We perform molecular dynamics (MD) simulations of a coarse-grained model of linear low-density polyethylenes (LLDPEs) having short-chain branching in an implicit solvent and calculate basic configurational properties (radius of gyration R_g, hydrodynamic radius R_h, and intrinsic viscosity [η]) using the path-integration program ZENO. Solvent quality effects in our model are accounted for through the introduction of an attractive polymer-polymer interaction potential with solvent quality "strength" λ that is tuned from a "good" solvent limit, where the inter-polymer interactions are purely repulsive, to a "very poor" solvent regime, where the polymers collapse due to their self-attractive intermolecular interactions. We also identify a compensation condition or ``θ point'' in our model between these limits, where the polymers are "ideal" in the sense in which attractive interactions effectively nullify inter-polymer repulsions so that the chains behave akin to Gaussian polymer chains in their average conformational properties. In order to compare with experiments performed in variable solvent qualities, we define a dimensionless measure of excluded volume interaction parameter δ in terms of the mass scaling exponent ν for R_g or ν_h for R_h, which can be determined from both experiment and simulation. We illustrate our variable solvent approach to estimate polymer solution properties in the case of polyethylenes (PEs) and evaluate the δ value that corresponds to the experimental solvent conditions. Our combined use of MD and ZENO allows for the numerical estimation of polymer solution properties for polymers having general monomer structures and solvent qualities in a computationally tractable fashion and should be useful as a general computational tool for polymer structural characterization.

Kathryn Beers

NIST

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