The Concentration Dependence of the Size and Symmetry of a Bottlebrush Polymer in a Good Solvent.

Macromolecules
Daniel F SundayRobert H Grubbs

Abstract

Bottlebrush polymers consist of a linear backbone with densely grafted side chains which impact the rigidity of the molecule. The persistence length of the bottlebrush backbone in solution is influenced by both the intrinsic structure of the polymer and by the local environment, such as the solvent quality and concentration. Increasing the concentration reduces the overall size of the molecule due to the reduction in backbone stiffness. In this study we map out the size of a bottlebrush polymer as a function of concentration for a single backbone length. Small-angle neutron scattering (SANS) measurements are conducted on a polynorbornene-based bottlebrush with polystyrene side chains in a good solvent. The data are fit using a model which provides both the long and short axis radius of gyration (Rg,2 and Rg,1, respectively), providing a measure for how the conformation changes as a function of concentration. At low concentrations a highly anisotropic structure is observed (Rg,2/Rg,1 ≈ 4), becoming more isotropic at higher concentrations (Rg,2/Rg,1 ≈ 1.5). The concentration scaling for both Rg,2 and the overall Rg are evaluated and compared with predictions in the literature. Coarse-grained molecular dynamics simulations were al...Continue Reading

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