Study of the Hydrodynamic Effect on Molecular Parameters of the Isoprene Polymerization Product with the Neodymium-Containing Catalytic Complex Present

Abstract

The results of studying kinetic regularities in the process of obtaining polyisoprene in the presence of neodymium-containing catalytic systems for various technological modes of industrial production are presented. The process kinetic scheme is provided under conditions of the used catalyst monocenter, according to which a mathematical model of the process of isoprene polymerization for the process periodic and continuous modes is compiled. Kinetic approach to solving problems of chemical kinetics in combination with the method of moments was applied in the process mathematical description. To evaluate hydrodynamic influence exerted by the process implementation in a reactor cascade, the constructed kinetic model was supplemented with a macro-kinetic module that takes into account the relevant patterns. Features of the starting and static modes calculation in continuous production were determined. Numerical calculation methods were introduced to obtain dependences of alterations in the molecular parameters of the resulting product for a different number of reactors used in the continuous production system under static conditions. The hydrodynamic mode influence was shown in the reaction zone on the molecular weight distribution of the resulting product. As a result of computational experiments aimed at increasing the length of the reactor cascade, increase in the average molecular weights and approximation of the obtained values to the those characterizing the process periodic mode were noted

The study was carried out within the framework of the State Task of the Ministry of Education and Science of the Russian Federation (scientific topic code FZWU-2020-0027)

Please cite this article in English as:

Miftakhov E.N., Mustafina S.A., Podvalny S.L., et al. Study of the hydrodynamic effect on molecular parameters of the isoprene polymerization product with the neodymium-containing catalytic complex present. Herald of the Bauman Moscow State Technical University, Series Natural Sciences, 2022, no. 5 (104), pp. 120--138 (in Russ.). DOI: https://doi.org/10.18698/1812-3368-2022-5-120-138

References

[1] Ren C., Li G., Dong W., et al. Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization. Polymer, 2007, vol. 48, iss. 9, pp. 2470--2474. DOI: https://doi.org/10.1016/j.polymer.2007.02.027

[2] Marina N.G., Monakov Yu.B., Sabirov Z.M., et al. Lanthanide compounds --- catalysts of stereospecific polymerization of diene monomers. Review. Polym. Sci. USSR, 1991, vol. 33, iss. 3, pp. 387--417. DOI: https://doi.org/10.1016/0032-3950(91)90237-K

[3] Zhavoronkov D.A., Miftakhov E.N., Mustafina S.A., et al. Modeling and theoretical research polymerization process isoprene in presence microheterogenous neodymium catalytic systems. Vestnik Bashkirskogo gosudarstvennogo universiteta [Bulletin of Bashkir University], 2018, vol. 23, no. 4, pp. 1079--1083 (in Russ.).

[4] Levkovskaya E.I., Bubnova S.V., Bodrova V.S., et al. Polymerization of isoprene in the presence of catalytic systems based on gadolinium. Kauchuk i rezina, 2014, no. 1, pp. 12--15 (in Russ.).

[5] Zakharov V.P., Mingaleev V.Z., Zakharova E.M., et al. Improvement of the neodymium catalyst preparation step in isoprene rubber production. Russ. J. Appl. Chem., 2013, vol. 86, no. 6, pp. 909--913. DOI: https://doi.org/10.1134/S1070427213060219

[6] Berlin A.A., Dyumaev K.M., Minsker K.S., et al. Tubular turbulent reactors --- the basis of energy and resource saving technologies. Khimicheskaya promyshlennost’, 1995, no. 9, pp. 550--559 (in Russ.).

[7] Minsker K.S., Zakharov V.P., Berlin A.A. Plug-flow tubular turbulent reactors: a new type of industrial apparatus. Theor. Found. Chem. Eng., 2001, vol. 35, no. 2, pp. 162--167. DOI: https://doi.org/10.1023/A:1010333707619

[8] Zakharov V.P., Mingaleev V.Z., Berlin A.A., et al. Kinetic heterogeneity of titanium and neodymium catalysts for the production of 1,4-cis-polyisoprene. Khimicheskaya fizika, 2015, vol. 34, no. 3, pp. 69--75 (in Russ.). DOI: https://doi.org/10.7868/S0207401X15030139

[9] Miftakhov E.N., Nasyrov I.Sh., Mustafina S.A., et al. Study of kinetics of isoprene polymerization in the presence of neodymium-containing catalytic systems modified in turbulent flows. Russ. J. Appl. Chem., 2021, vol. 94, no. 1, pp. 77--83. DOI: https://doi.org/10.1134/S1070427221010110

[10] Usmanov T.S., Spivak S.I., Usmanov S.M. Obratnye zadachi formirovaniya molekulyarno-massovykh raspredeleniy [Inverse problems of molecular weight distributions formation]. Moscow, Khimiya Publ., 2004.

[11] Friebe L., Nuyken O., Obrecht W. Neodymium-based Ziegler/Natta catalysts and their application in diene polymerization. In: Nuyken O. (eds). Neodymium based Ziegler catalysts --- fundamental chemistry. Advances in Polymer Science, vol. 204. Berlin, Heidelberg Springer, 2006, pp. 1--154. DOI: https://doi.org/10.1007/12_094

[12] Usmanov T.S., Maksyutova E.R., Gataullin I.K., et al. Inverse kinetic problem for ion-coordination polymerization of dienes. Polym. Sci. Ser. A, 2003, vol. 45, no. 2, pp. 79--84.

[13] Podvalny S.L. Modelirovanie promyshlennykh protsessov polimerizatsii [Modeling of industrial polymerization processes]. Moscow, Khimiya Publ., 1979.

[14] Podvalny S.L., Barabanov A.V. Strukturno-molekulyarnoe modelirovanie nepreryvnykh tekhnologicheskikh protsessov mnogotsentrovoy polimerizatsii [Structural and molecular modeling of continuous technological processes of multicenter polymerization]. Voronezh, Nauchnaya kniga Publ., 2011.

[15] Miftakhov E., Mustafina S., Petrenko V., et al. Modeling of a continuous process of isoprene polymerization in the presence of titanium-based catalyst systems under polycentric conditions. J. Phys.: Conf. Ser., 2020, vol. 1479, art. 012072. DOI: https://doi.org/10.1088/1742-6596/1479/1/012072

[16] Aminova G.A., Bronskaya V.V., Ignashina T.V., et al. Analysis of molecular weight distribution and main characteristics of polymer branching during synthesis of rubber on a neodymium-containing catalyst in a cascade of continuous reactors. Khimicheskaya promyshlennost’ segodnya [Chemical Industry Today], 2007, no. 12, pp. 36--44 (in Russ.).

[17] Manuiko G.V., Aminova G.A., Bronskaya V.V., et al. Calculation of the molecular weight distribution of the polymer produced in a cascade of reactors with allowance for chain transfer to the polymer. Theor. Found. Chem. Eng., 2008, vol. 42, no. 3, pp. 336--339. DOI: https://doi.org/10.1134/S0040579508030159

[18] Ostrovskiy G.M., Volin Yu.M., Ziyatdinov N.N. Optimizatsiya v khimicheskoy tekhnologii [Optimization in chemical technology]. Kazan, Fen Publ., 2005.

[19] Miftakhov E.N., Mustafina S.A. Reshenie pryamoy zadachi nepreryvnogo protsessa polimerizatsii izoprena v prisutstvii mikrogeterogennykh kataliticheskikh system [Solving the problems of gradient optimization of cascade-reactor circuits using conjugated systems]. Patent RU 2020610226. Appl. 16.12.2019, publ. 10.01.2020 (in Russ.).

[20] Podvalny S.L. Solution of the problem for cascade reactor schemes gradient optimization using the adjoint method. Vestnik Voronezhskogo gosudarstvennogo tekhnicheskogo universiteta [Bulletin of Voronezh State Technical University], 2013, vol. 9, no. 2, pp. 27--32 (in Russ.).

[21] Ostrovskiy G.M., Ziyatdinov N.N., Lapteva T.V. Optimizatsiya tekhnicheskikh system [Optimization of technical systems]. Moscow, KnoRus Publ., 2012.