The Synthesis and Properties of Liquid Crystalline Polyurethanes, Chemically Modified by Polyhedral Oligomericsilsesquioxanes.

In this work, we report for the first time on the influence of polyhedral oligomericsilsesquioxanes (POSS) on the structure and properties of liquid crystalline polyurethane (LCPU). LCPU/POSS hybrids were synthesized via a two-step method. In the first step, 4,4'-methylenephenyl diisocyanate (MDI) and polytetramethylene ether glycol (PTMG) reacted with functionalized trisilanolphenyl POSS (TSP-POSS) bearing three hydroxyl groups. In the second step, the growing chain was extended with 4,4'-bis(hydroxyhexoxy)biphenyl (BHHBP). FTIR measurements confirmed the chemical bonding between the POSS and LCPU matrix and showed the influence of the silsesquioxane modification on the intensity of hydrogen bonds. The DSC and POM techniques confirmed the formation of liquid crystalline phases. The incorporation of silsesquixanes into the LC matrix leads to higher melting and isotropization temperatures along with the broadening phase transition effect. Scanning electron microscopy showed a good distribution of POSS moieties, both in the bulk and on the surface of the liquid crystalline PU matrix, whereby wide-angle X-ray diffraction (WAXD) patterns revealed halos from both the liquid crystalline and unmodified polyurethane matrix. The stress at the breaking points for LCPU/POSS hybrids containing 50% and 60% of elastic segments is greater than the stress at the breaking point of the reference material (LCPU), what is due to good dispersion of POSS in less elastic matrix. Thermal properties of the LCPU/POSS materials obtained, determined by TGA, revealed that the char residue increased with the amount of POSS for 40% of elastic segments materials.