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Thin films in the range of 50 nm to 10 mm thickness have been prepared from NMP solutions of silicon-containing polyphenylquinoxaline-amides which had been synthesized by the polycondensation reaction of aromatic diaminophenylquinoxalines with bis(p-chlorocarbonylphenyl)diphenylsilane. A spin-coating technique onto glass plates or onto silicon wafers was used to make the film, followed by gradual heating to remove the solvent. The resulting films were very smooth and free of pinholes when studied by atomic force microscopy (AFM). They showed a strong adhesion to silicon wafers, were thermally stable in air to above 400 °C and their dielectric constant was in the range of 3.5-3.7. Thermal treatment of the films was performed in order to induce crosslinking. Such treated films became completely insoluble in organic solvents, maintained their smoothness and strong adhesion to the silicon substrate, and did not show any Tg, in DSC experiments. Their FTIR spectra in reflection mode did not show any changes compared with the untreated films, meaning on the one hand that the polymers maintain their structural integrity at high temperature and on the other hand that the number of crosslinks was very low and could not be detected by IR spectroscopy.
New aromatic poly(amide-ether)s (II) have been synthesized by solution polycondensation of various aromatic diamines having two ether bridges (I) with a diacid chloride containing silicon, namely bis(chlorocarbonylphenyl)- diphenyIsilane. These polymers are easy soluble in polar amidic solvents such as N-methylpyrrolidinone or dimethylformamide and can be cast into thin flexible films or coatings from such solutions. They show high thermal stability with initial decomposition temperature being above 400 °C. Their glass transition temperatures lie in the range of 220-250 °C, except for polymer He which did not show a clear Tg when heated in a differential scanning calorimetry experiment up to 300 °C. The large interval between the glass transition and decomposition temperatures of pnlymers Ia-Id could be advantageous for their processing via compression molding. The polymer coatings deposited by the spincoating, technique onto silicon wafers showed a very smooth, pinhole-free surface in atomic force microscopy investigations. The free-standing films of 20-30 mm thickness show low dielectric constant, in the range of 3.65-3.78, which is promising for future application as high performance dielectrics.
Translational diffusion of poly(1,4-phenylene-1,3,4-oxadiazole) in 96% H2S04 was studied, and the intrinsic viscosity of the polymer solution was measured in various stages of degradation at temperatures from 82 to 105°C. The rate constant of the degradation process was determined from variation of the molecular mass of the degradation products with time at a fixed solution temperature, and the activation energy of the process was calculated using the temperature dependence of the rate constant. The activation energy (E = 103 ± 7 kJ/mol) is lower than that for the hydrolysis of aromatic polyamides in sulfuric acid. According to the hydrodynamic data, the degree of coiling of the degradation products is the saine as that of the intact (non-degraded) macromolecules. This indicates that elements of the chernical structure responsible for the short-range order in the macromolecular chain are retained in the course of degradation.
The translational diffusion coefficient and intrinsic viscosity of poly(1,4-phenylene-1,3,4-oxadiazole) molecules in 96% H2S04 have been determined at different stages of degradation of the molecules in acid solution at temperature ranging from 82 to 105 °C. The degradation rate constant, k, has been obtained from the change in the molecular weight, M, of the product degraded in solution with time at high temperature. The activation energy of the hydrolysis process was 103 ± 7 kJmol-1, which is smaller than that of aromatic polyamides in the same solvent. According to our hydrodynamic data, the degree of coiling of the molecules of degraded products does not differ from that of undegraded samples, and our conclusion was that the degradation is not accompanied with a noticeable change in the short- range interactions in the molecular chain and may be understood as a random chain scission.
The electrochemical behaviour of new amphiphilic 1,3,4-oxadiazoles were studied by cyclic voltammetry. The influence of the supra- molecular structure on the redox behaviour in liquid or solid solutions, in Langmuir-Blodgett multilayers, and in amorphous films is investigated in detail. The reversible reduction of amphiphilic 2,5-diarylene- 1,3,4-oxadiazoles is significantly influenced by substituents in the para position of the phenylene ring. In the solid states the reduction peak potentials are shifted to more negative values compared to data measured in solution. This shift increases as the film thickness is increased. An influence of the supramolecular order in the solid films was not found. In-situ UV-vis spectroelectrochemistry of LB-multilayers deposited onto indium tin oxide (ITO) glass give evidence for the formation of radical anions in the highly ordered layer.
Crystalline 2,5-di(4-nitrophenyl)-1,3,4-oxadiazole (DNO) has been investigated at pressures up to 5 GPa using Raman and optical spectroscopy as well as energy dispersive X-ray techniques. At ambient pressure DNO shows an orthorhombic unit cell (a = 0.5448 nm, b = 1.2758 nm, c = 1.9720 nm, density 1.513 g cm-3) with an appropriate space group Pbcn. From Raman spectroscopic investigations three phase transitions have been detected at 0.88, 1.28, and 2.2 GPa, respectively. These transitions have also been confirmed by absorption spectroscopy and X-ray measurements. Molecular modeling simulations have considerably contributed to the interpretation of the X-ray diffractograms. In general, the nearly flat structure of the oxadiazole molecule is preserved during the transitions. All subsequent structures are characterized by a stack-like arrangement of the DNO molecules. Only the mutual position of these molecular stacks changes due to the transformations so that this process may be described as a topotactical reaction. Phases II and III show a monoclinic symmetry with space group P21/c with cell parameters a = 1.990 nm, b = 0.500 nm, c = 1.240 nm, ß = 91.7°, density 1.681 g cm-3 (phase II, determined at 1. 1 GPa) and a = 1.890 nm, b = 0.510 nm, C = 1.242 nm, ß = 89.0°, density 1.733 g cm-3 (phase 111, determined at 2.0 GPa), respectively. The high-pressure phase IV stable at least up to 5 GPa shows again an orthorhombic structure with space group Pccn with corresponding cell parameters at 2.9 GPa: a = 0.465 nm, b = 1.920 nm, c = 1.230 nm and density 1.857 g cm-3 . For the first phase a blue pressure shift of the onset of absorption by about 0.032 eV GPa has been observed that may be explained by pressure influences on the electronic conjugation of the molecule. In the intermediate and high-pressure phases II-IV the onset of absorption shifts to increased wavelengths due to larger intermolecular interactions and enhanced excitation delocalization with decreasing intermolecular spacing.