Deuteron Magnetic Resonance Study of Order and Dynamics in Liquid Crystal Polymers

Thermotropic nematic polyesters, specifically deuterated at different positions of the polymer chain are studied by multiple pulse dynamic NMR. Analysis of the NMR experiments is achieved, employing a comprehensive model, based on the stochastic Liouville equation. Computer simulations provide the orientational distributions and conformations of the polymer chains and the correlation times of the various motions. In the anisotropic melt the correlation times for chain reorientation and trans-gauche-isomerization are in the range of 0.1–10 ns. Decreasing the temperature of the solid polymer first freezes the intermolecular motions. Thus, below the glass transition only intramolecular motions such as trans-gauche isomerization and ring flips can be detected. The chain order parameter of the nematic melt is S(ZZ) = 0.85. In addition, the chains adopt a highly extended conformation, evidenced by a trans population of n(t) = 0.8 throughout the entire spacer. This microorder is retained, when the polymer is cooled below the melting point and glass transition, respectively.