2017 (1) 7

https://doi.org/10.15407/polymerj.39.01.49

Intensification of hydrogen-peroxide-initiated polymerization of isoprene. The use of mixtures of solvents and replacement of alcohols as solvents

V.P. Boiko, V.К. Grishchenko, V.P. Valovyy

Institute of Macromolecular Chemistry NAS of Ukraine

48, Kharkivske shose, Kyiv, 02160, Ukraine

Polym. J., 2017, 39, No. 1: 49-54.

Section: Synthesis polymers.

Language: Ukrainian.

Abstract:

The results of kinetic studies of the isoprene oligomerization under the action of hydrogen peroxide (HP) in the presence of solvent mixtures and in solvents – wastes of ethyl alcohol production have been present. The isoprene polymerization in the mixtures of isopropyl alcohols (IPA) and ketones showed synergism in rates and oligomer yields. The maximum excess over additive yield amounts to 10 % at IPA-acetone composition 60:40 vol. %, and to 27 % at IPA-cyclohexanone-composition 20:80 vol. % against pure IPA. The rate of polymerization in the latter mixture increases by twice what permits to approach a yield in a pure IPA during a quarter shorter time at cyclohexanone content 25 vol. %. The appreciable effects were approached in the systems where IPA was completely changed with waste products of ethyl alcohol production – ether-aldehyde (top) fraction and fusel oil. In the former solvent a yield growth consists nearly two times through 6 h., in the latter does 47 %. The ether-aldehyde (top) fraction can be recommended for the industrial use in process of isoprene polymerization. The possible activation mechanisms of described substances were discussed. In the mixtures IPA-ketenes acceleration is explained by forming hydroxyhydroperoxydes at a reaction with HP. Ether-aldehyde fraction and fusel oil consist of aldehyde admixtures that activate HP decomposition. Benzoic acid seemed to be a perspective activator at very low molar proportions, about thousands relative to hydrogen peroxide. The investigation of its action mechanism opens the possibility of creation a new high-activity agents for intensification of diene polymerization under the action of HP.

Key words: isoprene, hydrogen peroxide, oligomerization, solvents, activators.

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