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Kinetic Study of 1,5‐Hydrogen Transfer Reactions of Methyl Acrylate and Butyl Acrylate Using Quantum Chemistry
Author(s) -
Yu Xinrui,
Broadbelt Linda J.
Publication year - 2012
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.201200005
Subject(s) - methyl acrylate , chemistry , hydrogen atom abstraction , radical , acrylate , hydrogen atom , quantum chemistry , atom transfer radical polymerization , polymerization , computational chemistry , kinetic energy , transition state , quantum chemical , transition state theory , polymer chemistry , photochemistry , polymer , molecule , kinetics , organic chemistry , reaction rate constant , monomer , alkyl , physics , quantum mechanics , catalysis , supramolecular chemistry
1,5‐Hydrogen transfer reactions in methyl acrylate and butyl acrylate free‐radical polymerization are studied using quantum chemistry and transition state theory to estimate the kinetic parameters ( k tr , E a , and A ) with tetrameric radicals, requiring a number of atoms that ranks among the largest polymeric mimics to date. A two‐step transformation accounted for the overall reaction: rotation from an extended conformation to a coiled conformation and abstraction of the fifth hydrogen atom by the end‐chain radical. UB3LYP/6‐31G(d) was used for geometry optimization, validation of the transition states, and calculation of frequencies that were used to obtain thermodynamic properties. The more computationally demanding level of theory, MPWB1K/6‐31G(d,p), was used for calculation of the electronic energy.