Oligomerization of C9 hydrocarbon fraction initiated by amino peroxides with cyclic substitute





petroleum polymer resin, tert-butyl piperidinomethyl peroxide, 2- [4- (tert-butylperoxymethyl) piperazinomethylperoxy]-2-methylpropane, suspension oligomerization, bromine number, oil processing


This paper investigates the production of hydrocarbon resins by oligomerization in solution and suspension of the C9 fraction of by-products from oil refining. The disadvantage of existing technologies for oligomers by free radical oligomerization is the use of high reaction temperatures. The application of N-replaced amino peroxides as low-temperature initiators and a suspension oligomerization technology can reduce the temperature and duration of the reaction.

The correlation between oligomerization parameters and yield and characteristics of oligomers has been established. Owing to this, it will be possible to set optimal conditions and predict the properties of the resulting products. The high values of the yield and bromine number correlation in oligomerization in solution (–0.98 and –0.95) and suspension (–0.83 and –0.80) indicate the course of the oligomerization reaction.

The main factor influencing oligomerization in solution is the reaction temperature (correlation 0.80). The softening temperature of oligomers is in the range of 349‒353 K and does not depend on the oligomerization conditions in the solution (correlation indicator 0.18).

Suspension oligomerization in the studied intervals does not depend on temperature (correlation −0.08) and initiator concentration (correlation 0.40). It is proved that in the studied intervals of variables, the yield of oligomers depends on the duration of the reaction (correlation 0.88). The color indicator of suspension oligomerization products at the studied intervals varies slightly and is 20–30 mg I2/100 ml.

The established optimal conditions make it possible to effectively use oil refining by-products by synthesizing light oligomers.

Under the established optimal conditions, the product yield is 22.7 % with oligomerization in solution and 19.4 % with suspension oligomerization.

Author Biographies

Roman Subtelnyy, Lviv Polytechnic National University

PhD, Associate Professor

Department of Organic Products Technology

Yevhenii Zhuravskyi, Lviv Polytechnic National University

Postgraduate Student

Department of Organic Products Technology

Dariia Kichura, Lviv Polytechnic National University

PhD, Associate Professor

Department of Organic Products Technology

Bohdan Dzinyak, Lviv Polytechnic National University

Doctor of Technical Sciences, Professor

Department of Organic Products Technology


  1. Rahmatpour, A., Ghasemi Meymandi, M. (2021). Large-Scale Production of C9 Aromatic Hydrocarbon Resin from the Cracked-Petroleum-Derived C9 Fraction: Chemistry, Scalability, and Techno-economic Analysis. Organic Process Research & Development, 25 (1), 120–135. doi: https://doi.org/10.1021/acs.oprd.0c00474
  2. Mildenberg, R., Zander, M., Collin, G. (1997). Hydrocarbon Resins. Wiley Online Library. doi: https://doi.org/10.1002/9783527614653
  3. Zohuriaan-Mehr, M. J., Omidian, H. (2000). Petroleum Resins: An Overview. Journal of Macromolecular Science, Part C: Polymer Reviews, 40 (1), 23–49. doi: https://doi.org/10.1081/mc-100100577
  4. Pyshyev, S., Gunka, V., Grytsenko, Y., Bratychak, M. (2016). Polymer Modified Bitumen: Review. Chemistry & Chemical Technology, 10 (4s), 631–636. doi: https://doi.org/10.23939/chcht10.04si.631
  5. Nie, X., Hou, T., Yao, H., Li, Z., Zhou, X., Li, C. (2019). Effect of C9 petroleum resins on improvement in compatibility and properties of SBS-modified asphalt. Petroleum Science and Technology, 37 (14), 1704–1712. doi: https://doi.org/10.1080/10916466.2019.1602642
  6. Salari, D., Jodaei, A. (2006). Petroleum resin preparation by cationic polymerization of pyrolysis gasoline. Iranian Polymer Journal (English Edition), 15 (1), 55–64.
  7. Gnativ, Z., Nylukyshyn, I., Pikh, Z., Voronchak, T. et. al. (2014). Catalytic Cooligomerization of Styrene and Dicyclopentadiene: Yield and Properties Dependence on Reaction Mixture Composition. Chemistry & Chemical Technology, 8 (2), 165–170. doi: https://doi.org/10.23939/chcht08.02.165
  8. Dzinyak, B. (2014). Cooligomerization of C9 Fraction Unsaturated Hydrocarbons Initiated by Organic Peroxides. Chemistry & Chemical Technology, 8 (2), 183–188. doi: https://doi.org/10.23939/chcht08.02.183
  9. Dzumedzei, M. V., Kucher, R. V., Turovskyi, A. A., Koshovskyi, B. I. (1971). Doslidzhennia kinetyky termichnoho rozpadu azotumisnykh perekysnykh spoluk z tret-alkilnym radykalom. Ukrainskiy khimicheskiy zhurnal, 39, 1142–1145.
  10. Turovskyi, A. A., Dzumudzei, M. V. (1973). Pro kinetyku peredachi lantsiuha cherez azotvmisni perekysy z tret-butylnym radykalom pry polimeryzatsiyi styrolu v masi. Dopovidi NAN Ukrainy, 5, 1106–1108.
  11. Voronchak, T., Nykulyshyn, I., Pikh, Z., Rypka, A. (2012). Synthesis and Properties of Epoxydized Cooligomers Obtained from Petroleum Resins Synthesized by Heterogeneous Catalytic Oligomerization. Chemistry & Chemical Technology, 6 (4), 397–403. doi: https://doi.org/10.23939/chcht06.04.397
  12. Fuch, U., Dzinyak, B., Subtelnyy, R. (2015). Study of emulsifier nature effect on the process of hydrocarbon fraction cooligomerization in the emulsion. Eastern-European Journal of Enterprise Technologies, 4 (6 (76), 54–57. doi: https://doi.org/10.15587/1729-4061.2015.47205
  13. Subtelnyy, R., Kichura, D., Dzinyak, B. (2021). Correlation between the emulsion oligomerization parameters for C9 fraction and the characteristics of hydrocarbon resins. Eastern-European Journal of Enterprise Technologies, 3 (6 (111)), 6–11. doi: https://doi.org/10.15587/1729-4061.2021.232684
  14. Kovačič, S., Slugovc, C. (2020). Ring-opening Metathesis Polymerisation derived poly(dicyclopentadiene) based materials. Materials Chemistry Frontiers, 4 (8), 2235–2255. doi: https://doi.org/10.1039/d0qm00296h
  15. Yao, Z., Xu, X., Dong, Y., Liu, X., Yuan, B., Wang, K. et. al. (2020). Kinetics on thermal dissociation and oligomerization of dicyclopentadiene in a high temperature & pressure microreactor. Chemical Engineering Science, 228, 115892. doi: https://doi.org/10.1016/j.ces.2020.115892




How to Cite

Subtelnyy, R., Zhuravskyi, Y., Kichura, D., & Dzinyak, B. (2022). Oligomerization of C9 hydrocarbon fraction initiated by amino peroxides with cyclic substitute . Eastern-European Journal of Enterprise Technologies, 3(6(117), 23–31. https://doi.org/10.15587/1729-4061.2022.259892



Technology organic and inorganic substances