Petroleum ChemistryPetroleum ChemistryНефтехимия0028-24213034-5626The Russian Academy of Sciences65561710.31857/S0028242123030103JCIADOArticlesСтатьиResearch ArticlePromising Applications of Polyethyleneimine as a Ligand in Rhodium-Catalyzed Tandem Hydroformylation/Hydrogenation of OlefinsПерспективы применения полиэтиленимина в качестве лиганда в родий-катализируемом тандемном гидроформилировании-гидрировании олефиновGorbunovD. N.ГорбуновД. Н.gorbunovdn@petrol.chem.msu.ruNenashevaM. V.НенашеваМ. В.petrochem@ips.ac.ruKuvandykovaE. A.КувандыковаЕ. А.petrochem@ips.ac.ruKardashevS. V.КардашевС. В.petrochem@ips.ac.ruKarakhanovE. A.КарахановЭ. А.petrochem@ips.ac.ruFaculty of Chemistry, Lomonosov Moscow State UniversityМосковский государственный университет имени М.В. Ломоносова15062023633NO3 (2023)№3 (2023)40141511022025Copyright ©; 2023, Russian Academy of SciencesCopyright ©; 2023, Российская академия наук2023Russian Academy of SciencesРоссийская академия наукhttps://journals.eco-vector.com/0028-2421/article/view/655617

Three rhodium-containing catalytic systems active in tandem hydroformylation/hydrogenation of unsaturated substrates were developed based on polyethyleneimine (PEI): a homogeneous system with distillation of the product; a biphasic system with segregation of the product and catalyst into a non-polar phase and a polar phase, respectively; and a solid catalyst prepared from PEI and (3-chloropropyl)triethoxysilane with its centrifugation from the product mixture. All the systems were shown to be reusable over multiple cycles in hydroformylation/hydrogenation, with the catalytic activity being partially sustained in both steps of the tandem process. Methylation of PEI (or its NH and NH2 moieties in the case of solid material) was found to be critical for the catalytic activity in hydroformylation.

Разработаны три родиевые каталитические системы на основе полиэтиленимина (ПЭИ, PEI), активные в тандемном гидроформилировании-гидрировании непредельных субстратов: гомогенная система с дистилляционным отделением продукта; двухфазная система с распределением продукта и катализатора в неполярную и полярную фазы соответственно; твердый катализатор, полученный из ПЭИ и (3-хлорпропил)триэтоксисилана, отделяемый от смеси продуктов центрифугированием. Для всех систем показана возможность многократного использования в гидроформилировании-гидрировании с частичным сохранением активности в обеих стадиях тандемного процесса. Установлена важная роль метилирования ПЭИ (или его NH- и NH2-фрагментов в твердом материале) для обеспечения активности систем в гидроформилировании.

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