Journal article
Theoretical Study of Intermolecular Chain Transfer to Polymer Reactions of Alkyl Acrylates
Industrial & engineering chemistry research, v 54(16), pp 4148-4165
29 Apr 2015
Abstract
Mechanisms Of intermolecular chain transfer to polymer (CTP) reactiOns in Trionoiner self-initiated polymerization of alkyl acrylates, such as methyl acrylate, ethyl acrYlate, and tz-butyl acrylate, are studied using density functional theory calculations. Dead polymer chains with three different structure S are considered, and three types of hybrid density functionals and four basis sets are used. The energy barrier and rate constant of each reaction are calculated using the transition state theory and the rigid rotor harmonic oscillator approximation. The study indicates, that tertiary hydrogens of dead polymers formed by disproportionation reactions are most likely to be transferred to live polYmer chains, in CTP reactions. The length of the polymer chain has little effect on the calculated activation energies and transition-state geometries in all CTP mechanisms explored in this study. Moreover, CTP reactions of methyl, ethyl, and butyl acrylates have similar energy barriers and rate constants. The application of the integral equation formalism-polarizable continuum model results in higher CTP energy barriers. This increase in-the predicted CTP energy barriers is larger in ri-butanol.thari in p-xylene. However, the application of the conductor-like screening model does not affect the predicted CTP kinetic parameters.
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Details
- Title
- Theoretical Study of Intermolecular Chain Transfer to Polymer Reactions of Alkyl Acrylates
- Creators
- Nazanin Moghadam - Drexel UniversityShi Liu - University of PennsylvaniaSriraj Srinivasan - Arkema Inc., 900 First Avenue, King of#R#Prussia, Pennsylvania 19406, United StatesMichael C. Grady - Wilmington UniversityAndrew M. Rappe - University of PennsylvaniaMasoud Soroush - Drexel University
- Publication Details
- Industrial & engineering chemistry research, v 54(16), pp 4148-4165
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 18
- Grant note
- CBET-1160169; CBET-1159736 / National Science Foundation; National Science Foundation (NSF) DE-FG02-07ER15920 / Department of Energy Office of Basic Energy Sciences; United States Department of Energy (DOE) 1159736 / Div Of Chem, Bioeng, Env, & Transp Sys; National Science Foundation (NSF); NSF - Directorate for Engineering (ENG)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemical and Biological Engineering
- Web of Science ID
- WOS:000353931200017
- Scopus ID
- 2-s2.0-84929486184
- Other Identifier
- 991019168604904721
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- Collaboration types
- Industry collaboration
- Domestic collaboration
- Web of Science research areas
- Engineering, Chemical