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Poly(1,3,4-oxadiazole)s have been the focus of considerable interest with regard to the- production of high- performance materials, particularly owing to their high thermal stability in oxidative atmosphere and specific properties determined by the structure of 1,3,4-oxadiazole ring, which, from the spectral and electronic points of view, is similar to a p-phenylene structure.[1] Besides their excellent resistance to high temperature, polyoxadiazoles have many desirable characteristics, such as good hydrolytic stability, high glass transition temperatures, low dielectric constants, and tough mechanical properties. Some polyoxadiazoles have semiconductive properties, other structures can be electrochemically doped and thus made conductive, and other have liquid-crystalline properties, which make them very attractive for a wide range of high-performance applications. They exhibit excellent fiber- and film-forming capabilities, thus being considered for use as heat-resistant reinforcing fibers for advanced composite materials, highly resistant fabrics for the filtration of hot gases, special membranes for gas separation or reverse osmosis, precursors for highly oriented graphite fibers, films, and blocks to be used in the construction of electronic instruments based on X-rays, neutron beams, or a-particles, or in the construction of nuclear reactor walls. Since they were first reported in 1961,[2] a wide variety of polymers containing 1,3,4-oxadiazole rings have been synthesized, and their preparation, characterization, and physico-mechanical properties have been periodically reviewed .[3-8] This article will present a general overview of this class of polymers and will refer to the work carried out by different researchers in the last ten years with the emphasis on the potential uses of such polymers as advanced materials.
The surface structures of crystals based on aromatic oxadiazoles were investigated by AFM. The crystal structure for 2,5-di(p-tolyl)-1,3,4-oxadiazole (DTO) differs from that of 2,5-di (4-methoxycarbonyl-phenyl)-1,3,4- oxadiazole (DMPO). In DMPO all molecules show parallel orientation to the surface in such a way that the surface is formed as well as by the nitrogen atoms of the heterocyclic rings and the methyl groups of the ester substituents. By contrast, the oxadiazole molecules in DTO crystals are oriented perpendicular to the crystal surface. The experimental data are interpreted by molecular modelling. It is shown that there is a difference between molecular structure of the surface, as detected by AFM, and the bulk structure determined by X-ray diffraction.
Two series of aromatic polyamides incorporating silicon together with phenylquinoxaline or with hexafluoroisopropylidene groups have been synthesized and their properties have been characterized and compared with those of related polymers. These polymers are easily soluble in polar amidic solvents such as N-rnethyl-2-pyrrolidinone and dimethylformamide, and in tetrahydrofuran, and can be cast into thin, transparent films from solution. The polyamides have weight- and number-average molecular weights in the range of 10000-40000 and 3000-6000, respectively, and polydispersities in the range of 3-10. They show glass transition temperatures in the range of 236 °C-275 °C and decomposition temperatures above 400 °C. The polymer films have low dielectric constants in the range of 3.26-3.68, and good mechanical properties (tensile strength 74-100 MPa, tensile modulus 180-386 MPa), thus being comparable with other high performance dielectrics.
Flow birefringence induced in dilute solutions of poly[(1,4-naphthylene)-2,5-diyl-1,3,4-oxadiazole] and poly[2,6-naphthylene)-2,5-diyl-1,3,4-oxadiazole] in conc. sulphuric acid has been investigated. The shear optical coefficient was found for these polymers to be approximately double the value of that obtained in the same solvent for poly[(para-phenylene) -2,5-diyl-1,3,4-oxadiazole]. Rigid-chain behaviour of the polymers was characterized by hydrodynamic and dynamo-optical parameters evaluated with application of the worm-like chain model and the "method of similar structures". Change in optical anisotropy of a chain unit induced by incorporation of naphthylene groups into the main chain has been evaluated.
New heterocyclic polyamides have been synthesized by solution polycondensation of aromatic diamines containing phenyl- quinoxaline units with diacid chlorides having both imide and hexafluoroisopropylidene (6F) groups. These polymers are soluble in polar aprotic solvents, such as N-methylpyrrolidone (NMP) or N,N-dimethylformamide (DMF), and can be cast into flexible thin films from solutions. They show high thermooxidative stability with decomposition temperatures above 400°C and glass transition temperatures in the range of 225 - 300°C. The polymer films exhibit good chemical resistance towards deluted acids and good electrical insulating properties with dielectric constants in the range of 3.2 - 3.7.
Translational diffusion of the macromolecules, intrinsic viscosity and flow birefringence induced in dilute solutions of poly(1,3-phenylene-1,3,4-oxadiazole) (PMOD) in conc. sulphuric acid has been investigated. Molecular-weight dependences of hydrodynamic and dynamo-optical properties are established over the M range from 8.1 103 to 87 103. Experimental data agree well with the theories developed for translational friction and intrinsic viscosity of the wormlike chains with the following molecular parameters: mass per chain unit ML = 22.7 Dalton/Å, the Kuhn segment length A = 59 ± 4 Å, the chain diameter d = 4 ± 1.5 Å. Hindrance to intramolecular rotation is characterized by the parameter s = 1.7. The shear optical coefficient was found to be approximately 1.7 times lower the value of that obtained in the same solvent for the para-phenylene isomer of this polymer, being in good agreement with higher equilibrium flexibility of the PMOD molecule chains in solutions as determined herein from the hydrodynamic data.
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.