At pyrolysis of hydrocarbon raw materials on ethylene plants significant amounts of liquid by-products are formed. It is possible to synthesize hydrocarbon resins that are used as film forming agents in anti-corrosion and lacquer coatings based on the C9 fraction of liquid by-products of pyrolysis. The use of low temperature emulsion oligomerization can simplify the purification of the target product and whie the synthesis can be performed at low durations and temperatures.
It is proposed to use low-temperature emulsion oligomerization of hydrocarbon fraction C9 initiated metal stearates - hydrogen peroxide oxidation-reduction system. To study the emulsion oligomerization of the C9 fraction in the presence of redox systems as oxidation-reducing initiating systems, stearic acid salts of copper, tin, zinc and nickel were used. The process was carried out at a temperature - 303 K, a volume ratio of components [fraction C9]: [water] = [1: 2], concentration of emulsifier E-30 – 0,7% by weight, concentration of hydrogen peroxide – 1,0% by weight, mixing intensity - Re = 10120, duration of oligomerization - 3 hours. The highest yield of oligomer (28,0% by weight) was achieved with the usage of the tin stearate - hydrogen peroxide oxidation-reducing initiating system. The influence of qualitative and quantitative composition of the redox system on the yield and the physical and chemical properties of oligomers was investigated. It was shown that the use of the oxidation-reduction system of the stearate of the state - hydrogen peroxide provided an yield increase in the of oligomers to 14,4% by weight. in comparison with the initiation by hydrogen peroxide under the same conditions.
Chromatographic analysis showed that, as a result of low-temperature emulsion oligomerization, the styrene monomers and their derivatives are involved into the reaction. A mixture of unreacted hydrocarbons after emulsion oligomerization contains a high boiling point dicyclopentadiene, indene, residual styrene, vinyltoluene and non-polymerizing hydrocarbons.
The possibility the initiation by oxidation-reduction system initiation of metal stearates and hydrogen peroxide low-temperature emulsion oligomerisation of hydrocarbons of fraction C9 was established. It was determined that the use of an oxidation-reducing system was able to increase the oligomer yield in comparison with the radical oligomerization initiated by hydrogen peroxide. Physical and chemical characteristics of oligomers obtained by different initiation methods remain unchanged.
1. DzInyak B. O. NaukovI osnovi I tehnologIya koolIgomerIv z pobIchnih produktIv pIrolIzu vuglevodnIv: avtoref. dis. … d-ra tehn. nauk.: spets. 05.17.04 / B. O. DzInyak // Nats. un-t "LvIvska polItehnIka". - LvIv, 2013. - 40 s.
2. Fuch U. V. KoolIgomerizatsIya v emulsIYi sumIshI nenasichenih vuglevodnIv pobIchnih produktIv pIrolIzu: avtoref. dis. … kand. tehn. nauk: spets. 05.17.04 "TehnologIya produktIv organIchnogo sintezu" / U. V. Fuch. - LvIv, 2016. - 21s.
3. MItIna N.E., ZaIchenko O. S., Bratichak M. M., PolItIkova L. G. Vodno-dispersIynI plIvkoutvoryuvachI na osnovI kopolImerIv nenasichenoYi fraktsIYi C9 termolIzu nafti. Sintez ta vlastivostI // HImIchna promislovIst UkraYini, 2006. - № 3. - S. 14-17.
4. DvostadIyniy sposIb InItsIyovanoYi koolIgomerizatsIYi nenasichenih vuglevodnIv fraktsIYi S9 / O. M. Orobchuk, R. O. Subtelniy, Z. Yu. Maresh, B. O. DzInyak // VIsnik Natsionalnogo universitetu "Lvivska politehnika". HImIya, tehnologIya rechovin ta Yih zastosuvannya. - 2014. - №787. - S. 154-159.
5. KoolIgomerizatsIya v emulsIYi vuglevodnIv fraktsIYi S9 z vikoristannyam persulfatu kalIyu / R. O. Subtelniy, U. V. Fuch, L. V. Revenko, B. O. DzInyak // VIsnik NatsIonalnogo unIversitetu " Lvivska politehnika". HImIya, tehnologIya rechovin ta Yih zastosuvannya. - 2013.- № 761. - S.209-212.
6. Fuch U. V. Vivchennya vplivu prirodi emulgatora na protses koolIgomerizatsIYi v emulsIYi vuglevodnevoYi fraktsIYi / U. V. Fuch, B. O. DzInyak, R. O. Subtelniy // Vostochno-Evropeyskiy zhurnal peredovyih tehnologiy. - 2015. - № 4/6 (65). - S. 54 - 57.
7. The effect of pH on emulsion polymerization of styrene in the presence of an amphoteric emulsifier / K. Kato, H. Kondo, M. Takeda at all // Colloid and Polymer Science. - 1987. - Vol. 265( 11), - P. 950-956.
https://doi.org/10.1007/BF01412396
8. Redox for Main Polymerization of Emulsion Polymers / P. Fithian, M. O'Shaughnessy, M. Lubik, S. Mark // PCI magazine. - 2017. - P. 24-30.