Vibrational Dynamics,Phonon Dispersion and Specific Heat in Gas Permeable Poly(4-Methyl-2-Pentyne)

Poly(4-methyl-2-pentyne) (PMP) is an amorphous glassy disubstituted acetylene based polymer. The excellent gas-separation and mechanical properties of these polymers have stipulated their use as membrane material for vapor and gas separation. PMP is among the hydrocarbon disubstituted polyacetylenes which have been synthesized to date. This polymer combines excellent gas and vapor permeability with good resistance to organic solvents. As was shown recently, PMP offers promise in the manufacture of nanocomposite membranes for the separation of various hydrocarbon mixtures. It is also of importance as its monomer, 4-methyl- 2-pentyne, can be easily derived from commercial compounds, 4-methyl-2-pentene or methyl isobutyl ketone, produced on a large scale. It is known that PMP exists in cis and trans configurations. Synthetic conditions, e.g., the used catalyst, temperature, solvent etc., of substituted polyacetylenes decide percentage of different configurations (cis or trans). Different geometries of macromolecules can influence the supramolecular structure of the polymer, which primarily defines its properties, such as solubility, permeability, sorption, etc. Qualitative assignments of few bands of IR spectra are reported earlier. We present here, complete normal mode analysis and dispersion curves for PMP using Wilson GF matrix method modified by Higgs using Urey-Bradley force field. Dispersion curves for PMP are drawn and salient features are discussed. Predicted values of specific heat via density-of-states are also reported.