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1.
Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) has been crosslinked using 4,4′‐diazidobenzophenone bisazide to improve its chemical and physical stability over time. Crosslinking PTMSP renders it insoluble in good solvents for the uncrosslinked polymer. Gas permeability and fractional free volume decreased as crosslinker content increased, while gas sorption was unaffected by crosslinking. Therefore, the reduction in permeability upon crosslinking PTMSP was due to decrease in diffusion coefficient. Compared with the pure PTMSP membrane, the permeability of the crosslinked membrane is initially reduced for all gases tested due to the crosslinking. By adding nanoparticles (fumed silica, titanium dioxide), the permeability is again increased; permeability reductions due to crosslinking could be offset by adding nanoparticles to the membranes. Increased selectivity is documented for the gas pairs O2/N2, H2/N2, CO2/N2, CO2/CH and H2/CH4 using crosslinking and addition of nanoparticles. Crosslinking is successful in maintaining the permeability and selectivity of PTMSP membranes and PTMSP/filler nanocomposites over time. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

2.
The permeability and diffusivity properties of four gases—oxygen, nitrogen, carbon dioxide and methane—have been obtained for membranes prepared by the photocrosslinking of a mixture of chlorosulfonated polyethylene, acting as a binder, and a series of acrylic and methacrylic monomers. These measurements have been performed in the range 20°C to 50°C, and the activation energies have also been determined. These data are presented in comparison with those previously obtained in a crosslinked system in which the binder was not chlorosulfonated polyethylene but an aliphatic polyurethane. Both polymeric systems show similar permselectivities for the gas pairs O2/N2 (near 5) and CO2/CH4 (near 12), though overall permeability is about three times lower in the chlorosulfonated polyethylene—based polymer because of the smaller diffusion coefficients. The permeation and diffusion results are discussed in terms of the final structure of the photocrosslinked polymeric system, and it is concluded that it is the binder which is mostly responsible for the gas transport properties of these crosslinked materials.  相似文献   

3.
Here, we report the synthesis and the study of gas‐transport properties of crosslinked highly permeable copolymers from Si‐containing norbornene derivatives. The initial high‐molecular‐weight copolymers were prepared via addition copolymerization of 3‐trimethylsilyltricyclo[4.2.1.02,5]non‐7‐ene (TCNSi1) with 3‐triethoxysilyltricyclo[4.2.1.02,5]non‐7‐ene (TCNSiOEt) in good or high yields using a Pd‐catalyst. The obtained copolymers included up to 10 mol% of TCNSiOEt units bearing reactive Si–O–C‐containing substituents. The crosslinking was readily realized by using simple sol–gel chemistry in the presence of Sn‐catalyst. The formed crosslinked copolymers were insoluble in common organic solvents. Permeability coefficients of various gases (He, H2, O2, N2, CO2, CH4, C2H6, C3H8, n‐C4H10) in these copolymers before and after crosslinking were determined and the influence of the incorporated TCNSiOEt units as well as the crosslinking on gas transport properties were established. As a result, it was found that only a small reduction of gas‐permeability was observed when TNCSiOEt units were incorporated into the main chains, and the copolymers were crosslinked. At the same time, the selectivity for C4H10/CH4 pair was increased. The suggested approach has allowed obtaining crosslinked polymers from Si‐containing monomers without a loss of the main membrane characteristics. POLYM. ENG. SCI., 59:2502–2507, 2019. © 2019 Society of Plastics Engineers  相似文献   

4.
In this article, three novel polymers based on poly(2,5‐benzimidazole) (ABPBI) were synthesized by introducing propyl, isobutyl or n‐butyl groups to its side chain through an alkyl substitution reaction. FTIR and 13C NMR were applied to confirm the formation of corresponding chemical groups. Their physical properties including crystallinity, thermal stability, mechanical strength, and micro‐morphology were also characterized. Their solubility in common solvents were also tested to see if the modification will bring any improvement. Gas permeation properties of three derivative membranes prepared by a casting and solvent‐evaporation method were tested with pure gases including H2, N2, O2, CH4, and CO2. It has been revealed that gas with a smaller molecular size owned a larger permeability. This means gas permeation in all prepared membranes should be diffusivity selective. Among all three modified ABPBI membranes, isobutyl substitution modified ABPBI (IBABPBI) showed the best selectivity of H2 over other gases such as N2 (~185) and CO2 (~6.3) with a comparable permeability (~9.33 barrer) when tested at 35°C and 3.0 atm. Testing temperature increase facilitated gas permeation for all three membranes obviously; while in term of gas selectivity temperature increase showed diverse alteration because it brought variable impact on gas solubility of different gases. Even so, IBABPBI membrane still owned acceptable selectivity of H2 over N2 (~118) and CO2 (~6.3) with an almost doubled permeability (~17.5 barrer) when tested at 75°C and 3.0 atm. Additional tests showed that running at high pressure did not bring any obvious deterioration to gas separation performance of IBABPBI membrane. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40440.  相似文献   

5.
Ion beam irradiation is an easily controlled method to modify the chemical structure and microstructure of polymers including the fractional free volume, free volume distribution and chain mobility, thus altering the gas transport properties of the irradiated polymers. The previous paper focused on the impact of H+ ion beam irradiation on chemical structural evolution of the polyimide Matrimid®. This paper focuses on the impact of H+ ion beam irradiation on microstructure and gas permeation properties of Matrimid®. Irradiation at low ion fluence resulted in slight decreases in permeabilities for five gases (i.e., He, CO2, O2, N2, and CH4) with increases in permselectivities for some gas pairs (e.g., He/CH4 and He/N2). In contrast, irradiation at relatively high ion fluences resulted in simultaneous increases in permeabilities and permselectivities for most gas pairs (e.g., He/CH4, He/N2, O2/N2, and CO2/CH4). While Matrimid® has bulk gas permeation properties that are below the range of commercially interesting polymers, samples irradiated at high ion fluences exhibited significant improvement in gas separation performances. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1670–1680, 2007  相似文献   

6.
Mixed matrix membranes (MMMs) prepared with 6FDA‐DAM polymer using ordered mesoporous silica MCM‐41 spheres (MSSs), Grignard surface functionalized MSSs (Mg‐MSSs) and hollow zeolite spheres are studied to evaluate the effects of surface modification on performance. Performance near or above the so‐called permeability‐selectivity trade‐off curve was achieved for the H2/CH4, CO2/N2, CO2/CH4, and O2/N2 systems. Two loadings (8 wt % and 16 wt %) of MSSs were tested using both constant volume and Wicke–Kallenbach sweep gas permeation systems. Besides single gas H2, CO2, O2, N2, and CH4 tests, mixed gas (50/50 vol %) selectivities were obtained for H2/CH4, CO2/N2, CO2/CH4, and O2/N2 and found to show enhancements vs. single gases for CO2 including cases. Mg‐MSS/6FDA‐DAM was the best performing MMM with H2/CH4, CO2/N2, CO2/CH4, and O2/N2 separation selectivities of 21.8 (794 Barrer of H2), 24.4 (1214 Barrer of CO2), 31.5 (1245 Barrer of CO2), and 4.3 (178 Barrer of O2), respectively. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4481–4490, 2015  相似文献   

7.
A series of copolyimides were prepared from 2,4,6-trimethyl-1,3-phenylenediamines (3MPDA), 3,3′,4,4′-benzophenone tetracarboxyl dianhydride (BTDA), and pyromellitic dianhydride (PMDA). Modification of the copolyimides by ultraviolet irradiation were carried out. Gas permeabilities of H2, O2, and N2 through the copolyimides and photochemically crosslinked copolyimides were measured at temperatures from 30 to 90°C. The relationships between gas permeabilities and temperature are in agreement with the Arrhenius equation. The structure of photochemically crosslinked copolyimides were characterized by Fourier transform infrared and gel measurement methods. Linear relationships between both log P and Ep and the volume fraction of PMDA–3MPDA exist. Photochemically crosslinking modification result in a decrease in gas permeability and an increase in Ep and α(H2/N2) for all the copolyimides. For H2/N2 separation, photochemically crosslinked copolyimides are of higher gas permeabilities and permselectivities simultaneously than normal polyimides. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 521–526, 1999  相似文献   

8.
C/CMS composite membranes derived from poly(furfuryl alcohol) (PFA) polymerized by iodine catalyst were prepared. Gas separation performance was investigated by molecular probe study with pure gases (H2, CO2, O2, N2, and CH4) at 25 °C. The pyrolysis behaviour of PFA was studied by TG and DTG. The surface morphology of C/CMS composite membranes was observed by SEM and HRTEM. The results show a C/CMS composite membrane with uniform and defect-free thin top layer can be prepared by the PFA liquid in only one coating step. The C/CMS composite membranes have excellent gas separation properties for the gas pairs such as H2/N2, CO2/N2, O2/N2 and CO2/CH4, the permselectivities for above gas pairs in same sequence were 124.72, 12.74, 9.12 and 15.91 respectively. Compared to carbon membranes derived from PFA polymerized by acid catalyst, the carbon membranes obtained from PFA polymerized by iodine catalyst have slightly lower permselectivity, but higher permeance.  相似文献   

9.
A series of blend membranes of poly(phenyl sulfone) (PPSU) with poly(bisphenol A‐co‐4‐nitrophthalic anhydride‐co‐1,3‐phenylenediamine) (PBNPI) were prepared through a solution casting method. This was done to examine the permeation characteristics of oxygen and nitrogen. The effect of the PPSU/PBNPI ratio on the membrane structure and O2/N2 separation performance were investigated. The results show that the permeability increased remarkably with the content of PPSU, whereas the selectivity decreased slightly. To enhance the selectivity of O2/N2, the blend membranes were further crosslinked with a p‐xylylenediamine agent via the immersion method. According to the Fourier transform infrared analysis, the N? H group was formed on the imide group of PBNPI. Therefore, we suggest that during the crosslinking modification, the PBNPI served as a crosslinkable polymer; this resulted in increased crosslinking efficiency with PBNPI content. The high‐resolution X‐ray diffraction and melting point method results show that crosslinking modification improved the selectivity with an acceptable loss in permeability along with increased crystallinity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

10.
Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO2/N2 and CO2/CH4 selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO2/CH4 and CO2/N2 at the three examined feed pressures of 4, 8 and 12 atm.  相似文献   

11.
Permeation properties of pure H2, N2, CH4, C2H6, and C3H8 through asymmetric polyetherimide (PEI) hollow‐fiber membranes were studied as a function of pressure and temperature. The PEI asymmetric hollow‐fiber membrane was spun from a N‐methyl‐2‐pyrrolidone/ethanol solvent system via a dry‐wet phase‐inversion method, with water as the external coagulant and 50 wt % ethanol in water as the internal coagulant. The prepared asymmetric membrane exhibited sufficiently high selectivity (H2/N2 selectivity >50 at 25°C). H2 permeation through the PEI hollow fiber was dominated by the solution‐diffusion mechanism in the nonporous part. For CH4 and N2, the transport mechanism for gas permeation was a combination of Knudsen flow and viscous flow in the porous part and solution diffusion in the nonporous part. In our analysis, operating pressure had little effect on the permeation of H2, CH4, and N2. For C2H6 and C3H8, however, capillary condensation may have occurred at higher pressures, resulting in an increase in gas permeability. As far as the effect of operating temperature was concerned, H2 permeability increased greatly with increasing temperature. Meanwhile, a slight permeability increment with increasing temperature was noted for N2 and CH4, whereas the permeability of C2H6 and C3H8 decreased with increasing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 698–702, 2002  相似文献   

12.
This work reports the synthesis and assessment of random aromatic co‐polyamides containing two different bulky pendant groups. The random aromatic co‐polyamides are synthesized combining the monomers 5‐tert‐butylisophthalic acid and 5‐(9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarboximido)isophthalic acid with three different diamines. The random aromatic co‐polyamides are readily soluble and possess inherent viscosities in the range of 0.47–0.60 dL g−1. Co‐polyamide dense membranes are amorphous, and flexible with both good tensile strength (56.2–57.5 MPa) and tensile modulus (1.3–1.6 GPa). Permeability coefficients of the co‐polyamide dense membranes are assessed for the gases He, O2, N2, CH4, and CO2. It is found that the combination of two bulky pendant groups, dibenzobarrelene and tert‐butyl, in the backbone of the co‐polyamides improves the gas permeability coefficient in comparison with their corresponding homopolyamides. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45884.  相似文献   

13.
Composite membranes containing carbon nanofibers (CNFs) and Matrimid were prepared by a solution‐casting method. Prepared Matrimid–CNF composite membranes were characterized with X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and mechanical testing techniques. The mechanical properties of the composite membranes increased over that of the pristine polymeric membranes. To develop a broad fundamental understanding of the connection between the composite architecture and gas‐transport properties, both the gas‐permeability and gas‐separation characteristics were evaluated. The gas‐transport properties of the Matrimid–CNF composite membrane was measured with a single gas‐permeation setup (He, H2, N2, CH4 and CO2) at ambient temperature with the variable‐volume method. The incorporation of CNFs (0.5–10 wt %) into the Matrimid matrix resulted in approximately a 22% reduction in the gas permeation of various gases, (H2, He, CO2, N2, and CH4). Moreover, an improvement of 1.5 times in the gas selectivity was observed for CO2/CH4, H2/CH4, He/CH4, and H2/N2 compared to pristine polymeric membrane. Hence, such polymer–CNF composite membranes could be suitable for gas‐separation applications with high purity requirements. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46019.  相似文献   

14.
Permeability coefficients of H2, O2, and N2 were measured under 10 atm at the temperature from ambient temperature up to 150°C in a series of structurally different aromatic homo-and copolyimides, which were prepared from 4,4′-oxydianiline (ODA) or 4,4′-methylene dianiline (MDA) with various aromatic dianhydrides. The study shows that the molecular structure of the polyimides strongly influences gas permeability and permselectivity. As a result, the permeability coefficients of the polyimide membranes for each gas vary by over two orders of magnitude. In general, among the polyimide membranes studied, the increase in permeability of polymers is accompanied by the decrease in permselectivity, and the MDA-based polyimide membranes have higher permeability than ODA-based ones. Among the polyimides prepared from bridged dianhydrides, the permeability coefficients to H2, O2, and N2 are progressively increased in the order BPDA <BTDA <ODPA ∼ TDPA <DSDA <SiDA <6FDA, while H2/N2 and O2/N2 permselectivity coefficients are progressively decreased in the same order. The copolyimide membranes, which were prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride (SiDA), and ODA, have favorable gas separation properties and are useful for H2/N2 separation applications. © 1996 John Wiley & Sons, Inc.  相似文献   

15.
A crosslinked nanofibrous cation exchange membrane with high ion permeability and robust mechanical properties was fabricated by electrospinning. Copolymer, poly(sodium styrene sulfonate‐co‐2‐hydroxyethyl methacrylate), was selected as the electrospun material. Fourier transform infrared spectroscopy, 1H‐nuclear magnetic resonance, and scanning electron microscopy were employed to characterize the copolymer and nanofibrous mat. After a series of preliminary experiments, the proper solvents and their ratio, H2O/tetrahydrofuran/N,N′‐dimethylformamide (2/1/3 vol/vol/vol), was selected and the electrospinning optimal parameters were determined by orthogonal experiments. Formaldehyde vapor was employed to crosslink the mat. It was observed that the water sorption decreased from 47.9% to 18.4% as the crosslinking time increased from 20 to 32 h. The robust mat with the high tensile strength of 4.85 MPa and 40% elongation at break was obtained at 28 h. The permselectivities of Na+, K+, and Ca2+ were 89%, 85%, and 81%, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45541.  相似文献   

16.
A series of poly(amide‐co‐poly(propylene glycol)) (PA‐PPG) random copolymers with different content of PPG were designed by polycondensation reaction. These random copolymers were blended up to 60% with commercially available Pebax 2533. The blend membranes were characterized by Fourier‐transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), scanning electron microscope (SEM). Gas permeation properties of these blend membranes were investigated using five single‐gases (CO2, H2, O2, CH4, and N2) at different temperature of 25–55°C and 1.0 atm. The impacts of content of PA‐PPG with different PPG content and operating temperature on CO2 separation properties of Pebax/PA‐PPG blend membranes were studied. The results showed that CO2 permeability gradually increased with the increasing operating temperature, whereas CO2 permeability gradually decreased with the increase in content of PA‐PPG. CO2/N2 selectivity gradually increased with the increase in content of PA‐PPG. In particular, Pebax/PA‐PPG (50)–60% displayed excellent CO2 and O2 separation properties (PCO2 = 79.7 Barrer and PO2 = 13.6 Barrer, CO2/N= 34.7 and O2/N= 5.9) at 25°C and 1.0 atm. POLYM. ENG. SCI., 59:E14–E23, 2019. © 2018 Society of Plastics Engineers  相似文献   

17.
《Polymer Composites》2017,38(7):1363-1370
Mixed matrix membranes offer major advantages in gas separation processes due to desirable properties found in both organic and inorganic membranes. In this study, a novel mixed matrix membrane was prepared for such application by incorporating iron benzene‐1,3,5‐tricarboxylate (Fe‐BTC) into the poly(amide‐6‐b‐ethylene oxide) (Pebax1657) polymer. Membranes with various loadings of 5, 10, and 20 wt% Fe‐BTC in the polymer matrix were fabricated to investigate the effect of filler loading on the membrane performance. Membranes, prepared by solution‐casting were characterized by scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared, X‐ray diffraction, and tensile test. Pure gas separation of CO2, CH4, and N2 and ideal gas selectivity of CO2/CH4 and CO2/N2 were performed and permeation tests were carried out under 4, 8, and 12 bar pressures. Results show that adding Fe‐BTC into the Pebax1657 matrix improved both permeability and selectivity of the filled membranes. For instance, 10 wt% loading of Fe‐BTC into the Pebax1657 matrix led to CO2 permeability increase of 49% as well as CO2/CH4 and CO2/N2 selectivities enhancements of about 36% and 16%, respectively. POLYM. COMPOS., 38:1363–1370, 2017. © 2015 Society of Plastics Engineers  相似文献   

18.
Cellulose acetate (CA) is well known glassy polymer used in the fabrication of gas‐separation membranes. In this study, 5,11,17,23‐tetrakis(N‐morpholinomethyl)‐25,26,27,28‐tetrahydroxycalix[4]arene (CL) was blended with CA to study the gas‐permeation behavior for CO2, N2, and CH4 gases. We prepared the pure CA and CA/CL blended membranes by following a diffusion‐induced phase‐separation method. Three different concentrations of CL (3, 10, and 30 wt %) were selected for membrane preparation. The CA/CL blended membranes were then characterized via Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X‐ray diffraction analysis. The homogeneous blending of CL and CA was confirmed in the CA/CL blended membranes by both SEM and AFM analysis. In addition to this, the surface roughness of the CA/CL blended membranes also increased with increasing CL concentration. FTIR analysis described the structural modification in the CA polymer after it was blended with CL too. Furthermore, CL improved the tensile strength of the CA membrane appreciably from 0.160 to 1.28 MPa, but this trend was not linear with the increase in the CL concentration. CO2, CH4, and N2 gases were used for gas‐permeation experiments at 4 bars. With the permeation experiments, we concluded that permeability of N2 was higher in comparison to those of CO2 and CH4 through the CA/CL blended membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39985.  相似文献   

19.
The development of desirable chemical structures and properties in nanocomposite membranes involve steps that need to be carefully designed and controlled. This study investigates the effect of adding multiwalled nanotubes (MWNT) on a Kapton–polysulfone composite membrane on the separation of various gas pairs. Data from Fourier transform infrared spectroscopy and scanning electron microscopy confirm that some studies on the Kapton–polysulfone blends are miscible on the molecular level. In fact, the results indicate that the chemical structure of the blend components, the Kapton–polysulfone blend compositions, and the carbon nanotubes play important roles in the transport properties of the resulting membranes. The results of gas permeability tests for the synthesized membranes specify that using a higher percentage of polysulfone (PSF) in blends resulted in membranes with higher ideal selectivity and permeability. Although the addition of nanotubes can increase the permeability of gases, it decreases gas pair selectivity. Furthermore, these outcomes suggest that Kapton–PSF membranes with higher PSF are special candidates for CO2/CH4 separation compared to CO2/N2 and O2/N2 separation. High CH4, CO2, N2, and O2 permeabilities of 0.35, 6.2, 0.34, and 1.15 bar, respectively, are obtained for the developed Kapton–PSF membranes (25/75%) with the highest percentage of carbon nanotubes (8%), whose values are the highest among all the resultant membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43839.  相似文献   

20.
Composite carbon molecular sieve membranes (c-CMSM) were prepared in a single dipping–drying–carbonization step from phenolic resin solutions (12.5–15 wt.%) loaded with boehmite nanoparticles (0.5–1.2 wt.%). A carbon matrix with well-dispersed Al2O3 nanowires was formed from the decomposition of the resin and dehydroxylation of boehmite. The effect of the carbon/Al2O3 ratio on the porous structure of the c-CMSM was accessed based on the pore size distribution and gas permeation toward N2, O2, CO2, He, H2, C3H6 and C3H8. c-CMSM with higher carbon/Al2O3 ratios had a more open porous structure, exhibiting higher permeabilities and lower permselectivities. c-CMSM performance was above the upper bound curves for polymeric membranes for several gas pairs, particularly for C3H6/C3H8 (permeability toward C3H6 of 420 barrer and permselectivity of 18.1 for a c-CMSM with carbon/Al2O3 ratio of 4.4).  相似文献   

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