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Practical procedure for a theoretical investigation of thermodynamics and kinetics aspects of different-scale radical reactions from addition and cyclization to cyclocopolymerization involving maleic anhydride and divinyl etherстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 27 октября 2021 г.
- Авторы: Bolshchikov Boris D., Tsvetkov Vladimir B., Serbin Alexander V.
- Журнал: Polymer
- Том: 146
- Год издания: 2018
- Издательство: Elsevier BV
- Местоположение издательства: Netherlands
- Первая страница: 429
- Последняя страница: 445
- DOI: 10.1016/j.polymer.2018.05.032
- Аннотация: Quantum chemical techniques reasonable in practical simulation of carbon-centered radical reactions were evaluated scaling up from addition and cyclization of small radicals to growing chains in homo-, cross- and cyclo-polymerization. The methods preselected via “cost – deviation from experiment” criteria were explored relative to growing molecular systems of radical cyclocopolymerization between divinyl ether and maleic anhydride: alternating cross-propagation with cyclization and side homopolymerization reactions. The following methods were found to be optimal for estimation of activation barriers and thermodynamics parameters: DFT M06-2X with 6-311+G(d) and 6-311+G (2df,p) basis sets or ONIOM M06-2X/6-311+G(d):B3LYP/6-31G(d) – for more complex systems. Spin-restricted open shell calculations by ROMP2/6-311+G (3df, 2p) have shown unfeasible increase in computational costs retaining similar accuracy. The optimal techniques facilitated new mechanistic insights into regulating the polymerization including kinetic-thermodynamic control factors for regulation of furan-/pyran-related isomerism within the chain that is essential for tailoring functionality of the derivatives. The approach builds methodology basis for research of similar macromolecular systems including alike polymeric platforms for preparations of broad biomedical applications.
- Добавил в систему: Tsvetkov Vladimir Borisovich