kaz29Вестник Казахстанско-Британского технического университетаHerald of the Kazakh-British Technical University1998-66882959-8109Казахстанско-Британский Технический Университетkaz29-148Research ArticleХИМИКО-ТЕХНОЛОГИЧЕСКИЕ НАУКИ И ЭКОЛОГИЯCHEMICAL, TECHNOLOGICAL AND ENVIRONMENTAL SCIENCESСИНТЕЗ И ИЗУЧЕНИЕ СОСТАВА ПОЛИМЕРМЕТАЛЛИЧЕСКОГО КОМПЛЕКСА НА ОСНОВЕ ХЛОРИДА МЕДИ(II) И ПОЛИЭТИЛЕНГЛИКОЛЯSYNTHESIS AND STUDY OF THE COMPOSITION OF A POLYMERMETALLIC COMPLEX BASED ON COPPER(II) CHLORIDE AND POLYETHYLENE GLYCOLБакироваБ. С.BakirovaB. S.

ст. преподаватель

СмагуловаИ. А.SmagulovaI. A.

PhD-докорант

АкбаеваД. Н.AkbayevaD. N.

д.х.н., доцент

СейлхановаГ. А.SeilkhanovaG. A.

д.х.н., профессор

Казахский Национальный университет им. аль-ФарабиКазахстанКазахский Национальный университет им. аль-ФарабиKazakhstan2020071120211725967Copyright © Бакирова Б.С., Смагулова И.А., Акбаева Д.Н., Сейлханова Г.А., 20212021Бакирова Б.С., Смагулова И.А., Акбаева Д.Н., Сейлханова Г.А.Bakirova B.S., Smagulova I.A., Akbayeva D.N., Seilkhanova G.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vestnik.kbtu.edu.kz/jour/article/view/148

Cинтезирован полимерметаллический комплекс на основе хлорида меди (II) и полиэтиленгликоля, и установлен его состав потенциометрическим и кондуктометрическим методами. Были рассчитаны величины функций образования Бьеррума. Были построены кривые титрования и найдены оптимальные мольные соотношения реагирующих компонентов. Полученные данные свидетельствуют об образовании полимерных комплексов меди, в которых на два составных монозвена полиэтиленгликоля приходится один ион металла-комплексообразователя. Координационная насыщенность металла-комплексообразователя в этом комплексе осуществляется за счет молекул растворителя или аниона солей металла. Рассчитаны термодинамические характеристики процесса комплексообразования: ΔrG0, ΔrН0, ΔrS0. Отрицательные значения изменения энергии Гиббса указывают на потенциальную возможность протекания исследуемого процесса в направлении образования полимерметаллического комплекса. Положительное значение изменения энтальпии (ΔrН0) в интервале температур 298-318К свидетельствует об эндотермическом характере образования поликомплекса в указанном интервале. Изменения значений энтропии связаны с разрушением сольватных оболочек лигандных групп ПЭГ и иона меди, вытеснением молекул растворителя и образованием хелатных структур. Методом ИК-спектроскопии установлено, что атомы кислорода полимерного лиганда принимают участие в образовании координационной связи с ионом металла-комплексообразователя.

Вased on copper(II) chloride and polyethylene glycol a polymer-metal complex was synthesized, and its composition was established by potentiometric and conductometric methods. The values of the Bierrum’s formation functions were calculated. Titration curves were constructed. The optimal molar ratios of the reacting components were found. The data obtained indicate the formation of polymer complexes of copper, in which two complex mono units of polyethylene glycol account for one metal complexing ion. The coordination saturation of the metal-complexing agent in this complex is due to solvent molecules or the anion of metal salts. The thermodynamic characteristics of the complexation process were calculated: ΔrG0, ΔrН0, ΔrS0. Negative values of the Gibbs’ energy change indicate the potential possibility for the process under study in the direction of the formation of the polymer-metal complex. A positive value of the change in enthalpy (ΔrН0) in the temperature range 298-318K indicates the endothermic nature of the formation of the polycomplex in the indicated range. Changes in entropy values are associated with the destruction of the solvate shells of the PEG’s ligand groups and copper ions, the displacement of solvent molecules and the formation of chelate structures. Using IR spectroscopy, it was confirmed that the oxygen atoms of the polymer ligand are involved in the formation of coordination bonds with the metal complexing ion.

полимерметаллический комплексионы меди(II)полиэтиленгликольтермодинамические характеристикиустойчивостьpolymer-metal complexcopper(II) ionspolyethylene glycolthermodynamic characteristicsstabilityReferencesBekturov Ye.A., Bimendina L.A., Kudaybergenov S.Ye. Polymer complexes and catalysts. – Almaty: Nauka, 1982. – 191 p.Bekturov Ye.A., Bimendina L.A., Kudaybergenov S.Ye. Polymer complexes and catalysts. – Almaty: Nauka, 1982. – 191 p.Pomogaylo A.D. Polymer immobilized metal complex catalysts. – M: Nauka, 1988. – 303 p.Pomogaylo A.D. Polymer immobilized metal complex catalysts. – M: Nauka, 1988. – 303 p.Atkins P., Paula de J. Physical chemistry. – Great Britain: Oxford Univ. Press, 2006. – 1085 p.Atkins P., Paula de J. Physical chemistry. – Great Britain: Oxford Univ. Press, 2006. – 1085 p.Umland F., Yansen A., Tirig D., Vyunsh G. Complex compounds in analytical chemistry. – M.: Mir, 1975. – 531 p.Umland F., Yansen A., Tirig D., Vyunsh G. Complex compounds in analytical chemistry. – M.: Mir, 1975. – 531 p.Kolate A., Baradia D., Patil S., Vhora I., Kore G., Misra A. PEG – A versatile conjugating ligand for drugs and drug delivery systems // J. Control. Release. – 2014. – Vol. 192. – P. 67-81.Kolate A., Baradia D., Patil S., Vhora I., Kore G., Misra A. PEG – A versatile conjugating ligand for drugs and drug delivery systems // J. Control. Release. – 2014. – Vol. 192. – P. 67-81.Takafuji Y., Jo J.-I., Tabata Y. Simple PEG Modification of DNA Aptamer Based on Copper Ion Coordination for Tumor Targeting // J. Biomater. Sci. Polym. Ed. – 2011. – Vol. 22, № 9. – P. 1179-1195.Takafuji Y., Jo J.-I., Tabata Y. Simple PEG Modification of DNA Aptamer Based on Copper Ion Coordination for Tumor Targeting // J. Biomater. Sci. Polym. Ed. – 2011. – Vol. 22, № 9. – P. 1179-1195.Yoshida M., Tabata Y.Tumor Targeting of Protein Through Poly(ethylene glycol) Conjugation with Metal Coordination // J. Nanosci. Nanotechnol. – 2010. –Vol. 10, № 2. – Р. 877-885.Yoshida M., Tabata Y.Tumor Targeting of Protein Through Poly(ethylene glycol) Conjugation with Metal Coordination // J. Nanosci. Nanotechnol. – 2010. –Vol. 10, № 2. – Р. 877-885.Jin Y., Sun M., Mu D., Ren X., Wang Q., Wen L. Investigation of PEG adsorption on copper in Cu2+-free solution by SERS and AFM // Electrochim. Acta. – 2012. – Vol. 78. – P. 459-465.Jin Y., Sun M., Mu D., Ren X., Wang Q., Wen L. Investigation of PEG adsorption on copper in Cu2+-free solution by SERS and AFM // Electrochim. Acta. – 2012. – Vol. 78. – P. 459-465.Dang Th.M.D., Le Th.T.Th., Fribourg-Blanc E., Dang M.Ch. Synthesis and optical properties of copper nanoparticles prepared by a chemical reduction method // Adv. Nat. Sci.: Nanosci. Nanotechnol. – 2011. – Vol. 2, № 1. – Р. 015009.Dang Th.M.D., Le Th.T.Th., Fribourg-Blanc E., Dang M.Ch. Synthesis and optical properties of copper nanoparticles prepared by a chemical reduction method // Adv. Nat. Sci.: Nanosci. Nanotechnol. – 2011. – Vol. 2, № 1. – Р. 015009.Bunchuk L.V. Investigation of the properties of nanostructured silicon and carbon-containing materials and the process of forming nanostructured polymer-metal films based on them to develop a technology for the synthesis of structures for sorption and catalysis: abstract of cand. diss. chem. of sciences: 02.09. 04. – Almaty: KazNU, 2006. – 65 p.Bunchuk L.V. Investigation of the properties of nanostructured silicon and carbon-containing materials and the process of forming nanostructured polymer-metal films based on them to develop a technology for the synthesis of structures for sorption and catalysis: abstract of cand. diss. chem. of sciences: 02.09. 04. – Almaty: KazNU, 2006. – 65 p.Antipina A.D., Baranovskiy V.Yu., Papisov I.M., Kabanov V.A. The formation of polymer-metal nanocomposites by the reduction of divalent copper from its complexes with polyethyleneimine // Polymer Science. – 1972. – № 14. – Р. 941-949.Antipina A.D., Baranovskiy V.Yu., Papisov I.M., Kabanov V.A. The formation of polymer-metal nanocomposites by the reduction of divalent copper from its complexes with polyethyleneimine // Polymer Science. – 1972. – № 14. – Р. 941-949.Akbayeva D.N., Seilkhanova G.А., Bakirova B.S., Smagulova I.A., Salkhay А.К., Borangaziyeva A.K. Studying the composition of complexes on the basis of palladium(II), copper(II), iron(III) chlorides and polyvinylpyrrolidone // News AS RK. Ser. Chemistry and technology. 2019.– №5. – P. 92-100.Akbayeva D.N., Seilkhanova G.А., Bakirova B.S., Smagulova I.A., Salkhay А.К., Borangaziyeva A.K. Studying the composition of complexes on the basis of palladium(II), copper(II), iron(III) chlorides and polyvinylpyrrolidone // News AS RK. Ser. Chemistry and technology. 2019.– №5. – P. 92-100.Akbayeva D.N., Bakirova B.S., Seilkhanova G.A., Sitzmann H. Synthesis, characterization, and catalytic activity of palladium-polyvinylpyrrolidone complex in oxidation of octene-1 // Bulletin of Chemical Reaction Engineering and Catalysis. – 2018. – Vol. 13, № 3. – P. 560-572.Akbayeva D.N., Bakirova B.S., Seilkhanova G.A., Sitzmann H. Synthesis, characterization, and catalytic activity of palladium-polyvinylpyrrolidone complex in oxidation of octene-1 // Bulletin of Chemical Reaction Engineering and Catalysis. – 2018. – Vol. 13, № 3. – P. 560-572.Tager A.A. Physics and chemistry of polymers. – M: Khimiya, 1968. – 536 p.Tager A.A. Physics and chemistry of polymers. – M: Khimiya, 1968. – 536 p.Ergozhin E.E., Menligaziev E.Zh. Multifunctional ion exchanges. – Alma-Ata: Nauka, 1986. – 300 p.Ergozhin E.E., Menligaziev E.Zh. Multifunctional ion exchanges. – Alma-Ata: Nauka, 1986. – 300 p.Bjerrum J. Stability Constants of Metal–Ion Complexes: Part I. Organic Ligands: Part II. Inorganic Ligands/J. Bjerrum, G.Schwarzenbach, L.G. Sillen(eds.). – London: Chemical Society, 1957,1958. – 754 p.Bjerrum J. Stability Constants of Metal–Ion Complexes: Part I. Organic Ligands: Part II. Inorganic Ligands/J. Bjerrum, G.Schwarzenbach, L.G. Sillen(eds.). – London: Chemical Society, 1957,1958. – 754 p.Ospanova A.K. Physico-chemical bases of the formation of coordination compounds of metals IB, IIB and IV subgroups with polyethyleneimine and unitiol: dis. ... dr. chemical science: 02.00.04. Almaty: KazGU, 2002. – 305 p.Ospanova A.K. Physico-chemical bases of the formation of coordination compounds of metals IB, IIB and IV subgroups with polyethyleneimine and unitiol: dis. ... dr. chemical science: 02.00.04. Almaty: KazGU, 2002. – 305 p.Seylkhanova G.A. Physico-chemical laws of the formation of complex compounds of polyethyleneimine and polyacrylamide: abstract of dr. diss. chem. of sciences. – Almaty, 2010. – 43 p.Seylkhanova G.A. Physico-chemical laws of the formation of complex compounds of polyethyleneimine and polyacrylamide: abstract of dr. diss. chem. of sciences. – Almaty, 2010. – 43 p.Safronov A.P., Gabdrafikova Yu.M., Ukhalina O.L., Ostroushko A.A. Enthalpy of complexation of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone with copper and cadmium ions in an aqueous solution // Polymer Science. – 2004. – Vol. 46, N 5. – P. 867-874.Safronov A.P., Gabdrafikova Yu.M., Ukhalina O.L., Ostroushko A.A. Enthalpy of complexation of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone with copper and cadmium ions in an aqueous solution // Polymer Science. – 2004. – Vol. 46, N 5. – P. 867-874.Lyashchenko A.K., Lileyev A.S., Palitskaya T.A., Ostroushko A.A. Dielectric relaxation characteristics of water in mixed solvents water-polyvinyl alcohol and water-polyvinylpyrrolidone // Russian Journal of Physical Chemistry A. – 2001. – Vol.75, N 2. – P. 257-262.Lyashchenko A.K., Lileyev A.S., Palitskaya T.A., Ostroushko A.A. Dielectric relaxation characteristics of water in mixed solvents water-polyvinyl alcohol and water-polyvinylpyrrolidone // Russian Journal of Physical Chemistry A. – 2001. – Vol.75, N 2. – P. 257-262.Umland F., Yansen A., Tirig D., Vyunsh G. Complex compounds in analytical chemistry. – M.: Mir, 1975. – 531 p.Umland F., Yansen A., Tirig D., Vyunsh G. Complex compounds in analytical chemistry. – M.: Mir, 1975. – 531 p.Tunc S., Duman O. The effect of different molecular weight of poly (ethylene glycol) on the electrokinetic and rheological properties of Na-bentonite suspensions // Colloids Surf. A Physicochem. Eng. Asp. – 2008. – Vol. 37. – P. 93–99.Tunc S., Duman O. The effect of different molecular weight of poly (ethylene glycol) on the electrokinetic and rheological properties of Na-bentonite suspensions // Colloids Surf. A Physicochem. Eng. Asp. – 2008. – Vol. 37. – P. 93–99.Shameli K., Ahmad M.B., Jazayeri S.D., Sedaghat S., Shabanzadeh P., Jahangirian H., Mahdavi M., Abdollahi Y. Synthesis and characterization of polyethylene glycol mediated silver nanoparticles by the green method // Int. J. Mol. Sci. – 2012. - № 13. – P. 6639 – 6650.Shameli K., Ahmad M.B., Jazayeri S.D., Sedaghat S., Shabanzadeh P., Jahangirian H., Mahdavi M., Abdollahi Y. Synthesis and characterization of polyethylene glycol mediated silver nanoparticles by the green method // Int. J. Mol. Sci. – 2012. - № 13. – P. 6639 – 6650.Healy J.P., Pletcher D., Goodenough M. The chemistry of the additives in an acid copper electroplating bath: Part I. Polyethylene glycol and chloride ion // J. Electroanal. Chem. – 1992. – V. 338, № 1–2. – P. 155-165.Healy J.P., Pletcher D., Goodenough M. The chemistry of the additives in an acid copper electroplating bath: Part I. Polyethylene glycol and chloride ion // J. Electroanal. Chem. – 1992. – V. 338, № 1–2. – P. 155-165.Golks F., Gründer Y., Drünkler A., Roy J., Stettner J., Zegenhagen J., Magnussen O.M. In Situ Surface X-Ray Diffraction Studies of the Influence of the PEG-Cl-Complex on Homoepitaxial Electrodeposition on Cu(001) // J. Electrochem. Soc. – 2013. – V. 160, № 12. – Р. D3165-D3170.Golks F., Gründer Y., Drünkler A., Roy J., Stettner J., Zegenhagen J., Magnussen O.M. In Situ Surface X-Ray Diffraction Studies of the Influence of the PEG-Cl-Complex on Homoepitaxial Electrodeposition on Cu(001) // J. Electrochem. Soc. – 2013. – V. 160, № 12. – Р. D3165-D3170.Wang W., Li Y.-B. Effect of Cl − on the adsorption–desorption behavior of PEG // J. Electrochem. Soc. – 2008. – V. 155, № 4. – Р. D263-D269.Wang W., Li Y.-B. Effect of Cl − on the adsorption–desorption behavior of PEG // J. Electrochem. Soc. – 2008. – V. 155, № 4. – Р. D263-D269.Feng Z.V., Li X., Gewirth A.A. Inhibition due to the interaction of polyethylene glycol, chloride, and copper in plating baths: a surface-enhanced raman study // J. Phys. Chem. B. – 2003. – V. 107, № 35. – Р. 9415-9423.Feng Z.V., Li X., Gewirth A.A. Inhibition due to the interaction of polyethylene glycol, chloride, and copper in plating baths: a surface-enhanced raman study // J. Phys. Chem. B. – 2003. – V. 107, № 35. – Р. 9415-9423.

The authors declare that there are no conflicts of interest present.