CONFORMATIONAL ANALYSIS AND MOLECULAR MODELING OF CHOLESTERIC LIQUID CRYSTAL POLYESTERS BASED ON XRD,RAMAN, AND TRANSITION THERMAL ANALYSIS

Molecular modeling of the cholesteric liquid crystal polyester polyoxy(1,2 - dodecane)oxycarbonyl-1,4-phenyleneoxycarbonyl-1,4-phenylenecarbonyloxy-1,4-phenylenecarbonyl] (PTOBDME), C₃₄H₃₆O₈] _n , synthesized in our laboratory and thermally characterized by differential scanning calorimetry (DSC), was performed to explain both its cholesteric mesophase and 3D crystalline structure. Conformational analysis (CA) was run for the monomer both by systematic search and with molecular dynamics (MD) simulations. Minima energy conformers were “polymerized” with Cerius² and helical, cholesteric molecules were obtained in all cases. Our models agree with the chiral behavior observed by X-ray diffraction (XRD), thermooptical analysis (TOA) and circular dichroism (CD) experiments. Crystal packing of the polymer molecules were simulated in cells with parameters a and b obtained from experimental powder X-ray diffraction patterns and c calculated from the translational repetitive unit during the theoretical polymerization. Recalculated X-ray powder diffraction patterns of our models matched the observed ones. Morphology simulation from those crystal models is in good agreement with the crystals observed by optical microscopy. We have also modeled the self-associating nature of those polyesters when dispersed in aqueous media. Simulation of our models surrounded by different solvents, such as water and chloroform, were performed by calculating their interaction energies, coordination numbers, and mixing energies, applying Monte Carlo simulation techniques based on the Flory-Huggins theory. These results were compared with their experimental vibrational Fourier transform (FT)–Raman spectra in the regions in which structural marker bands of the polymer appear.