Intrinsic microporosity and gas transport in polyphenylene oxide polymers

Ilinitch, O.M.; Фенелонов, В. Б.; Lapkin, Alexei; Okkel, L. G.; Terskikh, V. V.; Zamaraev, K. I.

doi:10.1016/s1387-1811(99)00060-8

Cited by 64 publications

(45 citation statements)

References 61 publications

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“…The introduction of hydroxyl groups decreased the BET surface area determined with nitrogen from 66 m 2 g -1 for 6FDA-mPDA to 54 m 2 g -1 for 6FDA-DAP and to 45 m 2 g -1 for 6FDA-DAR (in all cases ±3 m 2 /g), which was anticipated based on the effect of interchain hydrogen bonding due to the introduction of hydroxyl groups to the polymer backbone [31]. Similar N 2 -based BET surface areas have previously been reported for other moderate-free-volume glassy polymers, such as poly(phenylene oxides) and polyimides [39][40][41][42]. Interestingly, the gravimetric CO 2 sorption uptake increased in the reverse order of the BET surface areas of the polymers, that is, 6FDA-DAR > 6FDA-DAP > 6FDA-mPDA, indicating that (i) hydroxyl functionalization increases CO 2 sorption and (ii) higher OH concentration per polymer repeat unit also leads to increased CO 2 uptake.…”

Section: Physical Properties Of the Polyimidessupporting

confidence: 82%

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Alaslai

Ghanem

Alghunaimi

et al. 2016

Journal of Membrane Science

116

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The effect of hydroxyl functionalization on the m-phenylene diamine moiety of 6FDA dianhydride-based polyimides was investigated for gas separation applications. Pure-gas permeability coefficients of He, H 2 , N 2 , O 2 , CH 4 , and CO 2 were measured at 35 °C and 2 atm.The introduction of hydroxyl groups in the diamine moiety of 6FDA-diaminophenol (DAP) and 6FDA-diamino resorcinol (DAR) polyimides tightened the overall polymer structure due to increased charge transfer complex formation compared to unfunctionalized 6FDA-m-phenylene diamine (mPDA). The BET surface areas based on nitrogen adsorption of 6FDA-DAP (54 m 2 g -1 )and of 6FDA-DAR (45 m 2 g -1 ) were ~18% and 32% lower than that of 6FDA-mPDA (66 m 2 g -1 ).6FDA-mPDA had a pure-gas CO 2 permeability of 14 Barrer and CO 2 /CH 4 selectivity of 70. The hydroxyl-functionalized polyimides 6FDA-DAP and 6FDA-DAR exhibited very high pure-gas CO 2 /CH 4 selectivities of 92 and 94 with moderate CO 2 permeability of 11 and 8 Barrer, respectively. It was demonstrated that hydroxyl-containing polyimide membranes maintained very high CO 2 /CH 4 selectivity (~ 75 at CO 2 partial pressure of 10 atm) due to CO 2 plasticization resistance when tested under high-pressure mixed-gas conditions. Functionalization with hydroxyl groups may thus be a promising strategy towards attaining highly selective polyimides for economical membrane-based natural gas sweetening.

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Section: Physical Properties Of the Polyimidessupporting

confidence: 82%

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Alaslai

Ghanem

Alghunaimi

et al. 2016

Journal of Membrane Science

116

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“…A general decrease in the permeability coefficients with increase in the PDPPO content is consistent the results reported by Ilinich et al 40 Using 129 Xe NMR spectroscopy they observed that the effective pore size decreases from 0.56 nm for PDMPO to 0.50 nm for PDPPO. A decrease in the effective pore size must be associated with a decrease in the diffusion coefficient.…”

Section: Gas Permeation Propertiessupporting

confidence: 90%

Development and characterization of homopolymers and copolymers from the family of polyphenylene oxides

Tran

Kruczek

2007

J of Applied Polymer Sci

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Poly(2,6-dimethyl-1,4-phenylene oxide), PDMPO, poly(2,6-diphenyl-1,4-phenylene oxide), PDPPO, as well as their copolymers of different compositions, having both random and block structures, have been synthesized and characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, and gel permeation chromatography. Solution-cast films were prepared from all synthesized polymers using chloroform as a solvent. The thermal properties of the resulting films were characterized by differential thermal analysis and differential scanning calorimetry, whereas their morphology was investigated using X-ray diffraction. Ultimately, the potential of the synthesized polymers for gas separation was studied by examining gas permeation properties of the respective thin films in single gas permeation tests involving N 2 , O 2 , CH 4 , and CO 2 . In general, the O 2 and CO 2 permeability coefficients decrease with the PDPPO content. However, the largest drop in the permeability coefficients occurs between PDMPO and a copolymer having the lowest PDPPO content, and the permeability coefficients PDPPO are comparable or even lower than the permeability coefficients of the copolymers having the largest PDDPO content. On the basis of combination of the permeability coefficients and their ratios for CO 2 /CH 4 and O 2 / N 2 , random copolymers appear to be a better candidate for gas separation membranes than their block counterparts.

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“…The PIMs exhibit pronounced hysteresis, the N 2 desorption curve lying above the adsorption curve, with the hysteresis extending down to low relative pressures. Low pressure hysteresis like this has occasionally been observed for other microporous materials, and may be attributed either to sorbate‐induced swelling or to a complex micropore structure with throats and cavities 34. In PIMs, for which the microporosity arises from a complex distribution of interconnected free volume, it is likely that the low pressure hysteresis arises primarily from the presence of constrictions.…”

Section: Introductionmentioning

confidence: 64%

Microporous Polymers as Potential Hydrogen Storage Materials

McKeown

Budd

Book

2007

Macromol. Rapid Commun.

181

124

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Microporous organic polymers offer the possibility of storing hydrogen safely at low temperatures and moderate pressures via physisorption. A range of polymers of intrinsic microporosity (PIMs) have been studied. The best PIM to date is based on a triptycene monomer and takes up 2.7% H2 by mass at 10 bar/77 K. Hypercrosslinked polymers (HCPs) also show promising performance, particularly at pressures >10 bar. The form of the H2 isotherm is influenced by the micropore distribution, a higher concentration of ultramicropores (pore size <0.7 nm), as found in PIMs, being associated with enhanced low pressure adsorption. The performance of polymers relative to other microporous materials (carbons and metal‐organic frameworks) is compared and promising methods to enhance the hydrogen uptake of microporous polymers are suggested.magnified image

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Intrinsic microporosity and gas transport in polyphenylene oxide polymers

Cited by 64 publications

References 61 publications

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Pure- and mixed-gas permeation properties of highly selective and plasticization resistant hydroxyl-diamine-based 6FDA polyimides for CO2/CH4 separation

Development and characterization of homopolymers and copolymers from the family of polyphenylene oxides

Microporous Polymers as Potential Hydrogen Storage Materials

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