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Polymer membranes with excellent thermomechanical properties and good gas separation performance are desirable for efficient CO2 separation. A series of copolyimide membranes are prepared for the first time using PIM-PI-1, a hard segment with high CO2 permeability, and poly(ethylene glycol)/poly(propylene glycol) (PEG/PPG), a soft segment with high CO2 selectivity. Two different unit polymers are combined to compensate the limitations of each polymer (e.g., the fast aging and moderate selectivity of PIM-PI-1 and the poor mechanical properties and lower permeability of PEG/PPG). The corresponding PIM-(durene-PEG/PPG) membranes exhibit an excellent combination of mechanical properties and gas separation performance compared to the typical PI-PEG-based copolymer membrane. The improved mechanical property is attributed to the unique chain threading and the reinforcement between the spiro unit of PIM and the flexible PEG/PPG at the molecular level, which has not previously been exploited for membranes. The PIM-(durene-PEG/PPG) membranes show a high CO2 permeability of 350-669 Barrer and a high CO2/N2 selectivity of 33.5-40.3. The experimental results are further evaluated with theoretical results obtained from molecular simulation studies, and a very good agreement between the experimental results and simulation results is found. Moreover, the PIM-(durene-PEG/PPG) copolymer membranes display excellent anti-aging performance for up to 1 year.

Mixed-matrix membranes (MMMs) with an ideal polymer-filler interface and high gas separation performance are very challenging to fabricate because of incompatibility between the fillers and the polymer matrix. This work provides a simple technique to prepare a series of cross-linked MMMs (xMMM@n) by covalently attaching UiO-66-NB metal-organic frameworks (MOFs) within the PEG/PPG-PDMS copolymer matrix via ring-opening metathesis polymerization and in situ membrane casting. The norbornene-modified MOF (UiO-66-NB) is successfully copolymerized and dispersed homogeneously into a PEG/PPG-PDMS matrix because of very fast polymer formation and strong covalent interaction between MOFs and the rubbery polymer. A significant improvement in gas permeability is achieved in membranes up to a 5 wt % MOF loading compared to the pristine polymer membrane without affecting selectivity. The CO2/N2 separation performance of xMMM@1, xMMM@3, and xMMM@5 with 1, 3, and 5 wt % MOF loading, respectively, surpassed Robeson's 2008 upper bound. In addition, the best performing membrane, xMMM@3 (PCO2 = 585 Barrer and CO2/N2 ∼53), approaches the 2019 upper bound, indicating that the cross-linked MMMs (xMMM@n) are very promising for CO2 separation from flue gas. The experimental results of our study were evaluated and are supported by theoretical data obtained using the Maxwell model for MMMs. Moreover, the developed MMMs, xMMM@ns, displayed outstanding antiplasticization performance at pressures of up to 25 atm and very stable antiaging performance for up to 11 months with good temperature switching behaviors.

We chemically modify a commercially available elastomeric triblock copolymer, poly(styrene-b-ethylene-co-butylene-b-styrene) SEBS, to produce quaternary ammonium-functionalized hexyl bis(quaternary ammonium)-mediated partially-crosslinked SEBSs with different grafting degree of the conducting head groups as highly conductive and stable anion exchange membranes (AEMs). In an attempt to achieve a high ion exchange capacity and hence conductivity of the corresponding membranes without causing ‘gelation’, which these types of SEBS polymers typically experience, we use a SEBS with a high content (57%) of styrene, and graft the quaternary ammonium (QA) as both a crosslinker and the conducting head group on the side chain of the SEBS. The partial crosslinking approach, in combination with introducing these QA-conducting head groups as the side chain of the SEBS, helps to form larger ion clusters, and also to form a nano-phase morphology with long-range connecting channels. This induced the highest ion conductivity, 174.8 mS cm−1 at 80 °C, reported to date among these types of SEBS series. In addition, we obtain excellent cell performance with a current density of 450 mA cm−2 at 0.6 V and a peak power density of 315 mW cm−2 at 95% RH and 60 °C using the corresponding AEM.

Rubbery polymer membranes prepared from CO2-philic PEO and/or highly permeable PDMS are desired for efficient CO2 separation from light gases (CH4 and N2). Poor mechanical properties and size-sievi...

A series of bisimidazolium PEG-mediated crosslinked polyimides (BI-PEG-xPIs) with different PEG chain lengths were prepared for CO2 separation membranes. Both the ionic group (bisimidazolium) and PEG were used not only as CO2-solubilizing groups to enhance the CO2 selectivity but also as crosslinkers to inhibit plasticization. The crosslinked BI-PEG-xPI membranes displayed excellent chemophysical properties, together with high CO2/N2 (up to 31) and CO2/CH4 (up to 46) permselectivities while maintaining high CO2 permeability (up to 350 Barrer) due to their high solubility and solubility selectivity. Moreover, the crosslinked membrane showed good plasticization resistance up to 25 atm. Finally, the chain length effects of the crosslinkers on the physicochemical properties and the gas separation performance of the corresponding membranes are also discussed.

Polymer membranes with excellent thermomechanical properties and good gas separation performance are desirable for efficient CO

Thin-film composite mixed matrix membranes (CMMMs) were fabricated using interfacial polymerization to achieve high permeance and selectivity for CO2 separation. This study revealed the role of substrate properties on performance, which are not typically considered important. In order to enhance the affinity between the substrate and the coating solution during interfacial polymerization and increase the selectivity of CO2, a mixture of polyethylene glycol (PEG) and dopamine (DOPA) was subjected to a spinning process. Then, the surface of the substrate was subjected to interfacial polymerization using polyethyleneimine (PEI), trimesoyl chloride (TMC), and sodium dodecyl sulfate (SDS). The effect of adding SDS as a surfactant on the structure and gas permeation properties of the fabricated membranes was examined. Thin-film composite hollow fiber membranes containing modified graphene oxide (mGO) were fabricated, and their characteristics were analyzed. The membranes exhibited very promising separation performance, with CO2 permeance of 73 GPU and CO2/N2 selectivity of 60. From the design of a membrane substrate for separating CO2, the CMMMs hollow fiber membrane was optimized using the active layer and mGO nanoparticles through interfacial polymerization.

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.

We synthesized copolymers consisting mostly of physically stable rigid polyimide (PI) and a low content of highly permeable rubbery polydimethylsiloxane (PDMS), that were crosslinked by CO2-philic ionic piperazinium groups attached to the side chains of the copolymers. These crosslinked copolymers (xPI-PDMSs) were fashioned into membranes that showed very high levels of thermochemical stability and excellent CO2 separation performance (PCO2 of 799 Barrer and CO2/N2 permselectivity of 15.7). The inclusion of the piperazinium groups not only endowed these xPI-PDMS membranes with increased selectivity for CO2, but also good resistance to CO2 plasticization. The effect of PDMS content on morphology and CO2 separation properties of xPI-PDMS was also investigated.

Random copolymers made of both (PIM-polyimide) and (6FDA-durene-PI) were prepared for the first time by a facile one-step polycondensation reaction. By combining the highly porous and contorted structure of PIM (polymers with intrinsic microporosity) and high thermomechanical properties of PI (polyimide), the membranes obtained from these random copolymers [(PIM-PI)-(6FDA-durene-PI)] showed high CO2 permeability (&gt, 1047 Barrer) with moderate CO2/N2 (&gt, 16.5) and CO2/CH4 (&gt, 18) selectivity, together with excellent thermal and mechanical properties. The membranes prepared from three different compositions of two comonomers (1:4, 1:6 and 1:10 of x:y), all showed similar morphological and physical properties, and gas separating performance, indicating ease of synthesis and practicability for production in large scale. The gas separation performance of these membranes at various pressure ranges (100&ndash, 1500 torr) was also investigated.

Multiblock copolymers based on both a PIM-PI block and a 6FDA-PI block, that are [(PIM-PI)x-b-(PI)y], with different block compositions (x:y = 1:4, 1:6 and 1:8) have been prepared for the first time. Through a combination of experimental and simulation approaches, the effects of the compositions of the PIM-PI units on the void distribution and gas transport properties in [(PIM-PI)x-b-(PI)y] block copolymer membranes are fully explored. By combining the effects of the high free volume of amorphous PIMs (polymers with intrinsic microporosity) brought about by the rigidity of the macromolecular chains and their contorted backbones with the excellent chemophysical properties of PIs (polyimides) in a block copolymer approach, our [(PIM-PI)x-b-(PI)y] membranes showed excellent thermomechanical properties as well as very good gas-separation performances, placing them well above the upper bound for CO2/N2 and CO2/CH4, especially at low pressures, and making them comparable to even the highly permeable PIM-1. The block copolymer membrane, with a 1:4 block ratio between the (PIM-PI) and (6FDA-PI) units, denoted here as (PIM-PI)-b-(PI)(1:4), showed a well-connected morphology of the permeable phase and displayed very high CO2 permeability of 3011 Barrer as well as moderate CO2/CH4 (16.0) and CO2/N2 (17.0) permselectivities, together with Tmax above 520 °C and Young’s modulus above 2.1 GPa.

In this study, precursor molecules based on PEG/PPG and polydimethylsiloxane (PDMS), both widely used rubbery polymers, were copolymerized with bulky adamantane into copolymer membranes. Ring-opening metathesis polymerization (ROMP) was employed during the polymerization process to create a structure with both ends crosslinked. The precursor molecules and corresponding polymer membranes were characterized using various analytical methods. The polymer membranes were fabricated using different compositions of PDMS and adamantane, to determine how the network structure affected their gas separation performance. PEG/PPG, in which CO2 is highly soluble, was copolymerized with PDMS, which has high permeability, and adamantane, which controlled the crosslinking density with a rigid and bulky structure. It was confirmed that the resulting crosslinked polymer membranes exhibited high solubility and diffusivity for CO2. Further, their crosslinked structure using ROMP technique made it possible to form good films. The membranes fabricated in the present study exhibited excellent performance, i.e., CO2 permeability of up to 514.5 Barrer and CO2/N2 selectivity of 50.9.

Poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) triblock copolymers are prepared with 50% hexyl quaternary ammonium (HQA) and 20% alkyl chains of different chain lengths: C4 (50HQA-20C4-SEBS) and C12 (50HQA-20C12-SEBS). Their physicochemical and electrical properties are investigated for use as novel alkaline anion exchange membranes. In most other comb-type polymers, the alkyl chain is introduced as a hydrophilic spacer unit between the polymer backbone and conducting head group. In the current study, additional alkyl chains are grafted onto the SEBS polymer as hydrophobic side chains as well as typical hydrophilic side chains. Introduction of this extra hydrophobic alkyl spacer group is done to obtain well-connected morphology, increased free volume, enhanced water uptake and related conductivity, together with improved physicochemical properties of the membranes obtained. The results are compared with HQA-functionalized SEBS without the hydrophobic alkyl spacer group (50HQA-20C0-SEBS), and the effects of the alkyl chain lengths on the structure of polymers and physicochemical properties of the corresponding membranes are investigated.

We synthesized copolymers consisting mostly of physically stable rigid polyimide (PI) and a low content of highly permeable rubbery polydimethylsiloxane (PDMS), that were crosslinked by CO