Abstract
Thermolysis of polytriarylcarbinol (PTAC-Li) (lithium salt of polydiphenylenesulfophthalide (PDSP)) was studied in the temperature range from 100 to 500 °С by thermogravimetric analysis (TG) and IR and electronic spectroscopy to check the available data on the higher thermal stability of PDSP salts over the initial polymer. The mass losses detected by the TG method in the polymer salt at 80—150 and 240—350 °С are mainly caused by the desorption of weakly and strongly bound water. According to the calculations in the B3LYP/6-311+G(d,p) approximation, the С—ОН and C—SO -3 Li+ bonds are weakest in the carbinol model for PTAC-Li (D(C—O) ~ D(C—S) ~ 72 kcal mol–1). The thermolysis of PDSP is accompanied by SO2 evolution, whereas hydroxy and sulfo groups detached from PTAC-Li macromolecules remain in the thermolyzate. Phenol fragments and an inorganic phase, the final form of which is lithium sulfate, are formed in this process. An analysis of the IR and UV spectra of the thermolyzates of PTAC-Li and PDSP confirmed that fluorenyl fragments are predominantly formed upon the thermolysis of these polymers. The data obtained do not confirm a higher stability of PTAC-Li compared to that of PDSP.
Similar content being viewed by others
References
M. G. Zolotukhin, S. S. Akhmetzyanov, N. M. Shishlov, A. N. Latchinov, V. S. Sultanova, L. V. Spirikhin, L. M. Khalilov, Die Makromolekulare Chemie, 1992, 193, 975.
N. M. Shishlov, S. S. Akhmetzyanov, S. L. Khursan, J. Polymer Res., 2015, 22, 1.
N. M. Shishlov, S. S. Akhmetzyanov, I. V. Novoselov, G. I. Nikiforova, Macromolecular Chemistry and Physics, 1997, 198, 3397.
L. Z. Rogovina, V. G. Vasil’ev, G. G. Nikiforova, T. P. Bragina, L. I. Komarova, G. I. Timofeeva, M. I. Buzin, S. N. Salazkin, V. V. Shaposhnikova, A. N. Ryabev, V. S. Papkov, Vysokomol. Soedin., Ser. A, 2002, 44, 1302 [Polym. Sci., Ser. A, 2002, 44].
V. G. Vasil’ev, G. G. Nikiforova, L. Z. Rogovina, L. V. Dubrovina, T. P. Bragina, L. I. Komarova, G. I. Timofeeva, M. I. Buzin, S. N. Salazkin, V. V. Shaposhnikova, V. S. Papkov, Dokl. Akad. Nauk, 2002, 382, 649 [Dokl. Chem. (Engl. Transl.), 2002, 382].
N. M. Shishlov, S. L. Khursan, Sh. S. Akhmetzyanov, Russ. Chem. Bull. (Int. Ed.), 2013, 62, 1422 [Izv. Akad. Nauk, Ser. Khim., 2013, 1422].
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision C.1, Gaussian Inc., Wallingford (CT), 2009.
G. A. Zhurko, ChemCraft, Version 1.6, http://www.chemcraftprog.com.
A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
C. Lee, W. Yang, R. G. Parr, Phys. Rev. B, 1988, 37, 785.
K. Raghavachari, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys., 1980, 72, 650.
Y.-R. Luo, Handbook of Bond Dissociation Energies in Organic Compounds, CRC Press, Boca Raton, Washington, 2003.
N. M. Shishlov, Sh. S. Akhmetzyanov, S. L. Khursan, Khim. Fiz., 2010, 29, 78 [Chem. Phys. (Engl. Transl.), 2010, 29].
L. J. Bellamy, The Infra-Red Spectra of Complex Molecules, Chapman and Hall, London, 1975.
L. A. Kazitsyna, N. B. Kupletskaya, Primenenie UF-, IKi YaMR-spektroskopii v organicheskoi khimii [Application of UV, IR, and NMR Spectroscopy in Organic Chemistry], Vysshaya Shkola, Moscow, 1971, 264 pp. (in Russian).
S. Pinchas, B. L. Silver, I. Laulicht, J. Chem. Phys., 1967, 46, 1506.
K. Pielichowski, J. Njuguna, Thermal Degradation of Polymeric Materials, Smithers Rapra Publishing, 2005.
N. Grassi, Khimiya protsessov destruktsii polimerov [Chemistry of Polymer Destruction Processes], Izd-vo Inostran. Lit., Moscow, 1959, 252 pp. (in Russian).
K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, John Wiley & Song, 1986, 484 pp.
D. E. Chasan, G. Norwitz, Infrared Determination of Inorganic Sulfates and Carbonates by the Pellet Technique, Department of the Army, Frankford Arsenal, 1969.
D. D. Jiang, Q. Yao, M. A. McKinney, C. A. Wilkie, Polymer Degradation and Stability, 1999, 63, 423.
T. Kimura, McMaster University, Hamilton, 1986, 237 p.
S. J. Blanksby, G. B. Ellison, Acc. Chem. Res., 2003, 36, 255.
Y. Chen, Z. Chen, S. Xiao, H. Liu, Thermochimica Acta, 2008, 476, 39.
K. Ouchi, Carbon, 1966, 4, 59.
R. Basnayake, G. R. Peterson, D. J. Casadonte, C. Korzeniewski, J. Phys. Chem. B, 2006, 110, 23938.
M. Laporta, M. Pegoraro, L. Zanderighi, Phys. Chem. Chem. Phys., 1999, 1, 4619.
J. Ostrowska, A. Narbska, Colloid and Polymer Science, 1984, 262, 305.
A. V. Pimenov, Ph. D. (Chem.) Thesis, SPGU, St. Petersburg, 1992 (in Russian).
G. Zundel, Hydration and Intermolecular Interaction. Infrared Investigations of Polyelectrolyte Membranes, Academic Press, New York, 1969.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2437—2443, October, 2016.
Rights and permissions
About this article
Cite this article
Shishlov, N.M., Akhmetzyanov, S.S. & Khursan, S.L. On thermal stability of polydiphenylenesulfophthalide lithium salt. Russ Chem Bull 65, 2437–2443 (2016). https://doi.org/10.1007/s11172-016-1603-9
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-016-1603-9