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The incorporation of small amounts of 3,5-diaminobenzoic acid (DABA) comonomer (usually 5-20 mol %) into an ortho-hydroxypolyimide (HPI) precursor constitutes a new methodology to easily improve the gas transport performance of thermally rearranged (TR) polymer membranes. Thermogravimetric analysis (TGA) profiles of HPI with DABA copolyimides (HPID) suggests that there is an overlap between the temperature ranges of two processes: the degradation of DABA carboxyl groups and the actual thermal rearrangement process. During thermal treatment at 450 °C, carboxyl pendant groups in DABA degrade while a more rigid biphenyl cross-linked structure is formed either following or at the same time as the rearrangement of imide to benzoxazole. Mixed-gas CO2/CH4 (1:1) experiments proved this new series of cross-linked TR poly(benzoxazole-co-imide) (XTR-PBOI) membranes as superior materials for CO2/CH4 separation applications, with enhanced permeability and selectivity, as well as high resistance to plasticization up to 40 bar. [ABSTRACT FROM AUTHOR]

Abstract: The effect of bulky side groups on the molecular mobility and chain packing of three polyimides derived from dianhydrides with m-terphenyl moieties and 2,4,6-trimethyl-m-phenylenediamine has been studied. Moreover, structure–properties relationships in terms of gas transport have been established. One of the polyimides has no side groups, while the other two have a t-butyl group in 5′ (meta) position on the central ring of the m-terphenyl moiety and one of them has also a pivaloylimino group placed in the 2′ (ortho) position. The changes in chain packing of the membranes were evidenced by wide angle X-ray diffraction (WAXS), whilst the molecular mobility was evaluated from the dielectric sub-ambient secondary relaxation, γ relaxation. The WAXS pattern of the polyimide containing both t-butyl and pivaloylimino side groups evidenced a greater degree of packing regularity than in the other two polyimides. Moreover, the additional pivaloylimino group strongly restricted the local molecular mobility associated with the phenylene-imide ring flips. On the other hand, the gas permeability of the polyimides strongly increased with the introduction of side groups. This increase was mainly related to the increase in the gas diffusivity, which could not be explained by an increase in fractional free volume (FFV). The results presented in this work indicate that the difference in gas diffusivity of the substituted polyimides is consistent with a difference in size distribution of free volume elements. [Copyright &y& Elsevier]

Abstract: This study demonstrates that thermal treatment of ortho-hydroxy containing polyimides (HPIs) in the solid state certainly leads to the formation of polybenzoxazoles (PBOs). Thermal conversion protocol, including temperature and dwell time, and the form of the sample (film or powder) determine the rearrangement reaction rate of HPI into PBO. Thermal rearrangement kinetics seems to be faster for film samples rather than for powder ones. Also, mild thermal treatment conditions (i.e., low temperatures and short times) seem to result in negligible or low degrees of conversion to PBO. Moreover, synthetic routes of HPI do not alter in any way the thermal conversion pathway. These findings validate the widely reported imide-to-benzoxazole thermal rearrangement mechanism, and contradict the alternative rearrangement pathway, proposed recently, of HPI into poly(biphenylene bisimide) polymers. [Copyright &y& Elsevier]

Abstract: An attempt was made to elucidate the relationship between chemical structure, in terms of glass transition temperature (T g), and conversion temperature (T TR ) of thermally rearranged polybenzoxazole membranes, by analyzing DSC and TGA data for a total of 15 sets of o-hydroxypolyimides and copolyimides, derived from two experimental and four commercial structurally different diamines, as well as four different dianhydride monomers. Our research revealed that T TR was influenced by chain ridigity of o-hydroxypolyimides, and exhibited a linear relationship with T g. Therefore, structure and thermal property of o-hydroxypolyimide should be considered when studying TR polymers to determine thermal conversion to polybenzoxazole. [Copyright &y& Elsevier]

Abstract: A series of polyimides has been obtained from the experimental diamine 1,4-bis(4-aminophenoxy)2,5-di-tert-butylbenzene (TBAPB) and three commercial dianhydrides, i.e. pyromellitic dianhydride (PMDA), 3,3′,4,4′-byphenyltetracarboxylic dyanhidride (BPDA) and 4,4′-hexafluoroisopropyliden diphthalic anhydride (6FDA), following classical polyimidation methods. Analogous polyimides with diamines 2,2-bis(4-aminophenyl)hexafluoropropane (6FpDA) and 1,4-bis(4-aminophenoxy)benzene (APB) have been also prepared for comparative purposes. All polyimides showed high thermal stability, with decomposition temperatures above 490°C, and glass transition temperatures higher than 270°C. The rigid, rod-like structure of PMDA, combined with bulky diamines TBAPB and 6FpDA, yielded polyimides with high fractional free volume (FFV), close to that of 6FDA–6FpDA. The high FFV of PMDA–TBAPB contrasts with its structure that has fairly large degree of short range order as evidenced by X-ray diffraction. The gas permeation properties were greatly dependent on the dianhydride moiety and, as a rule, they compared well with those of polyimides used for gas separation. The polymers from PMDA, PMDA–TBAPB and PMDA–6FpDA, showed the best gas productivity values. By means of molecular modelling calculations, it has been observed that monomer TBAPB preferably adopts a contorted, rotation-restricted conformation, what can explain the special characteristics observed in the reported polyimides. [ABSTRACT FROM AUTHOR]