Effect of Reaction Temperature on Tacticity in Polymerization of Methyl Methacrylate: A Study by Nuclear Magnetic Resonance Spectroscopy

Document Type : Research Paper

Authors

1 Iran Polymer and Petrochemical Institute, P.O. Box: 14965-115, Tehran, Iran

2 Department of Chemistry, Ahar Branch, Islamic Azad University, Postal Code 5451116714, Ahar, Iran

Abstract

Hypothesis: In the synthesis of vinyl polymers, one of the important parameters that play a significant role in the physical-mechanical properties is the tacticity of monomers within the polymer chain. Polymethyl methacrylate is considered one of the important industrial polymers. The method of its synthesis can have a major effect on this parameter and finally on the final properties. One of the parameters that has a significant effect on the stereoregularity of this polymer is the reaction temperature.
Methods: The poly methyl methacrylate was synthesized at three different temperatures of 50, 150, and 250 °C via bulk thermal polymerization method. The most important instrument that can be used to study tacticity order is nuclear magnetic resonance spectroscopy. The tacticity of the polymethyl methacrylate (PMMA) was investigated and studied through alpha-methyl protons splitting and alpha-methyl and carbonyl carbons splitting, respectively, by proton (1HNMR) and carbon (13CNMR) nuclear magnetic resonance spectroscopy in deuterated chloroform (CDCl3) and deuterated tetrahydrofuran (THF-d8). The assignment of all stereosequences at triad level for alpha-methyl proton and pentad level for alpha - methyl carbon and carbonyl carbon were carried out by liquid nuclear magnetic resonance spectroscopy in deuterated chloroform. Bernoullian and first-order Markov statistics models were calculated for the synthesized sample and compared with the experimental results.
Findings: The results indicated that probability of meso (Pm) was increased by increasing the methyl methacrylate polymerization temperature. The corresponding probability of meso values determined for synthesized polymethyl methacrylate at 50, 150, and 250°C were 0.203, 0.274, and 0.356, respectively. Finally, the effect of tacticity on glass transition temperature using differential scanning calorimetry (DSC) is discussed. The temperature glassy (Tg) values by DSC results were shown that the synthesized polymethyl methacrylate at 50, 150, and 250°C had 126.0, 125.1 and 102.9 oC, respectively.

Keywords

References

  1. Stevens P.M., Polymer Chemistry: An Introduction, 2nd ed., Oxford University, 1999.
  2. Wang D., Zhu J., Yao Q., and Wilkie C.A., A Comparison of Various Methods for the Preparation of Polystyrene and Poly(methyl methacrylate) Clay Nanocomposites, Mater., 14, 3837-3843, 2002.
  3. Boroujeny S.B., Atai M., Nodehi A., Ferdowsi M., and Nosratzadegan K., Synthesis and Characterization of Low Density PMMA-Based Microballoons, J. Polym. Sci. Technol. (Persian), 25, 467-475, 2013.
  4. O’Driscoll K.F., Monteiro M.J., and Klumperman B., The Effect of Benzyl Alcohol on Pulsed Laser Polymerization of Styrene and Methylmethacrylate, Polym. Sci., Part A: Polym. Chem., 35, 515-520, 1997.
  5. Smith L.M. and Coote M.L., Effect of Temperature and Solvent on Polymer Tacticity in the Free-Radical Polymerization of Styrene and Methyl Methacrylate, Polym. Sci. Part A: Polym. Chem., 51, 3351-3358, 2013.
  6. Randall J.C., Polymer Sequence Determination, Carbon-13 NMR Method, Academic, New York, 1977.
  7. Matsuura K., Kuboyama K., and Ougizawa T., Effect of Tacticity of Poly(methyl methacrylate) on Interfacial Region with Silica in Polymer Nanocomposite, Eng. Sci., 61, 77-84, 2021.
  8. Chat K., Tu W., Beena Unni A., and Adrjanowicz K., Influence of Tacticity on the Glass-Transition Dynamics of Poly(methyl methacrylate) (PMMA) under Elevated Pressure and Geometrical Nanoconfinement, Macromolecules, 54, 8526-8537, 2021.
  9. Bovey F. and Mirau P.A., NMR of Polymers, Academic, UK, 1996.
  10. Hsu W.P., Effect of Tacticity of Poly(methyl methacrylate) on the Miscibility with Poly(vinyl acetate), Appl. Polym. Sci., 91, 35-39, 2004.
  11. Vorenkamp E.J., ten Brinke G., Meijer J.G., Jager H., and Challa G., Influence of the Tacticity of Poly(methyl methacrylate) on the Miscibility with Poly(vinyl chloride), Polymer, 26, 1725-1732, 1985.
  12. Hsu W.P., Effect of Tacticity of Poly(methyl methacrylate) on the Miscibility with Poly(vinyl pyrrolidone), Appl. Polym. Sci., 81, 3190-3197, 2001.
  13. Süske E., Scharf T., Krebs H.U., Junkers T., and Buback M., Mechanism of Poly(methyl methacrylate) Film Formation by Pulsed Laser Deposition, Appl. Phys., 100, 014906-4, 2006.
  14. Sharma V.K., Pethrick R.A., and Affrossman S., Poly(methyl methacrylate): Influence of Tacticity on Its Use as an Electron Resist, Polymer, 23, 1732-17, 1982.
  15. Zhang B. and Blum F.D., Thermogravimetric Study of Ultrathin PMMA Films on Silica: Effect of Tacticity, Acta, 396, 211-217, 2003.
  16. Tribone J.J., O’Reilly J.M., and Greener J., Analysis of Enthalpy Relaxation in Poly(methyl methacrylate): Effects of Tacticity, Deuteration, and Thermal History, Macromolecules, 19, 1732-1739, 1986.
  17. Chang L. and Woo E.M., Tacticity Effects on Glass Transition and Phase Behavior in Binary Blends of Poly(methyl methacrylate)s of Three Different Configurations, Chem. 1, 198-202, 2010.
  18. Tung K.L. and Lu K.T., Effect of Tacticity of PMMA on Gas Transport Through Membranes: MD and MC Simulation Studies, Membr. Sci., 272, 37-49, 2006.
  19. Florjańczyk, Such K., and Wieczorek W., Effect of Tacticity of Poly(methyl methacrylate) on Conductivity of Poly(ethylene oxide)-Poly(methyl methacrylate) Blend-Based Polymeric Electrolytest, J. Macromol. Sci. Chem., 29, 853-863, 1992.
  20. Hamieh, Toufaily J., and Mouneimné A.H., Effect of the Tacticity of PMMA Adsorbed on Alumina and Silica on the Specific Entropy Change of Polymer by Inverse GC, Chromatographia, 73, 99-107, 2011.
  21. Carriere P., Feller J.F., Dupuis D., and Grohens Y., Rheological Properties of Silica Dispersions Stabilized by Stereoregular Poly(methyl methacrylate), Colloid Interf. Sci., 272, 218-224, 2004.
  22. Bovey F.A. and Tiers G.V.D., Polymer NSR Spectroscopy. II. The High Resolution Spectra of Methyl Methacrylate Polymers Prepared with Free Radical and Anionic Initiators, Polym. Sci. Polym. Chem., 44, 173-182, 1960.
  23. Nishioka A., Watanabe H., Abe K., and Sono Y., Grignard Reagent-Catalyzed Polymerization of Methyl Methacrylate, Polym. Sci. Polym. Chem., 48, 241-272, 1960.
  24. Ngueu G., Nicole D., Swistek M., Matlengiewicz M., and Wiegert B., Incremental Method for Determination of Sequence Distribution of Poly(methyl methacrylate) by
    13C NMR Spectroscopy, Analusis, 27, 847-853, 1999.
  25. Hatada K. and Kitayama T., NMR Spectroscopy of Polymers, Springer–Verlag Berlin Heidelberg, 2004.
  26. Brar A.S., Singh G., and Shankar R., Structural Investigations of Poly(methyl methacrylate) by Two-Dimensional NMR, Mol. Struct., 703, 69-81, 2004.
  27. Ziaee F., Nekoomanesh M., Salehi-Mobarakeh H., and Arabi H., Effect of Temperature on Tacticity for Bulk Thermal Polymerization of Styrene, e-Polymers, 041, 2008.
  28. Ziaee F. and Samadi-Khoshkhoo M., Effect of Temperature on Tacticity in Thermal Polymerization of p-Methylstyrene by 13CNMR Spectroscopy, Polym. J., 21, 21-29, 2012.
  29. Kawamura T., Toshima N., and Matsuzaki K., Comparison of 13C NMR Spectra of Polystyrenes Having Various Tacticities and Assignment of the Spectra, Rapid Comm., 15, 479-486, 1994.
  30. Ziaee F. and Salehi-Mobarakeh H., Effect of Temperature on Polystyrene Tacticity Through Para Aromatic Carbon Splitting in 13C NMR Spectroscopy, Polym. J., 20, 213-221, 2011.
  31. Jozaghkar M.R., Ziaee F., and Sepehrian-Azar A., Investigation of Poly(α‑methyl styrene) Tacticity Synthesized by Photo-Polymerization, Bull., 78, 5303-5314, 2021.
  32. Perry R.H. and Green D.W., Chemical Engineers Handbook, McGraw-Hill, New York, 1997.
  33. Biroš , Larina T., Trekoval J.,and Pouchlý J., Dependence of the Glass Transition Temperature of Poly(methyl methacrylates) on Their Tacticity, Colloid Polym. Sci., 260, 27-30, 1982.
  34. Li, Yang Q., Huang Y.,  Zhang Q.,  and Zhao W., Entropy Reduction Phenomenon in the Non-Equilibrium State of Freeze-Dried Polymethyl Methacrylate Samples, J. Polym. Res., 31, 392-401, 2014.
  35. Karasz F.E. and MacKnight W.J., Energetic Analysis of the Two PMMA Chain Tacticities and PMA Through Molecular Dynamics Simulations, Polymer, 43, 4269-4275, 2002.

 

Iranian Journal of Polymer Science and Technology
Volume 35, Issue 4 - Serial Number 180
November and December 2023
Pages 393-404

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