Ketonization of a Nitrile-Butadiene Rubber by Nitrous Oxide: Comparison with the Ketonization of Other Type Diene rubbers
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
European Polymer Journal
ISSN: 0014-3057
, E-ISSN: 1873-1945
|
| Вых. Данные |
Год: 2009,
Том: 45,
Номер: 12,
Страницы: 3355-3362
Страниц
: 8
DOI:
10.1016/j.eurpolymj.2009.10.007
|
| Ключевые слова |
Diene rubbers, Functional oligomers, Functional polymers, N2O, Nitrile-butadiene rubber, Polyketones |
| Авторы |
Semikolenov Sergey V.
1
,
Dubkov Konstantin A.
1
,
Ivanov Dmitry P.
1
,
Babushkin Dmitry E.
1
,
Matsko Mikhail A.
1
,
Panov Gennady I.
1
|
| Организации |
| 1 |
Институт катализа им. Г.К. Борескова СО РАН
|
|
Noncatalytic ketonization of a nitrile-butadiene rubber (21 mol% acrylonitrile units) by nitrous oxide was shown to yield polymeric products functionalized with carbonyl (mainly ketone) groups. The reaction was conducted in a benzene solvent at 180–230° and pressure of 3–6 MPa. An assumed ketonization mechanism includes a 1,3-dipolar cycloaddition of N2O to Cdouble bond; length as m-dashC bonds in butadiene units.
According to the NMR and GPC data, the main route of the reaction (ca. 85%) proceeds without cleavage of the Cdouble bond; length as m-dashC bonds and yields ketone groups in the polymer backbone. The minor route (ca. 15%) includes the cleavage of Cdouble bond; length as m-dashC bonds resulting in fragmentation of the macromolecules that leads to a decrease in their molecular weight. The nitrile (–CN) groups remain untouched. The resulting product is a bifunctional low-molecular rubber containing, in addition to originally present nitrile groups, a regulated amount of new ketone groups randomly distributed along the polymer backbone.
The results for nitrile-butadiene rubber are compared with the earlier studied ketonization of butadiene and isoprene rubbers. The molecular structure of monomeric units was shown to be an important characteristic of a parent rubber affecting the reaction rate, degree of fragmentation, and consistency (rubber-like, plastic, or liquid) of the resulting material.