Polymers of Intrinsic Microporosity Derived from Novel Disulfone-Based Monomers

Du, Naiying; Robertson, Gilles P.; Pinnau, Ingo; Guiver, Michael D.

doi:10.1021/ma900898m

Cited by 136 publications

(85 citation statements)

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“…Although pretreatment and cross-linking conditions are also crucial issues in determining the membrane performance, the chemical structure and physical properties of polymer precursors should be considered foremost. Based on the variety of high molecular weight PIMs reported in the literature, [6,[23][24][25][26] PIM-1 (Scheme 1) was selected as the representative polymer in this class of materials, since it is the most widely reported and characterized, due to its simple preparation from commercial monomers, high fractional free volume (FFV), high thermal stability, good processability and mechanical properties. Two diazides (Scheme 1) that are capable of thermal curing were investigated as cross-linking reagents to form the crosslinked PIM.…”

Section: Resultsmentioning

confidence: 99%

Azide‐based Cross‐Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation

Cin

Pinnau

et al. 2011

Macromol. Rapid Commun.

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141

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Cross‐linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross‐linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross‐linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT‐IR spectroscopy and gel content analysis. These resulting cross‐linked polymeric membranes showed excellent gas separation performance and can be used for O2/N2 and CO2/N2 gas pairs, as well as for condensable gases, such as CO2/CH4, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO2 plasticization up to 20 atm pressure of pure CO2 and CO2/CH4 mixtures. magnified image

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Section: Resultsmentioning

confidence: 99%

Azide‐based Cross‐Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation

Cin

Pinnau

et al. 2011

Macromol. Rapid Commun.

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141

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“…This membrane preparation method in which the final drying was performed under air at 70 °C, is a modification of that previously reported. [29] Thickness of the samples was (102±13) µm, and the mass of the membrane used for experiments was 1.1602 g.…”

Section: Membrane and Chemicalsmentioning

confidence: 99%

Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Vopička

Angelis

et al. 2014

Journal of Membrane Science

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The individual solubility of CH 4 and CO 2 from binary gas mixtures was measured at 35 °C and up to 35 bar in a polymer of intrinsic microporosity (PIM-1), at different compositions of the gas phase (from 0 to 50 mol% of CO 2 ). The experiments were conducted on a pressure-decay apparatus equipped with a gas chromatograph, allowing a highly flexible measuring procedure. The gas solubility was plotted versus gas phase composition, total pressure, gas fugacity and second gas concentration. The mixed gas solubility of both species, CH 4 and CO 2 , is lower than the pure gas value at the same fugacity, but the reduction of methane solubility due to the presence of CO 2 is generally more significant. Such behavior is due to the fact that CO 2 has normally higher solubility than methane: indeed the depression of the solubility coefficient with respect to the pure gas value is similar for both gases, when reported at the same concentration of the second gas.The real, mixed gas solubility selectivity is in general higher than the ideal value calculated from pure gas behavior. The ratio between real and ideal solubility selectivity increases with CO 2 concentration in the membrane, according to a single mastercurve, reaching a maximum value of 4, and increases also with the ratio between CO 2 and CH 4 concentration in the membrane. In particular, as in the case of other glassy polymers, the real solubility selectivity of CO 2 over CH 4 is higher than the ideal value if c(CO 2 )>c(CH 4 ), and it is lower than the ideal value if the opposite condition holds true. Such behavior occurs because the competition for sorption is normally less effective on the more abundant penetrant in the polymer. A selectivity-solubility performance plot can be drawn for this system.

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“…4,18 Although the distance between the spiro centers on the chains was the same as PIM-1, the gas permeability and selectivity of the new PIMs could be tuned by the type of pendent groups as a consequence of space filling and rigidity increase. In the present work, we focus on the design of new ladder-type PIM structures which contain other highly kinked units and/or those having a longer distance between the twist or spiro centers to improve the understanding of structure-property relationships.…”

Section: Introductionmentioning

confidence: 99%

Polymers of Intrinsic Microporosity with Dinaphthyl and Thianthrene Segments

et al. 2010

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Polymers of intrinsic microporosity with Dinaphtyl and Tianthrene segments Du, Naiying; Robertson, Gilles P.; Pinnau, Ingo; Guiver, Michael D.Contact us / Contactez nous: nparc.cisti@nrc-cnrc.gc.ca. University, Seoul 133-791, South Korea Received August 24, 2010; Revised Manuscript Received September 11, 2010 ABSTRACT: Novel intrinsically microporous homopolymers and copolymers derived from PIM-1 monomers (5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethylspirobisindane and 2,3,5,6-tetrafluoroterephthalonitrile) with two additional monomers;tetrahydroxydinaphthyl and tetrafluorotetraoxide thianthrene;are reported as potential materials for membrane-based gas separations. The resulting copolymers prevent efficient space packing of the stiff polymer chains and consequently exhibit analogous behavior to that of PIM-1, the most widely reported polymer in this class of materials. In addition, the copolymerization provides high molecular weight copolymers and low polydispersity if the polymerization reactions were conducted at elevated temperature for an extended period of time. Detailed structural characterization of the new monomers and polymers was determined by 1 Ha n d 19 F nuclear magnetic resonance spectroscopy (NMR). The thermal properties were detected by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer free volume was calculated from the polymer density and specific van der Waals volume. Under the same testing conditions, the homopolymer containing thianthrene units and most of the analogous copolymers have an excellent combination of properties with good film-forming characteristics. The gas transport properties show higher selectivity for gas pairs such as O 2 /N 2 ,C O 2 /N 2 , and H 2 /N 2 with a corresponding decrease in permeability compared to PIM-1. This work also demonstrates that significant improvements in properties may be obtained through copolymers of intrinsic microporosity (CoPIM)s. Furthermore, this work extends the spectrum of high molecular weight soluble PIMs beyond those reported previously.

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Polymers of Intrinsic Microporosity Derived from Novel Disulfone-Based Monomers

Cited by 136 publications

References 38 publications

Azide‐based Cross‐Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation

Azide‐based Cross‐Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation

Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Polymers of Intrinsic Microporosity with Dinaphthyl and Thianthrene Segments

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