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Prediction of Hildebrand solubility parameters of acrylate and methacrylate monomers and their mixtures by molecular simulation
Author(s) -
Lewin John L.,
Maerzke Katie A.,
Schultz Nathan E.,
Ross Richard B.,
Siepmann J. Ilja
Publication year - 2009
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.31232
Subject(s) - hildebrand solubility parameter , acrylate , methacrylate , solubility , upper critical solution temperature , polymer chemistry , chemistry , monomer , thermodynamics , virial coefficient , methacrylic acid , flory–huggins solution theory , materials science , organic chemistry , polymer , lower critical solution temperature , copolymer , physics
Hildebrand solubility parameters are predicted from molecular simulations using the transferable potentials for phase equilibrium‐united atom (TraPPE‐UA) and Dreiding force fields for the n ‐alkyl acrylate and methacrylate esters ( n ≤ 10), as well as the 2‐ethylhexyl acrylate, 2‐hydroxyethyl acrylate, isooctyl esters of acrylic acid, and the 2‐hydroxyethyl ester of methacrylic acid. The TraPPE‐UA force field yields very accurate solubility parameters (with a mean unsigned percent error of 2% or 0.2 Hildebrand units), whereas the Dreiding force field overpredicts the solubility parameter in every case examined. Correlations based on the normal boiling point or the refractive index do not yield satisfactory results for this monomer set with the former overestimating the magnitude and the latter yielding the incorrect sign for the decrease in the solubility parameter with chain length. Simulations with the TraPPE‐UA force field yield solubility parameters for binary mixtures of methyl methacrylate with 2‐ethylhexyl or isooctyl acrylate, which are very well described by a linear interpolation using the pure compound cohesive energies and molar volumes, whereas those for mixtures with 2‐hydroxyethyl acrylate or methacrylate small positive deviations due to structural microheterogeneity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010