Entropic Mixing of Ring/Linear Polymer Blends

G. S. Grest, T. Ge, S. J. Plimpton, M. Rubinstein, T. C. O'Connor, ACS Polymers, 3, 209-216 (2023).

The topological constraints of nonconcatenated ring polymers force them to form compact loopy globular conformations with much lower entropy than unconstrained ideal rings. The closed-loop structure of ring polymers also enables them to be threaded by linear polymers in ring/linear blends, resulting in less compact ring conformations with higher entropy. This conformational entropy increase promotes mixing rings with linear polymers. Here, using molecular dynamics simulations for bead-spring chains, ring/linear blends are shown to be significantly more miscible than linear/linear blends and that there is an entropic mixing, negative χ, for ring/linear blends compared to linear/linear and ring/ring blends. In analogy with small angle neutron scattering, the static structure function S(q) is measured, and the resulting data are fit to the random phase approximation model to determine χ. In the limit that the two components are the same, χ = 0 for the linear/linear and ring/ring blends as expected, while χ < 0 for the ring/linear blends. With increasing chain stiffness, χ for the ring/linear blends becomes more negative, varying reciprocally with the number of monomers between entanglements. Ring/linear blends are also shown to be more miscible than either ring/ring or linear/linear blends and stay in single phase for a wider range of increasing repulsion between the two components.

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