Gas separation properties of new polyoxadiazole and polytriazole membranes

The gas separation properties of new aromatic poly-1,2,4-triazole and poly-1,3,4-oxadiazole membranes have been systematically investigated. Various functional groups were incorporated as pendent groups onto the polymer backbone of poly-1,2,4-triazoles. A wide permeability/selectivity spectrum was covered with the choice of functional groups incorporated into the polymer backbone of poly-1,3,4-oxadiazoles. High permeabilities were found for poly-1,3,4-oxadiazoles with a 1,1,3-trimethyl-3-phenylindane (PIDA-POD) and a 4,4′(2,2′-diphenyl)hexafluor propane (HF-POD) unit in the polymer backbone, while incorporation of a 4,4′-diphenyl ether unit (DPE-POD) results in a polymer with a low permeability but an extremely high selectivity. While the permeabilities vary over four orders of magnitude, the solubility remains almost constant and, therefore, the increase in permeability is mainly due to an increase in diffusivity. The permeability is discussed in terms of the polymer free volume

Two reaction routes for the preparation of aromatic polyoxadiazoles and polytriazoles: Syntheses and properties

Two reaction routes for the preparation of aromatic poly-1,3,4-oxadiazoles and poly-1,2,4-triazoles are studied and their influence on the physical properties, i.e., inherent viscosity, glass transition, degradation temperature, and film integrity of the final products are discussed. Aromatic poly-1,3,4-oxadiazoles are prepared by means of a polycondensation reaction of terephthaloyl chloride and isophthalic dihydrazide yielding a precursor polymer, poly(p, m-phenylene) hydrazide, which is converted into the corresponding poly-1,3,4-oxadiazole by means of a cyclodehydration reaction. Poly-1,3,4-oxadiazoles are also prepared by means of a polycondensation reaction between terephthalic and isophthalic acid and hydrazine yielding poly-1,3,4-oxadiazoles with higher inherent viscosities. Flexible poly-1,3,4-oxadiazole films are obtained only if the inherent viscosities of the polymers used are higher than 2.7 dL/g. The thermal stability is found to increase with increasing content of p-phenylene groups in the polymer backbone. Aromatic poly-1,2,4-triazoles are prepared using polyhydrazides with alternating para- and meta-phenylene groups and poly-1,3,4-oxadiazoles with a random incorporation of para- and meta-phenylene groups in the main chain as precursor polymers. The glass transition temperatures are found to increase with increasing content of p-phenylene groups in the main chain of these polymers. Cold crystallization is observed only for the alternating polymer

On the mechanism of gas transport in rigid polymer membranes

Conventional polymers are compared as gas separation membrane materials with tailormade polymers. The increased permeability of the latter are due to their higher free volume available for gas transport. The increased free volume is associated with the rigidity polymer backbone. Free volume is obtained by subtracting the occupied volume, calculated using group contributions from the polymer specific volume. Wide Angle X-ray techniques are used to obtain average d-spacings that are interpreted in terms of average intermolecular space, and that are related to permeability data. These highly permeable rigid polymer membranes have high glass transition temperatures. The physical parameters, that is, Tg and the jump in heat capacity (ΔCp), are obtained with Differential Scanning Calorimetry, and are used to obtain an estimation of free volume. A good correlation for a series of random copoly[p, m-phenylene(4-phenyl)-1,2,4-triazoles] is obtained. A relationship between permeability and a free volume term, which can be estimated from thermodynamic properties, is equally valid for a wide variety of conventional polymers

Two reaction routes for the preparation of aromatic polyoxadiazoles and polytriazoles: Syntheses and properties

Two reaction routes for the preparation of aromatic poly-1,3,4-oxadiazoles and poly-1,2,4-triazoles are studied and their influence on the physical properties, i.e., inherent viscosity, glass transition, degradation temperature, and film integrity of the final products are discussed. Aromatic poly-1,3,4-oxadiazoles are prepared by means of a polycondensation reaction of terephthaloyl chloride and isophthalic dihydrazide yielding a precursor polymer, poly(p, m-phenylene) hydrazide, which is converted into the corresponding poly-1,3,4-oxadiazole by means of a cyclodehydration reaction. Poly-1,3,4-oxadiazoles are also prepared by means of a polycondensation reaction between terephthalic and isophthalic acid and hydrazine yielding poly-1,3,4-oxadiazoles with higher inherent viscosities. Flexible poly-1,3,4-oxadiazole films are obtained only if the inherent viscosities of the polymers used are higher than 2.7 dL/g. The thermal stability is found to increase with increasing content of p-phenylene groups in the polymer backbone. Aromatic poly-1,2,4-triazoles are prepared using polyhydrazides with alternating para- and meta-phenylene groups and poly-1,3,4-oxadiazoles with a random incorporation of para- and meta-phenylene groups in the main chain as precursor polymers. The glass transition temperatures are found to increase with increasing content of p-phenylene groups in the main chain of these polymers. Cold crystallization is observed only for the alternating polymer

Synthesis and properties of related polyoxadiazoles and polytriazoles

New aromatic poly-1,2,4-triazoles and poly-1,3,4-oxadiazoles are studied as thermally stable membrane materials. Various groups were introduced onto the pendant phenyl groups of poly-1,2,4-triazoles. Glass transition temperature, degradation temperature, and cold crystallization behavior were studied as a function of these groups. Cold crystallization appeared to be highly sensitive to macromolecular regularity. The solubility of poly-1,3,4-oxadiazoles was highly improved upon incorporation of 5-t-butylisophthalic, 1,1,3-trimethyl-3-phenylindane, 4,4-(2,2-diphenyl) hexafluoro propane, and diphenyl ether groups into the polymeric main chain, whereas the high glass transition temperatures and degradation temperatures typical for aromatic poly-1,3,4-oxadiazoles were maintained