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Journal of Applied Polymer Science, Vol.91, No.1, 1-9, 2004
Swelling of crosslinked polyacrylates in isotropic and anisotropic solvents
The purpose of this study was to examine the swelling and deswelling of photochemically crosslinked poly(n-butylacrylate) networks in isotropic and anisotropic solvents. The phase diagrams were established in terms of composition and temperature for five isotropic solvents, acetone, cyclohexane, methanol, tetrahydrofuran, and toluene, and two low-molecular-weight nematic liquid crystals, 4-cyano-4'-n-pentyl-biphenyl and an eutectic mixture of cyanoparaphenylenes. Networks were formed by ultraviolet curing in the presence of 0.5 wt % difunctional monomer (hexane diol-di-acrylate) and 0.5 wt % photoinitiator (Darocur 1173). Immersion in excess solvent allowed us to measure the solvent uptake by weight and to determine the size increase by optical microscopy in terms of temperature. We calculated weight and diameter ratios considering the swollen-to-dry network states of the samples. Phase diagrams were analyzed with the phantom network model according to the Flory-Rehner theory of rubber elasticity, and for the anisotropic solvents, modeling was supplemented with the Maier-Saupe theory of nematic order for free energy. The polymer-solvent interaction parameter was deduced as a function of temperature, but the values were in discrepancy with Fedors's model of solubility parameters, which overestimated the interaction. (C) 2003 Wiley Periodicals, Inc.