Kinetic Model and Mechanism of Heterogeneous Hydrogenation of Strained Polycyclic Compounds Derived from 5-Vinyl-2-norbornene

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

The main pathways of liquid-phase hydrogenation of 5-ethenylbicyclo[2.2.1]hept-2-ene (5-vinyl-2-norbornene, VNE) in the presence of PK-25 palladium catalyst (Pd/γ-Al2O3, 0.25% Pd) were studied. All the reaction products were identified, and the material balance was examined. The effect of the prevalent adsorption of the norbornene double bond on the Pd active site (AS) was confirmed. The parallel-consecutive scheme of the process mechanism, based on the set of experimental and theoretical data, was suggested. It involves the successive substrate hydrogenation and significant role of the isomerization of the vinyl group into the ethylidene group in intermediates on AS in a hydrogen atmosphere. The reaction is zero-order in a wide interval of initial VNE concentrations. An adequate kinetic model of the process, based on the Langmuir–Hinshelwood approach and the concept of multiple adsorption of substrates on one AS, was developed. Five steps, including two parallel steps, significantly contribute to the reaction rate. Their rate constants and the adsorption constants of AS complexes with unsaturated compounds were estimated.

About the authors

V. V Zamalyutin

Russian University of Technology, Lomonosov Institute of Fine Chemical Technologies

Email: zamalyutin@mail.ru
119571, Moscow, Russia

E. A. Katsman

Russian University of Technology, Lomonosov Institute of Fine Chemical Technologies

Email: petrochem@ips.ac.ru
119571, Moscow, Russia

V. R. Flid

Russian University of Technology, Lomonosov Institute of Fine Chemical Technologies

Author for correspondence.
Email: vitaly-flid@yandex.ru
119571, Moscow, Russia

References

  1. Cai Y., Zheng J., Hu Y., Wei J., Fan H. The preparation of polyolefin elastomer functionalized with polysiloxane and its effect in ethylene-propylene-diene monomer/silicon rubber blends // Eur. Polym. J. 2022. V. 177. P. 111468. https://doi.org/10.1016/j.eurpolymj.2022.111468
  2. Fein K., Bousfield D.W., Gramlich W.M. Thiol-norbornene reactions to improve natural rubber dispersion in cellulose nanofiber coatings // Carbohyd. Polym. 2020. V. 250. P. 117001. https://doi.org/10.1016/j.carbpol.2020.117001
  3. Ravishankar P.S. Treatise on EPDM // Rubber Chem. Technol. 2012. V. 85. P. 327-349. https://doi.org/10.5254/rct.12.87993
  4. Флид В.Р., Грингольц М.Л., Шамсиев Р.С., Финкельштейн Е.Ш. Норборнен, норборнадиен и их производные - перспективные полупродукты для органического синтеза и получения полимерных материалов // Усп. хим. 2018. Т. 87. С. 1169-1205 https://doi.org/10.1070/RCR4834
  5. Flid V.R., Gringolts M.L., Shamsiev R.S., Finkelshtein E.Sh. Norbornene, norbornadiene and their derivatives: promising semi-products for organic synthesis and production of polymeric materials // Russ. Chem. Rev. 2018. V. 87. P. 1169-1205. https://doi.org/10.1070/RCR4834.
  6. Kong P., Drechsler S., Balog S., Schrettl S., Weder C., Kilbinger A.F.M. Synthesis and properties of poly(norbornene)s with lateral aramid groups // Polym. Chem. 2019. V. 10. P. 2057-2063. https://doi.org/10.1039/C9PY00187E
  7. Roenko A.V., Nikiforov R.Y., Gringolts M.L., Belov N.A., Denisova Y.I., Shandryuk G.A., Bondarenko G.N., Kudryavtsev Y.V., Finkelshtein E.S. Olefin-metathesis-derived norbornene-ethylene-vinyl acetate/vinyl alcohol multiblock copolymers: impact of the copolymer structure on the gas permeation properties // Polymers. 2022. V. 14. P. 444. https://doi.org/10.3390/polym14030444
  8. Thomas J., Bouscher R.F., Nwosu J., Soucek M.D. Sustainable thermosets and composites based on the epoxides of norbornylized seed oils and biomass fillers // ACS Sustainable Chem. Eng. 2022. V. 10. P. 12342-12354. https://doi.org/10.1021/acssuschemeng.2c03434
  9. Belov N.A., Gringolts, M.L., Morontsev A.A. Starannikova L.E., Yampolskii Yu.P., Finkelstein E.Sh. Gas-transport properties of epoxidated metathesis polynorbornenes // Polym. Sci. Ser. B. 2017. V. 59. P. 560-569. https://doi.org/10.1134/S1560090417050025
  10. Vintila I.S., Iovu H., Alcea A., Cucuruz A., Mandoc A.C., Vasile B.S. The synthetization and analysis of dicyclopentadiene and ethylidene-norbornene microcapsule systems // Polymers. 2020. V. 12. P. 1052. https://doi.org/10.3390/polym12051052
  11. Morontsev A.A., Denisova Yu.I., Gringolts M.L., Filatova M.P., Shandryuk G.A., Finkelshtein E.Sh., Kudryavtsev Ya.V. Epoxidation of multiblock copolymers of norbornene and cyclooctene // Polym. Sci. Ser. B. 2018. V. 60. P. 688-698. https://doi.org/10.1134/S1560090418050111
  12. Li G., Shen R., Hu Sh., Wang B., Algadi H., Wang Ch. Norbornene-based acid-base blended polymer membranes with low ion exchange capacity for proton exchange membrane fuel cell // Adv. Compos Hybrid Mater. 2022. V. 5. P. 2131-2137. https://doi.org/10.1007/s42114-022-00559-3
  13. Le D., Samart Ch., Lee J.-T., Nomura K., Kongparakul S., Kiatkamjornwong S. Norbornene-functionalized plant oils for biobased thermoset films and binders of silicon-graphite composite electrodes // ACS Omega. 2020. V. 5. P. 29678-29687. https://doi.org/10.1021/acsomega.0c02645
  14. Sparaco R., Kędzierska E., Kaczor A.A., Bielenica A., Magli E., Severino B., Corvino A., Gibuła-Tarłowska E., Kotlińska J.H., Andreozzi G., Luciano P., Perissutti E., Frecentese F., Casertano M., Leśniak A., Bujalska-Zadrożny M., Oziębło M., Capasso R, Santagada V., Caliendo G. Fiorino F. Synthesis, docking studies and pharmacological evaluation of serotoninergic ligands containing a 5-norbornene-2-carboxamide nucleus // Molecules. 2022. V. 27. P. 6492. https://doi.org/10.3390/molecules27196492
  15. Çapan İ., Servi S., Dalkiliç S., Dalkiliç L.K. Synthesis and anticancer evaluation of benzimidazole derivatives having norbornene/dibenzobarrelene skeletons and different functional groups // ChemistrySelect. 2020. V. 5. P. 14393-14398. https://doi.org/10.1002/slct.202004034
  16. Fiorino F., Perissutti E., Severino B., Santagada V., Cirillo D., Terracciano S., Massarelli P., Bruni G., Collavoli E., Renner C., Caliendo G. New 5-hydroxytryptamine(1А) receptor ligands containing a norbornene nucleus: synthesis and in vitro pharmacological evaluation // J. Med. Chem. 2005. V. 48. № 17. P. 5495-5503. https://doi.org/10.1021/jm050246k
  17. Rao V.N., Mane S.R., Abhinoy K., Sarma J.D., Shunmugam R. Norbornene derived doxorubicin copolymers as drug carriers with pH responsive hydrazone linker // Biomacromolecules. 2012. V. 13. № 1. P. 221-230. https://doi.org/10.1021/bm201478k
  18. Ulla B. S., Binderup M.-L., Bolognesi C., Brimer L., Castle L., Di Domenico A., Engel K.-H., Franz R., Gontard N., Gürtler R., Husøy T., Jany K.-D., Kolf-Clauw M., Leclercq C., Lhuguenot J.-C., Mennes W., Milana M. R., Poças M. de F., Pratt I., Svensson K., Toldrá F., Wölfle D. Scientific оpinion on the safety assessment of the substance, 5-norbornene-2,3dicarboxylic anhydride, CAS No 826-62-0, for use in food contact materials // EFSA J. 2014. V. 12. № 6. P. 3714. https://doi.org/10.2903/j.efsa.2014.3714
  19. Shorunov S.V., Piskunova E.S., Petrov V.A., Bykov V.I., Bermeshev M.V. Selective hydrogenation of 5-vinyl-2-norbornene to 2-vinylnorbornane // Petrol. Chemistry. 2018. V. 58. P. 1056-1063. https://doi.org/10.1134/S0965544118120125
  20. Шорунов С.В., Пискунова Е.С., Петров В.А., Быков В.И., Бермешев М.В. Селективное гидрирование 5-винил-2-норборнена до 2-винилнорборнана // Нефтехимия. 2018. Т. 58. С. 712-719. https://doi.org/10.1134/S0028242118060126.
  21. Shorunov S.V., Zarezin D.P., Samoilov V.O., Rudakova M.A., Borisov R.S., Maximov A.L., Bermeshev M.V. Synthesis and properties of high-energy-density hydrocarbons based on 5-vinyl-2-norbornene // Fuel. 2021. V. 283. P. 118935. https://doi.org/10.1016/j.fuel.2020.118935.
  22. Zamalyutin V.V., Ryabov A.V., Nichugovskii A.I., Skryabina A.Yu., Tkachenko O.Yu., Flid V.R. Regularities of the heterogeneous catalytic hydrogenation of 5-vinyl-2-norbornene // Russ. Chem. Bull. 2022. V. 71. P. 70-75
  23. Замалютин В.В., Рябов А.В., Ничуговский А.И., Скрябина А.Ю., Ткаченко О.Ю., Флид В.Р. Особенности гетерогенно-каталитического гидрирования 5-винил-2-норборнена // Изв. АН. Сер. хим. 2022. С. 70-75. https://doi.org/10.1007/s11172-022-3378-5.
  24. Zamalyutin V.V., Ryabov A.V., Solomakha E.A., Katsman E.A., Flid V.R., Tkachenko O.Yu., Shpinyova M.A. Liquid-phase heterogeneous hydrogenation of dicyclopentadiene // Russ. Chem. Bull. 2022. V. 71. P. 1204-1208
  25. Замалютин В.В., Рябов А.В., Соломаха Е.А., Кацман Е.А., Флид В.Р., Ткаченко О.Ю., Шпынева М.А. Жидкофазное гетерогенное гидрирование дициклопентадиена // Изв. АН. Сер. хим. 2022. Т. 71. С. 1204-1208. https://doi.org/10.1007/s11172-022-3521-3.
  26. Zamalyutin V.V., Shamsiev R.S., Flid V.R. Mechanism of catalytic migration of the double bond in 2-vinylnorbonanes // Russ. Chem. Bull. 2022. P. 2142-2148
  27. Замалютин В.В., Шамсиев Р.С., Флид В.Р. Механизм каталитической миграции двойной связи в 2-винилнорборнанах // Изв. АН. Сер. хим. 2022. № 10. С. 2142-2148.
  28. Zamalyutin V.V., Katsman E.A., Danyushevsky V.Y., Flid V.R., Podol'skii V.V., Ryabov A.V. Specific features of the catalytic hydrogenation of the norbornadiene-based carbocyclic compounds // Russ. J. Coord. Chem. 2021. V. 47. № 10. P. 695-701
  29. Замалютин В.В., Кацман Е А., Данюшевский В.Я., Флид В.Р., Подольский В.В., Рябов А.В. Особенности каталитического гидрирования карбоциклических соединений на основе норборнадиена // Коорд. химия. 2021. Т. 47. С. 628-634. https://doi.org/10.31857/S0132344X21100091.
  30. Zamalyutin V.V., Katsman E.A., Ryabov A.V., Skryabina A.Y., Shpinyova M.A., Danyushevsky V.Y., Flid V.R. Kinetic model and mechanism of hydrogenation of unsaturated carbocyclic compounds based on norbornadiene // Kinet. Catal. 2022. V. 63. № 2. P. 234-242
  31. Замалютин В.В., Кацман Е.А., Рябов А.В., Скрябина А.Ю., Шпынева М.А., Данюшевский В.Я., Флид В.Р. Кинетическая модель и механизм гидрирования ненасыщенных карбоциклических соединений на основе норборнадиена // Кинетика и катализ. 2022. Т. 63. №2. С. 267-276. https://doi.org/10.31857/S0453881122020150.
  32. Осокин Ю.Г., Михайлов В.А., Зубович И.А., Фельдблюм В.Ш. // Доклады АН СССР. 1975. Т. 220. № 4. С. 851-853.
  33. Bermeshev M.V., Pozharskaya N.A., Antonova T.N., Shangareev D.R., Danilova A.S. Selective catalytic hydrogenation of alicyclic dienes with hydrogen in a liquid phase // Petrol. Chemistry. 2018. V. 58. № 10. P. 869-875. https://doi.org/10.1134/S0028242118050039
  34. Бермешев М.В., Антонова Т.Н., Шангареев Д.Р., Данилова А.С., Пожарская Н.А. // Нефтехимия. 2018. Т. 58. С. 580-587.
  35. Ushakov N.V. Selective hydrogenation of 5-vinylnorborn-2-ene and other methods for the synthesis of 2-vinylnorbornane // Russ. J. Appl. Chem. 2018. V. 91. P. 728-745. https://doi.org/10.1134/S1070427218050026
  36. Ушаков Н.В. Селективное гидрирование 5-винилнорборн-2-ена и другие методы синтеза 2-винилнорборнана (обзор) // Журн. прикл. химии. 2018. Т. 91. №5. С. 631-650.
  37. Vereshchagina N.V., Antonova T.N., Il'In A.A., Chirkova Z.V. Feature of dicyclopentene formation during hydrogenation of dicyclopentadiene // Petrol. Chemistry. 2016. V. 56. № 1. P. 38-43. https://doi.org/10.1134/S0965544115080198
  38. Верещагина Н.В., Антонова Т.Н., Ильин А.А., Чиркова Ж.В. Закономерности образования дициклопентена в процессе гидрирования дициклопентадиена // Нефтехимия. 2016. Т. 56. № 1. С. 46-51. https://doi.org/10.7868/S0028242115060192.
  39. Куттубаев С.Н., Рахимов М.Н., Павлов М.Л., Басимова Р.А., Кутепов Б.И. Исследование эффективности очистки этан-этиленовой фракции пиролиза от ацетиленовых соединений на различных катализаторах // Нефтегазовое дело. 2012. № 4. С. 165-178.
  40. Urmès С., Schweitzer J.-M., Cabiac A., Schuurman Y. Kinetic study of the selective hydrogenation of acetylene over supported palladium under tail-end conditions // Catalysts. 2019. V. 9. P. 180. https://doi.org/10.3390/catal9020180.
  41. Molero H., Bartlett B.F., Tysoe W.T. The hydrogenation of acetylene catalyzed by palladium: hydrogen pressure dependence // J. Catal. 1999. V. 181. P. 49-56.
  42. Borodzinski A., Bond G.C. selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts, Part 2: Steady-state kinetics and effects of palladium particle size, carbon monoxide, and promoters // Catal. Rev. 2008. V. 50. P. 379-469. https://doi.org/10.1080/01614940802142102
  43. Al-Wadhaf H.A., Karpov V.M., Katsman E.A. Activity and selectivity of carbon supported palladium catalysts prepared from bis(η3-allyl)palladium complexes in phenylacetylene hydrogenation // Catal. Commun. 2018. V. 116. P. 67-71. https://doi.org/10.1016/j.catcom.2018.08.010.
  44. Berenblyum A.S., Katsman E.A., Al-Wadhaf H.A. Supported palladium nanomaterials as catalysts for petroleum chemistry: 2. Kinetics and specific features of the mechanism of selective hydrogenation of phenylacetylene in the presence of carbon-supported palladium nanocatalysts // Petrol. Chemistry. 2015. V. 55. № 2. P. 118-126. https://doi.org/10.1134/S0965544115020048
  45. Беренблюм А.С., АльВадхав Х.А., Кацман Е.А. Нанесенные палладиевые наноматериалы как катализаторы для нефтехимии: 2. Кинетика и особенности механизма селективного гидрирования фенилацетилена в присутствии палладиевого нанокатализатора на угле // Нефтехимия. 2015. Т. 55. № 2. C. 125-133.

Supplementary files

Supplementary Files
Action
1. JATS XML
Download

Copyright (c) 2023 Russian Academy of Sciences