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A series of fluorinated co-polyimide films based on the 6FDA-FTPPA/BAFL backbone were prepared from 4-(3-fluoro-4- (trifluoromethyl)phenyl)-2,6-bis(4-aminophenyl)pyridine (FTPPA), commercial 9,9-bis(4-aminophenyl)fluorene (BAFL), and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), with varying ratios of FTPPA:BAFL units (3:1, 2:1, 1:1, 1: 2, and 1:3). Co-polyimides not only exhibit high thermal stability (Tg > 357°C), good optical properties (λcutoff > 327 nm) and hydrophobicity (contact angle >91.4°), but also favorable solubility properties in both high and low boiling organic solvents. The fractional free volume of the polymers was simulated using molecular mechanics and molecular dynamics and correlated with experimental gas separation data. The presence of bulky groups led to high FFVs (>17.8%) and the formation of large microcavities with diameters ranging from 5.48 to 5.72 A°, which efficiently increased gas permeability. In pure gas permeation experiments, the permeability coefficients of CO2 and He for the 6FDA-FTPPA/BAFL (3:1) film were 41.48 and 79.38 bar, respectively, which were superior to those of commercial Matrimid and Kapton in terms of gas permeability. In especial, the 6FDA-FTPPA/BAFL (1:2) and 6FDA-FTPPA/BAFL (1:3) in copolyimide membranes exhibited the most attractive separation performance for O2/N2 gas pairs, approaching the 1991 Roberson upper limit. [ABSTRACT FROM AUTHOR]

In this work, two kinds of dimaine monomers with spirocyclic structures, including 3,3,3′,3′-tetramethyl-6,6′-bis[3-amino-4-hydroxyphenoxy]-1,1′-spirobisindane (TBAHS) and 3,3,3′,3′-tetramethyl-bis(5-amino-6-hydroxyphenyl)-1,1′-spirobisindane (TBHAS) are firstly synthesized. Then, the two diamines TBAHS and TBHAS are copolymerized in different molar ratios with equimolar 4,4′-(hexafluoroisopropenyl)diphthalic anhydride (6FDA) to synthesize poly(amic acid) (PAA) solution, followed by thermal imidization to obtain a series of copolyimide (coPI) membranes. Next, these coPI(TBAHS-TBHAS) specimens are subjected to thermal rearrangement (TR) treatment at 450°C to obtain the corresponding coTR(TBAHS-TBHAS) copolymer membranes. The influences of the molar ratio of TBAHS to TBHAS, thermal treatment temperature and time on the microstructures and properties of the PI and TR copolymers are investigated. With the increase of rigid TBHAS molar ratio, the glass transition temperature (Tg) and d-spacing value of the coPI(TBAHS-TBHAS) samples are significantly enhanced. Furthermore, as the thermal treatment temperature increases, the mechanical properties of the copolymer membranes display a sharply decline trend, but the d-spacing values are obviously increased. When the molar ratio of TBAHS to TBHAS is 7:3, the gas permeabilities of the coTR membrane reach 1140.5, 1180.6, 306.6, and 44.9 Barrer for H2, CO2, O2, and N2, respectively. Meanwhile, the ideal selectivity of O2/N2 is 6.82, suggesting a superior separation performance close to the 2015 upper limit. Furthermore, with the increase of thermal treatment temperature and time, the gas permeabilities are also improved. [ABSTRACT FROM AUTHOR]

A set of ionic liquid capped polyimide membranes was prepared using 1-aminoethyl-3-methylimidazolium hexafluorophosphate (IL1) and 1-aminopropylimidazolium bis(trifluoromethylsulfonyl)imine (IL2) as the terminal groups. The products' molecular weights, mechanical properties, and separation permeability (CO2/CH4) were investigated. For CO2/CH4 separation, the selectivity of the ionic liquid capped polyimide membranes was higher than that of noncapped ones. Among them, the membrane synthesized by 4.4′- diaminodiphenyl ether and 4.4′-(hexafluoroisopropyl) diphthalic anhydride (6FDA) as monomer, with IL1 as terminal group, displayed the best selectivity. Its permeability was 7.47 Barrer and selectivity 102.42, which exceeded the 1991 Robeson curve. Polyimide membranes capped by ionic liquid showed high gas selectivity and good gas permeability as well as good physical and chemical properties. Consequently, it can be concluded that introducing an ionic liquid structure to polyimide chains could make attractive membrane materials for various gas separation and related applications. Graphical Abstract [ABSTRACT FROM AUTHOR]

Polyimides (PIs) with single phenyl pendant substitution were prepared based on three diamines containing phenyl pendant group, namely, 2,5-bis(4-aminophenoxy) biphenyl, 2-phenyl-4,4′-diaminodiphenyl ether, and 2,5-diaminobiphenyl (p-PDA), with the dianhydride component of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride, respectively. The physical properties of the membranes were examined, including thermal properties, fractional free volume (FFV), solubility, and morphological structures, and were compared with the analogues without phenyl pendant. Gas transport properties of the membranes were investigated and discussed from the viewpoint of structure–property relationship. For 6FDA-derived PI membranes, gas permeability increased as the degree of PI backbone rigidity leveled up. Gas transport properties were not improved by the incorporation of phenyl pendant group for 6FDA type containing ether linkage and marginally improved as compared between PI (6FDA/p-PDA) and PI (6FDA/p-phenylenediamine (PDA)). To increase the phenyl substitution density of 6FDA/PDA-type backbone, a novel diamine bearing two phenyl pendant groups, that is, 2,6-diphenyl-1,4-diaminobenzene (p, p′-PDA) was synthesized, and PI derived from 6FDA and p, p′-PDA was prepared. The gas permeability coefficients of PI (6FDA/p, p′-PDA) were remarkably larger than those of PI (6FDA/p-PDA) and PI (6FDA/PDA). [ABSTRACT FROM AUTHOR]

A series of polyimide (PI) membranes were prepared based on three triphenylamine-based diamines, namely 4,4′-diaminotriphenylamine, 4,4′-diamino-3′′,5′′-dimethyltriphenylamine, and 4,4′-diamino-3′′,5′′-ditrifluoromethyltriphenylamine, via thermal imidization procedure. The PI membranes displayed good thermal properties, with glass transition temperatures of 279–341°C and 5% weight loss temperatures above 515°C under a nitrogen atmosphere. The gas permeation properties of the membranes were investigated and interpreted from the viewpoint of the PI backbone structure. The gas permeation coefficients increased as the substituent pendant groups at the 3′′,5′′ positions of the triphenylamine varied from –H to –CH3 and –CF3, and the permselectivity of gas pairs (including hydrogen/nitrogen (N2), oxygen/N2, carbon dioxide (CO2)/N2, and CO2/methane) decreased in this order. The diffusion coefficients and solubility coefficients were calculated, and the results revealed the variation of the substituted triphenylamine units principally influenced the diffusion coefficients, indicating that the substituted triphenylamine affected the gas transport properties by “diffusivity-controlled” modification. [ABSTRACT FROM AUTHOR]