SOME KINETIC PARAMETERS OF PROCESS OF RADICAL POLYMERIZATION OF BUTYL ESTER OF METHACRYLIC ACID IN ION LIQUID

DOI: 10.6060/tcct.20165912.5432
Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2016. V. 59. N 12. P. 75-79

In the recent years one of the priority directions of researches in chemistry became processes which have received the general name "green chemistry" which means the imple-mentation of processes in the medium of organic liquid salts so-called the ionic liquids (IL). Absolutely other ionic nature of IL causes their catalytic activity that leads to increase in a rate and selectivity of many organic reactions. These regularities were observed by us in the processes of radical polymerization of butyl ether of methacrylic acid in the medium of ionic liquids which are synthesized by interaction of the formic and acetic acids with various amines. In the present article results of researches of polymerization of butyl ether of meth-acrylic acid in the medium of ionic liquid on the basis of acetic acid and N-methylpirrolidone comparatively with aromatic solvent –benzene. And some kinetic parameters of process are presented. By the carried-out cycle of researches it was established that use of the specified ionic liquid as the reactionary medium provides a high yield of polybutylmethacrylate ~ 95% and the received polymeric products were characterized by molecular weight – 520000 with a viscometric method. At the similar conditions in the medium of organic solvent – benzene the yield of polybutylmethacrylate was 75.0%, and molecular weight –379000. On the basis of experimental data the regression model has been constructed with use of the program Box-BenkinD module, the Matlab-7 program. The comparative analysis of values of rate con-stants of process polymerization of butyl ether of methacrylic acid at various temperatures of reaction confirms rather high rate of reaction in the medium of ionic liquid. Modern comput-er equipments represent a great opportunity for a treatment information and choice of a type of the equation of regression by an experimental method, for example, by comparison of size of residual dispersion ( S res2) calculated for various models. The received model has been used for the solution of a problem of optimization and kinetic regularities of process. Activa-tion energies calculated on Arrhenius formula depending on solvent nature also confirm mentioned above. For the polymerization process in medium of IL under study the activation energy was E = 6105.3 cal (26.2 kJ/mol) at K0 = 0.022. Given value is less then activation energy of E = 8109.3cal (34.87 кJ/mol) at K0=0.0052 for polymerization reaction of butyl ether of methacrylic acid in benzene medium. The received results confirm the high rate of polymerization reaction of butyl ether of methacrylic acid in the medium of IL which are ex-plained by influence of the ionic medium on growth reactions (decrease in energy of activa-tion) and break of a chain (increase in viscosity of reactionary system – gel effect).

Key words: ion liquid, organic solvent, reaction environment, methacrylic acid butyl ester, radi-cal polymerization

REFERENCES
1. Olivier-Bourbigou H., Magna L., Morvan D. Appl. Catal. 2010. V. 373. P. 1–56. DOI: 10.1016/j.apcata.2009.10.008
2. Paul T.A., Wasserscheid P., Stark A. Green Solvents, Ionic Liquids. 2013. 365 p.
3. Rogers R., Seddon K. Ionic liquids: industrial applications to green chemistry. ACS symposium series 818, Washington, DC: American Chemical Society; 2002. DOI: 10.1021/ bk-2002-0818
4. Tsarik L.Ya., Kazak S.V., Rokhin F.V., Fedorin A.Yu. Radical polymeryzation of diethyl fumarate in ionic liquids. Izv. Vyssh. Uchebn. Zaved. Khim. Tekhnol. 2012. V. 55. N 2. P. 74-77 (in Russian)
5. Hong H. L., Zhang H.W., Mays J.W., Visser A.E., Brazel C.S., Holbery J.D., Reichert W.M., Rogers R.D. Conventional free radical polymerization in room temperature ionic liquids: a green approach to commodity polymers with practical advantages. Chem. Commun. 2002. N 13. P. 1368-1369. DOI: 10.1039/b204319j
6. Ibragimova M.D., Azizov A.G., Pashayeva Z.N., Abdullayeva F.M., Yusifzade F.Yu., Dadasheva S.D. Use of ionic liquids as solvent and as catalyst in the processes of synthesis polymers. Khimiya v interesakh ustoychivoqo razvitiya. 2015. V. 23. N 3. P. 225-234 (in Russian).
7. Toroptseva A.M., Beloqorodskaya K.V., Bondarenko V.M. Laboratory workshop on chemistry and technology of high-molecular compounds. L.: Khimiya. 1972. 416 p.
8. S-plus 2000. Professional Release. Math Soft Inc. USA. 2000.
9. Matlab – 6,5. The Math Works. Inc. All Rights Reserved. USA, 2000.

2016, Т. 59, № 12, Стр. 75-79

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