Impact of Molecular-level Structural Disruption on Relaxation Dynamics of Polymers with End-on and Side-on Liquid Crystal Moieties.

In side-chain liquid crystal polymers (SCLCPs), short side chains are attached on a flexible polymer backbone, and each side chain can have a liquid crystal (LC) group attached at the final bead in either an end-on or a side-on configuration. SCLCPs with random sequences of end-on and side-on LC moieties exhibit nonmonotonic thermal behavior as a function of composition, with some mixed sequences having a lower isotropic to LC phase transition than either purely end-on or side-on configurations. The origin of this nonmonotonic thermal trend lies in the disruption of molecular-level positional ordering and alignment due to the different preferred types of ordering of the different LC attachment types. We compare coarse-grained molecular dynamics (MD) simulations and experiments on SCLCP systems with only one type of LC moiety and demonstrate qualitative agreement in the observed mesophases of end-on and side-on SCLCP systems. Specifically, end-on SCLCPs display a smectic B-like mesophase, with layers of polymer between LC layers, while side-on SCLCPs exhibit a quasi-hexagonal columnar structure of polymer and a nematic surrounding the LC mesophase. Detailed analysis of SCLCP systems with various compositions of these types of LC attachments via MD reveals structural disruption in systems with intermediate compositions. Simulation snapshots and anisotropy ratio measurements show how random SCLCP systems deviate from the expected behavior of prolate or oblate systems in terms of their conformation. This molecular disruption in random SCLCP systems, particularly with a high composition of side-on LC moieties, also significantly impacts the relaxation dynamics. Modifying the composition of the LC type of attachment (molecular structure) is a possible route to tuning both the phase behavior and mechanical response of these systems.