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Mechanistic study of transesterification in TBD-catalyzed ring-opening polymerization of methyl ethylene phosphateстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Nifant'ev Ilya E., Shlyakhtin Andrey V., Tavtorkin Alexander N., Kosarev Maxim A., Gavrilov Dmitry E., Komarov Pavel D., Ilyin Sergey O., Karchevsky Stanislav G., Ivchenko Pavel V.
- Журнал: European Polymer Journal
- Год издания: 2019
- Издательство: Pergamon Press Ltd.
- Местоположение издательства: United Kingdom
- DOI: 10.1016/j.eurpolymj.2019.06.015
- Аннотация: It is well known that ring-opening polymerization (ROP) of sterically unhindered cyclic ethylene phosphates, initiated by both organocatalysts and coordination catalysts, is accompanied by transesterification (TE) even at subzero temperatures. To clarify this phenomenon from the mechanistic point of view, we calculated (DFT, B3PW91/DGTZVP) the reaction profiles of the ROP for 2-methoxy-1,3,2-dioxaphospholane-2-oxide (methyl ethylene phosphate, MeOEP) and of the transesterification processes for poly(MeOEP) and trimethyl phosphate (TMP) in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) organocatalyst. We found that the free activation energy of TE is substantially higher (10–13 kcal/mol) than the ROP activation barrier. To verify the calculation results, we investigated the chemical behavior of low molecular weight trimethyl phosphate (TMP) in the TBDcatalyzed polymerization of MeOEP. We demonstrated that TMP was not affected by transesterification, which correlates with the calculation results.
- Добавил в систему: Нифантьев Илья Эдуардович