Molecularly Mixed Composite Membranes for Gas Separation Based on Macrocycles Embedded in a Polyimide
Ontology highlight
ABSTRACT:
SUBMITTER: Vuono D
PROVIDER: S-EPMC10892679 | biostudies-literature | 2024 Feb
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:To improve the interfacial compatibility of mixed matrix membranes (MMMs) for gas separation, microporous polyimide particle (AP) was designed, synthesized, and introduced into intrinsic microporous polyimide matrix (6FDA-Durene) to form "all polyimide" MMMs. The AP fillers showed the feature of thermal stability, similar density with polyimide matrix, high porosity, high fractional free volume, large microporous dimension, and interpenetrating network architecture. As expected, the excellent interfacial compatibility between 6FDA-Durene and AP without obvious agglomeration even at a high AP loading of 10 wt.% was observed. As a result, the CO2 permeability coefficient of MMM with AP loading as low as 5 wt.% reaches up to 1291.13 Barrer, which is 2.58 times that of the pristine 6FDA-Durene membrane without the significant sacrificing of ideal selectivity of CO2/CH4. The improvement of permeability properties is much better than that of the previously reported MMMs, where high filler content is required to achieve a high permeability increase but usually leads to significant agglomeration or phase separation of fillers. It is believed that the excellent interfacial compatibility between the PI fillers and the PI matrix induce the effective utilization of porosity and free volume of AP fillers during gas transport. Thus, a higher diffusion coefficient of MMMs has been observed than that of the pristine PI membrane. Furthermore, the rigid polyimide fillers also result in the excellent anti-plasticization ability for CO2. The MMMs with a 10 wt.% AP loading shows a CO2 plasticization pressure of 300 psi.
| S-EPMC8073420 | biostudies-literature
Project description:A series of CO2-selective polyimides (CE-PDMS-PI-x) was synthesized by copolymerizing crown ether diamine (trans-diamino-DB18C6) and PDMS-diamine with 4,4'-(hexafluoroisopropylidene) di-phthalic anhydride (6FDA) through the polycondensation reaction. The structural characteristics of the copolymers and corresponding membranes were characterized by nuclear magnetic resonance (NMR), infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and gel permeation chromatography (GPC). The effect of PDMS loading on the CE-PDMS-PI-x copolymers was further analyzed and a very good structure-property relationship was found. A well-distributed soft PDMS unit played a key role in the membrane's morphology, in which improved CO2-separation performance was observed at a low PDMS content (5 wt %). In contrast, the fine-grained phase separation adversely affected the separation behavior at a certain level of PDMS loading, and the PDMS was found to provide a flexible gas-diffusion path, affecting only the permeability without changing the selective gas-separation performance for the copolymers with a PDMS content of 20% or above.
| S-EPMC8227709 | biostudies-literature
Project description:The rigid V-shaped Tröger's base (TB) unit has been proven efficacious in creating microporosity, making TB-based polyimides (PIs) exhibiting significant advantages in simultaneously increasing gas permeability and selectivity for the separation industry. However, TB-based PIs commonly display undesired mechanical performance due to the low molecular weight resulting from the evident steric hindrance and low reactivity of TB-containing diamines. Herein, a novel diamine-containing bisimide linkage (BIDA) has been synthesized and then polymerized with paraformaldehyde via a moderate "TB polymerization" strategy to furnish polymers simultaneously, including imide linkages and TB units in the polymer main chains, namely, TB-PIs. This TB polymerization strategy avoids the direct polymerization of dianhydride with low-reactivity TB diamine. After incorporating a meta-methyl substituent into BIDA diamine, the m-MBIDA diamine-derived m-MTBPI ultimately exhibits a high molecular weight, good tensile strength (90.4 MPa) and an outstanding fracture toughness (45.1 MJ/m3). And more importantly, the m-MTBPI membrane displays an evidently enhanced gas separation ability in comparison with BIDA-derived TBPI, with overall separation properties much closer to the 1991 Robeson upper bound. Moreover, no sign of plasticization appears for the m-MTBPI membrane when separating a high-pressure CO2/CH4 mixture (v/v = 1/1) up to 20 bar, with the CO2/CH4 mixed-gas separation performance approaching the 2018 upper bound.
| S-EPMC11859751 | biostudies-literature
Project description:The 6FDA-based network PI has attracted significant attention for gas separation. A facile strategy to tailor the micropore structure within the network PI membrane prepared by the in situ crosslinking method is extremely significant for achieving an advanced gas separation performance. In this work, the 4,4'-diamino-2,2'-biphenyldicarboxylic acid (DCB) or 3,5-diaminobenzoic acid (DABA) comonomer was incorporated into the 6FDA-TAPA network polyimide (PI) precursor via copolymerization. The molar content and the type of carboxylic-functionalized diamine were varied in order to easily tune the resulting network PI precursor structure. Then, these network PIs containing carboxyl groups underwent further decarboxylation crosslinking during the following heat treatment. Properties involving thermal stabilities, solubility, d-spacing, microporosity, and mechanical properties were investigated. Due to the decarboxylation crosslinking, the d-spacing and the BET surface areas of the thermally treated membranes were increased. Moreover, the content of DCB (or DABA) played a key role in determining the overall gas separation performance of the thermally treated membranes. For instance, after the heating treatment at 450 °C, 6FDA-DCB:TAPA (3:2) showed a large increment of about ~532% for CO2 gas permeability (~266.6 Barrer) coupled with a decent CO2/N2 selectivity~23.6. This study demonstrates that incorporating the carboxyl-containing functional unit into the PI backbone to induce decarboxylation offers a practical approach with which to tailor the micropore structure and corresponding gas transport properties of 6FDA-based network PIs prepared by the in situ crosslinking method.
| S-EPMC10220741 | biostudies-literature
Project description:Membrane processes are promising for energy-saving industrial applications. However, efficient separation for some valuable gas mixtures with similar characteristics, such as CH4/N2 and O2/N2, remains extremely challenging. Metal-organic framework (MOF) membranes have been attracting intensive attention for gas sieving, but it is difficult to manufacture MOF membranes in scalability and precisely tune their transport property. In this study, Gel-thermal processing of linker-mixed MOF crystal-glass composite membranes is reported directly, with the mechanism of adjusting metal-linker bond strengths and angles to disrupt long-range periodicity of MOFs and promote glass phase formation, for sharply sorption-preferential gas separation. This strategy can be realized by using a simple, solvent/precursor-less, and cost-effective gel-thermal approach with two steps of gel coating and thermal conversion, thereby constructing crystal-glass composite membranes in a controllable, processable, versatile, and environmentally friendly route. Moreover, the mixed linkers enable preferential gas affinities and the ultramicroporous glasses can eliminate any membrane defects. The membranes exhibit outstanding gas separation performance for the challenging systems of CH4/N2 and O2/N2, with mixture selectivities up to 9.3 and 9.6, respectively, far exceeding those of polymer, MOF, and mixed-matrix membranes. The study provides an available route for architecting high-performance membranes for gas separations.
| S-EPMC11791987 | biostudies-literature
Project description:Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the polymer matrix, to produce so-called mixed matrix membranes. In the present work, four different organic cages were dispersed in the poly(ether ether ketone) with cardo group, PEEK-WC. The m-xylyl imine and furanyl imine-based fillers yielded mechanically robust and selective films after silicone coating. Instead, poor dispersion of p-xylyl imine and diphenyl imine cages did not allow the formation of selective films. The H2, He, O2, N2, CH4, and CO2 pure gas permeability of the neat polymer and the MMMs were measured, and the effect of filler was compared with the maximum limits expected for infinitely permeable and impermeable fillers, according to the Maxwell model. Time lag measurements allowed the calculation of the diffusion coefficient and demonstrated that 20 wt % of furanyl imine cage strongly increased the diffusion coefficient of the bulkier gases and decreased the diffusion selectivity, whereas the m-xylyl imine cage slightly increased the diffusion coefficient and improved the size-selectivity. The performance and properties of the membranes were discussed in relation to their composition and morphology.
| S-EPMC8470936 | biostudies-literature
Project description:Three new isomeric 6FDA-based polyimide-ionenes, with imidazolium moieties and varying regiochemistry (para-, meta-, and ortho- connectivity), and composites with three different ionic liquids (ILs) have been developed as gas separation membranes. The structural-property relationships and gas separation behaviors of the newly developed 6FDA polyimide-ionene + IL composites have been extensively studied. All the 6FDA-based polyimide-ionenes exhibited good compatibility with the ILs and produced homogeneous hybrid membranes with the high thermal stability of ~380 °C. Particularly, [6FDA I4A pXy][Tf2N] ionene + IL hybrids having [C4mim][Tf2N] and [Bnmim][Tf2N] ILs offered mechanically stable matrixes with high CO2 affinity. The permeability of CO2 was increased by factors of 2 and 3 for C4mim and Bnmim hybrids (2.15 to 6.32 barrers), respectively, compared to the neat [6FDA I4A pXy][Tf2N] without sacrificing their permselectivity for CO2/CH4 and CO2/N2 gas pairs.
| S-EPMC6681123 | biostudies-literature
Project description:Nanocrystalline UiO-66 and its derivatives (containing -NH2, -Br, -(OH)2) were developed via pre-synthetic functionalization and incorporated into a polyimide membrane to develop a mixed-matrix membrane (MMM) for CO2/N2 separation. Incorporation of the non-functionalized UiO-66 nanocrystals into the polyimide membrane successfully improved CO2 permeability, with a slight decrease in CO2/N2 selectivity, owing to its large accessible surface area. The addition of other functional groups further improved the CO2/N2 selectivity of the polymeric membrane, with UiO-66-NH2, UiO-66-Br, and UiO-66-(OH)2 demonstrating improvements of 12%, 4%, and 17%, respectively. Further evaluation by solubility-diffusivity analysis revealed that the functionalized UiO-66 in MMMs can effectively increase CO2 diffusivity while suppressing N2 sorption, thus, resulting in improved CO2/N2 selectivity. Such results imply that the structural tuning of UiO-66 by the incorporation of various functional groups is an effective strategy to improve the CO2 separation performance of MMMs.
| S-EPMC7407110 | biostudies-literature
Project description:Thin-film composite mixed-matrix membranes (TFC-MMMs) have potential applications in practical gas separation processes because of their high permeance (gas flux) and gas selectivity. In this study, we fabricated a high-performance TFC-MMM based on a rubbery comb copolymer, i.e., poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate)-co-poly(oxyethylene methacrylate) (PBE), and metal-organic framework MOF-808 nanoparticles. The rubbery copolymer penetrates through the pores of MOF-808, thereby tuning the pore size. In addition, the rubbery copolymer forms a defect-free interfacial morphology with polymer-infiltrated MOF-808 nanoparticles. Consequently, TFC-MMMs (thickness = 350 nm) can be successfully prepared even with a high loading of MOF-808. As polymer-infiltrated MOF is incorporated into the polymer matrix, the PBE/MOF-808 membrane exhibits a significantly higher CO2 permeance (1069 GPU) and CO2/N2 selectivity (52.7) than that of the pristine PBE membrane (CO2 permeance = 431 GPU and CO2/N2 selectivity = 36.2). Therefore, the approach considered in this study is suitable for fabricating high-performance thin-film composite membranes via polymer infiltration into MOF pores.
| S-EPMC10053294 | biostudies-literature
Project description:Polynorbornenes are already used in a wide range of applications. They are also considered materials for polymer gas separation membranes because of their favorable thermal and chemical resistance, rigid backbone and varied chemistry. In this study, the use of 5-vinyl-2-norbornene (VNB), a new monomer in the field of gas separations, is investigated by synthesizing two series of polymers via a vinyl-addition polymerization. The first series investigates the influence of the VNB content on gas separation in a series of homo and copolymers with norbornene. The second series explores the influence of the crosslinking of polyvinylnorbornene (pVNB) on gas separation. The results indicate that while crosslinking had little effect, the gas separation performance could be fine-tuned by controlling the VNB content. As such, this work demonstrates an interesting way to significantly extend the fine-tuning possibilities of polynorbornenes for gas separations.
| S-EPMC6523562 | biostudies-literature