Synthesis And Ionic Conductivity of Siloxane Based Polymer Electrolytes with Propyl Butyrate Pendant Groups

Natia Jalagonia; Tamara Tatrishvili; Eliza Markarashvili; Jimsher Aneli; Jouzas Vidas Gražulevičius; Omar Mukbaniani

Korean Chemical Engineering Research, Vol.54, No.1, 36-43, February, 2016

DOI10.9713/kcer.2016.54.1.36 Export Citation

Synthesis And Ionic Conductivity of Siloxane Based Polymer Electrolytes with Propyl Butyrate Pendant Groups

Natia Jalagonia^{1, 2}, Tamara Tatrishvili^{1, 2}, Eliza Markarashvili^{1, 2}, Jimsher Aneli³, Jouzas Vidas Gražulevičius⁴, and Omar Mukbaniani^{1, 2, †}

¹Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave., 1, Tbilisi 0179, Georgia
²Institute of Macromolecular Chemistry and Polymeric Materials, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave., 13, Tbilisi 0179, Georgia
³Institute of Macromolecular Chemistry and Polymeric Materials, Iv. Javakhishvili Tbilisi State University, I. Chavchavadze Ave., 13, Tbilisi 0179, Georgia, Korea
⁴Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas, Lithuania

E-mail:

Hydrosilylation reactions of 2.4.6.8-tetrahydro-2.4.6.8-tetramethylcyclotetrasiloxane with allyl butyrate catalyzed by Karstedt’s, H2PtCl6 and Pt/C catalyst were studied and 2.4.6.8-tetra (propyl butyrate)-2.4.6.8-tetramethylcyclotetrasiloxane was obtained. The reaction order, activation energies and rate constants were determined. Ringopening polymerization of 2.4.6.8-tetra (propyl butyrate)-2.4.6.8-tetramethylcyclotetrasiloxane in the presence of CaF2, LiF, KF and anhydrous potassium hydroxide in 60-70 oC temperature range was carried out and methylsiloxane oligomers with regular arrangement of propyl butyrate pendant groups were obtained. The synthesized products were studied by FTIR and NMR spectroscopy. The polysiloxanes were characterized by wide-angle X-ray, gel-permeation chromatography and DSC analyses. Via sol-gel processes of oligomers doped with lithium trifluoromethylsulfonate or lithium bis (trifluoromethylsulfonyl)imide, solid polymer electrolyte membranes were obtained. The dependences of ionic conductivity of obtained polyelectrolytes on temperature and salt concentration were investigated, and it was shown that electric conductivity of the polymer electrolyte membranes at room temperature changed in the range 3.5×10-4~6.4×10-7 S/cm.

Keywords:Polysiloxanes;Membranes;Cross-Linking;Polymer Electrolyte;Ionic Conductivity

[References]

Cardiano P, Sergi S, Lazzari M, Piraino P, Polymer, 43(25), 6635 (2002)
Guizard C, Bac A, Barboiu M, Hovnanian N, Sep. Purif. Technol., 25(1-3), 167 (2001)
Mukbaniani O, Tatrishvili T, Titvinidze G, Mukbaniani N, J. Appl. Polym. Sci., 104(4), 2168 (2007)
Gray FM, Armand M, Polymer electrolytes, in Handbook of Battery Materials. Besenhard JO, Ed., Wiley-VCH, Weinheim (1999).
Karatas Y, Kaskhedikar N, Burjanadze M, Wiemhofer HD, Macromol. Chem. Phys., 207, 419 (2006)
Vermeulen LA, Smith K, Wang JB, Electrochim. Acta, 45(7), 1007 (1999)
Zhang ZC, Sherlock D, West R, Amine K, Lyons LJ, Macromol, 36, 8907 (2003)
Funke K, Heimann B, Vering M, Wilmer D, J. Electrochem. Soc., 148(5), A395 (2001)
Allcock HR, Olmeijer DL, O’Connor SJM, Macromol, 31, 753 (1998)
Gray FM, Armand M, Polymer electrolytes, in Handbook of Battery Materials. Besenhard JO, Ed., Wiley-VCH, Weinheim (1999).
Hooper R, Lyons LJ, Moline DA, West R, Silicon Chemistry, 1, 121 (2002)
Hooper R, Lyons LJ, Moline DA, West R, Organometallics, 18, 3249 (1999)
Iwahara T, Kusakabe M, Chiba M, Yonezawa K, J. Polym. Sci. A: Polym. Chem., 31, 2617 (1993)
Mukbaniani O, Tatrishvili T, Markarashhvili E, Esartia I, Georgian Chem. J., 2, 153 (2011)
Tartakovskaia LM, Makarov IG, Kazakova VM, Kopilov VM, Zhdanov AA, Ser. Chim., 12, 2818 (1980)
Andrianov KA, Tartakovskaia LM, Kopilov VM, Sementsova ZN, Zhur. Obshch. Khim., 45, 112 (1975)
Corey EJ, Snider BB, J. Amer. Chem. Soc., 94, 6190 (1972)
Tartakovskaia LM, Kopilov VM, Zhdanov AA, Vysokomol. Soed., 26, 234 (1984)
Zhang ZC, Fang SB, Electrochim. Acta, 45(13), 2131 (2000)

[1] Cardiano P, Sergi S, Lazzari M, Piraino P, Polymer, 43(25), 6635 (2002)

[2] Guizard C, Bac A, Barboiu M, Hovnanian N, Sep. Purif. Technol., 25(1-3), 167 (2001)

[3] Mukbaniani O, Tatrishvili T, Titvinidze G, Mukbaniani N, J. Appl. Polym. Sci., 104(4), 2168 (2007)

[4] Gray FM, Armand M, Polymer electrolytes, in Handbook of Battery Materials. Besenhard JO, Ed., Wiley-VCH, Weinheim (1999).

[5] Karatas Y, Kaskhedikar N, Burjanadze M, Wiemhofer HD, Macromol. Chem. Phys., 207, 419 (2006)

[6] Vermeulen LA, Smith K, Wang JB, Electrochim. Acta, 45(7), 1007 (1999)

[7] Zhang ZC, Sherlock D, West R, Amine K, Lyons LJ, Macromol, 36, 8907 (2003)

[8] Funke K, Heimann B, Vering M, Wilmer D, J. Electrochem. Soc., 148(5), A395 (2001)

[9] Allcock HR, Olmeijer DL, O’Connor SJM, Macromol, 31, 753 (1998)

[10] Gray FM, Armand M, Polymer electrolytes, in Handbook of Battery Materials. Besenhard JO, Ed., Wiley-VCH, Weinheim (1999).

[11] Hooper R, Lyons LJ, Moline DA, West R, Silicon Chemistry, 1, 121 (2002)

[12] Hooper R, Lyons LJ, Moline DA, West R, Organometallics, 18, 3249 (1999)

[13] Iwahara T, Kusakabe M, Chiba M, Yonezawa K, J. Polym. Sci. A: Polym. Chem., 31, 2617 (1993)

[14] Mukbaniani O, Tatrishvili T, Markarashhvili E, Esartia I, Georgian Chem. J., 2, 153 (2011)

[15] Tartakovskaia LM, Makarov IG, Kazakova VM, Kopilov VM, Zhdanov AA, Ser. Chim., 12, 2818 (1980)

[16] Andrianov KA, Tartakovskaia LM, Kopilov VM, Sementsova ZN, Zhur. Obshch. Khim., 45, 112 (1975)

[17] Corey EJ, Snider BB, J. Amer. Chem. Soc., 94, 6190 (1972)

[18] Tartakovskaia LM, Kopilov VM, Zhdanov AA, Vysokomol. Soed., 26, 234 (1984)

[19] Zhang ZC, Fang SB, Electrochim. Acta, 45(13), 2131 (2000)