Light Scattering from Random Coils Dispersed in Solutions of Rodlike Polymers

Document Type

Article

Publication Date

1-1-1994

Abstract

The thermodynamics and mobility of a random-coil polymer were studied by light scattering in toluene solutions containing a rodlike polymer. The random-coil polymer was polystyrene (PS). The rodlike polymer was helical poly(γ-stearyl α,L-glutamate), or PSLG, which aggregates end-to-end in toluene to produce long filaments. As PSLG is almost isorefractive with toluene, the scattering of PS can be measured in PSLG/toluene mixtures with almost no interference from PSLG. The apparent second virial coefficient of the PS component decreases rapidly with addition of the “invisible” rodlike polymer component, while the PS radius of gyration does not. A θ condition is reached at slightly more than 1 % added PSLG. Although PSLG and PS probably have a disfavorable interaction parameter, enthalpic interactions are of secondary importance. This point was underscored by experiments involving the addition of 5% dodecane to binary PS/toluene solutions; the small, aliphatic solvent had virtually no effect. The reduction of the virial coefficient, but not the size, of the random-coil polymer in the presence of PSLG is due to the occupation of connected (and linearly correlated) space. Parallel effects were observed in the mutual diffusion coefficient of the coil component, which increased with PS concentration at low rod content but did the opposite when enough PSLG was added. Extrapolated to zero PS content, the mutual diffusion coefficient is expected to approach closely the self-diffusion of trace quantities of PS in the PSLG/toluene solution. So obtained, the self-diffusion coefficient decreased with added rodlike PSLG, but not as fast as the viscosity increased; thus, the Stokes-Einstein relationship was not obeyed by PS probes in PSLG/toluene solutions. Scaling arguments are presented for the dependence of the size of a random coil in the presence of rods and for the crossover from Stokes-Einstein diffusion of the coil to a reptative type of motion. The available data are not well suited to test these relationships, due to limitations in the matrix concentration imposed by polymer incompatibility. © 1994, American Chemical Society. All rights reserved.

Publication Source (Journal or Book title)

Macromolecules

First Page

171

Last Page

178

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