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A Combined Computational and Experimental Study on the Free‐Radical Copolymerization of Styrene and Hydroxyethyl Acrylate
Author(s) -
Mavroudakis Evangelos,
Liang Kun,
Moscatelli Davide,
Hutchinson Robin A.
Publication year - 2012
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201200165
Subject(s) - copolymer , acrylate , polymer chemistry , intermolecular force , monomer , intramolecular force , reactivity (psychology) , styrene , arrhenius equation , radical polymerization , polymerization , chemistry , materials science , molecule , organic chemistry , polymer , medicine , activation energy , alternative medicine , pathology
Bulk free‐radical copolymerization of styrene and 2‐hydroxyethyl acrylate (HEA) is investigated experimentally at 50 °C using pulsed‐laser polymerization and computationally using ab initio simulations. Arrhenius parameters for HEA chain‐end homopropagation are A = 1.72 × 10 7 L mol −1 s −1 and E a = 16.8 kJ mol −1 , based on experiments between 20 and 60 °C. Copolymer composition data are well fitted by the terminal model with reactivity ratios r ST = 0.44 ± 0.03 and r HEA = 0.18 ± 0.04, but the variation in the propagation rate coefficient with monomer composition is underpredicted. Results are compared with computational predictions assuming the terminal as well as the penultimate unit effect (PUE) model. Intramolecular H‐bonding is shown to have a significant influence on PUE calculations. Discrepancies between computational predictions and experiment are attributed to the influence of intermolecular H‐bonding.