Catalytic Oxidative Deformylation of Polyethylene Glycols with the Participation of Molecular Oxygen Научная публикация
| Журнал |
Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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| Вых. Данные | Год: 2001, Том: 42, Номер: 5, Страницы: 662-668 Страниц : 7 DOI: 10.1023/A:1012371630951 | ||
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Реферат:
The kinetics of oxidation of diethylene glycol, triethylene glycol, and polyethylene glycols (PEGs) with molecular weights ranging from 400 to 2000 in the presence of Cu(II) ions and bases was studied. It was found that ethylene glycols can be oxidized by molecular oxygen in anhydrous media in a temperature range of 30-60 degreesC at anomalouosly high rates which are higher than the rates of chain-radical PEG autoxidation by several orders of magnitude. Only terminal hydroxyl groups were subjected to oxidation. The reaction occurs with the cleavage of a C-C bond and results in the formation of formic acid and a PEG with the number of -(CH2CH2O)- groups lower than that in the parent compound by unity. The rate and selectivity of PEG oxidation were found to strongly depend on the molecular weight of the polymer; from diethylene glycol to PEG 2000, the specific rate of oxidation increased by a factor of 60 in terms of terminal hydroxyl groups. An oxidation mechanism was suggested, which involves the formation of ternary complexes [Cu2+...A(-)...O-2], which undergo further degradation by a many-electron concerted mechanism to form formic acid and. probably, an unstable hemiacetal {RO-CH2OH}. The rapid oxidative degradation of the latter leads to the formation of PEG with a lower molecular weight.
Библиографическая ссылка:
Sakharov A.M.
, Mazaletskaya L.I.
, Skibida I.P.
Catalytic Oxidative Deformylation of Polyethylene Glycols with the Participation of Molecular Oxygen
Kinetics and Catalysis. 2001. V.42. N5. P.662-668. DOI: 10.1023/A:1012371630951 WOS Scopus РИНЦ CAPlus OpenAlex
Catalytic Oxidative Deformylation of Polyethylene Glycols with the Participation of Molecular Oxygen
Kinetics and Catalysis. 2001. V.42. N5. P.662-668. DOI: 10.1023/A:1012371630951 WOS Scopus РИНЦ CAPlus OpenAlex
Оригинальная версия:
Сахаров А.М.
, Мазалецкая Л.И.
, Скибида И.П.
Окислительное каталитическое деформилирование полиэтиленгликолей с участием молекулярного кислорода
Кинетика и катализ. 2001. Т.42. №5. С.730-736. РЖ ВИНИТИ
Окислительное каталитическое деформилирование полиэтиленгликолей с участием молекулярного кислорода
Кинетика и катализ. 2001. Т.42. №5. С.730-736. РЖ ВИНИТИ
Даты:
| Поступила в редакцию: | 11 янв. 2000 г. |
| Опубликована в печати: | 1 сент. 2001 г. |
Идентификаторы БД:
| Web of science: | WOS:000171974100012 |
| Scopus: | 2-s2.0-0037563755 |
| РИНЦ: | 13376458 |
| Chemical Abstracts: | 2001:815699 |
| OpenAlex: | W150261488 |