Dynamic Mechanical and Dielectric Relaxational Behavior of Poly(cyclohexylalkyl methacrylate)s

The dynamic mechanical and dielectric behavior of three poly(cyclohexylalkyl methacrylate)s with different spacer groups has been studied. The study was performed by determining the components of the complex relaxation modulus E* and the complex dielectric permittivity ε*. Results are discussed in terms of the effect of the side chain structure and the insertion of flexible spacer groups. Molecular dynamic calculations for the repeating unit of the polymers under study are analyzed. Close to room temperature the interconversion between axial and equatorial conformations is not observed whitin the total time of 5 ns. The analysis was then performed from 1000 to 1500 K, and the results were extrapolated to lower temperatures. By this way the fraction of axial and equatorial conformations was calculated. The free energy change against the number of carbon atoms in the side chain is in excellent agreement with the experimental data. This means that the γ relaxation associated with the chair-to-chair conformational change in the cyclohexyl group is also influenced by the length of the spacer group. The molecular dynamics approach allows to observe the relative incidence of the two conformations of the cyclohexyl group which can be related to the motions responsible for the γ relaxation.