2006;18:1401–5.

    Article  CAS  Google Scholar 

  13. 13.

    Yang S, Fan H, Jiao Y, Cai Z, Zhang P, Li Y. Improvement in mechanical properties of NBR/LiClO4/POSS nanocomposites by constructing a novel network structure. Comp Sci Technol. 2017;138:161–8.

    Article  CAS  Google Scholar 

  14. 14.

    Miyagawa A, Ayerdurai V, Nobukawa S, Yamaguchi M. Viscoelastic properties of poly(methyl methacrylate) with high glass transition temperature by lithium salt addition. J Polym Sci B Polym Phys. 2016;54:2388–94.

    Article  CAS  Google Scholar 

  15. 15.

    Eisenberg A, Kim JS. Introduction to ionomers. New York, Wiley; 1998.

    Google Scholar 

  16. 16.

    Kim JS, Jackman RJ, Eisenberg A. Filler and percolation behavior of ionic aggregates in styrene-sodium methacrylate ionomers. Macromolecules. 1994;27:2789–803.

    Article  CAS  Google Scholar 

  17. 17.

    Hara M, Eisenberg A. Miscibility enhancement via ion-dipole interactions. 1. Polystyrene ionomer/poly(alkylene oxide) systems. Macromolecules. 1984;17:1335–40.

    Article  CAS  Google Scholar 

  18. 18.

    Zhou J, Lucas JP. Hygrothermal effects of epoxy resin. Part II: variations of glass transition temperature. Polymer. 1999;40:5513–22.

    Article  CAS  Google Scholar 

  19. 19.

    Shen J, Chen CC, Sauer JA. Effects of sorbed water on properties of low and high molecular weight PMMA: 1. Deformation and fracture behaviour. Polymer. 1985;26:511–8.

    Article  CAS  Google Scholar 

  20. 20.

    Smith LSA, Schmitz V. The effect of water on the glass transition temperature of poly(methyl methacrylate). Polymer. 1988;29:1871–8.

    Article  CAS  Google Scholar 

  21. 21.

    Israelachvili, JN, Intermolecular and Surface Forces, 3rd ed. Elsevier, Amsterdam; 2011.

  22. 22.

    Brandup, J, Immergut, EH, Grulke, EA, Polymer Handbook, 4th ed. Wiley Interscience, Hoboken; 1999.

  23. 23.

    Atkins, P, Paula, JD, Atkins’. Physical Chemistry, 8th ed. Oxford University Press, Oxford; 2006.

  24. 24.

    Saito Y, Yamamoto H, Nakamura O, Kageyama H, Ishikawa H, Miyoshi T, et al. Determination of ionic self-diffusion coefficients of lithium electrolytes using the pulsed field gradient NMR. J Power Sources. 1999;81–82:772–6.

    Article  Google Scholar 

  25. 25.

    Custelcean R, Moyer BA. Anion separation with metal-organic frameworks. Eur J Inorg Chem. 2007;10:1321–40.

    Article  CAS  Google Scholar 

  26. 26.

    Frech R, Huang W. Polymer conformation and ionic association in complexes of lithium, sodium and potassium triflate with poly (ethylene oxide) oligomers. Solid State Ion. 1994;72:103–7.

    Article  CAS  Google Scholar 

  27. 27.

    Londono JD, Annis BK, Habenschuss A, Borodin O, Smith GD, Turner JZ, et al. Cation environment in molten lithium iodide doped poly(ethylene oxide). Macromolecules. 1997;30:7151–7.

    Article  CAS  Google Scholar 

  28. 28.

    Tominaga Y, Izumi Y, Kwak G, Asai S, Sumita M. Effect of supercritical carbon dioxide processing on ionic association and conduction in a crystalline poly(ethylene oxide)-LiCF3SO3 complex. Macromolecules. 2003;36:8766–72.

    Article  CAS  Google Scholar 

  29. 29.

    Kobayashi S, Nagayama S, Busujima T. Lewis acid catalysts stable in water. Correlation between catalytic activity in water and hydrolysis constants and exchange rate constants for substitution of inner-sphere water ligands. J Am Chem Soc. 1998;120:8287–8.

    Article  CAS  Google Scholar 

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Acknowledgements

We express our sincere gratitude to Mitsubishi Chemical Holdings for their valuable suggestions and their kindness in supplying the sample employed in this study.

Funding

This work was supported by the COI program “Construction of next-generation infrastructure system using innovative materials”—Realization of safe and secure society that can coexist with the Earth for centuries—Supported by Japan Science and Technology Agency (JST).

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Correspondence to Masayuki Yamaguchi.

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Ito, A., Phulkerd, P., Ayerdurai, V. et al. Enhancement of the glass transition temperature of poly(methyl methacrylate) by salt. Polym J 50, 857–863 (2018). https://doi.org/10.1038/s41428-018-0080-4

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