Molecular Mobility and Gas Transport Properties of Mixed Matrix Membranes Based on PIM-1 and a Phosphinine Containing Covalent Organic Framework.

Polymers with intrinsic microporosity (PIMs) are gaining attention as gas separation membranes. Nevertheless, they face limitations due to their pronounced physical aging. In this study, a covalent organic framework containing λ5-phosphinine moieties, CPSF-EtO, was incorporated as a nanofiller (concentration range 0-10 wt %) into a PIM-1 matrix forming dense films with a thickness of ca. 100 µm. The aim of the investigation was to investigate possible enhancements of gas transport properties and mitigating effects on physical aging. The incorporation of the nanofiller occurred on an nanoaggregate level with domains up to 100 nm, as observed by T-SEM and confirmed by X-ray scattering. Moreover, the X-ray data show that the structure of the microporous network of the PIM-1 matrix is changed by the nanofiller. As molecular mobility is fundamental for gas transport as well as for physical aging, the study includes dielectric investigations of pure PIM-1 and PIM-1/CPSF-EtO mixed matrix membranes to establish a correlation between the molecular mobility and the gas transport properties. Using the time-lag method, the gas permeability and the permselectivity were determined for N2, O2, CH4, and CO2 for samples with variation in filler content. A significant increase in the permeability of CH4 and CO2 (50% increase compared to pure PIM-1) was observed for a concentration of 5 wt % of the nanofiller. Furthermore, the most pronounced change in the permselectivity was found for the gas pair CO2/N2 at a filler concentration of 7 wt %.

High Gas Permeability in Aged Superglassy Membranes with Nanosized UiO-66-NH2 /cPIM-1 Network Fillers.

Superglassy membranes synthesised by polymers of intrinsic microporosity (PIMs) suffer from physical aging and show poor gas permeance over time, especially thin membranes, due to the fast rearrangement of nonequilibrium polymer chains. Herein, we constructed a novel PIM-1 thin film nanocomposite membrane (TFN) using nanosized UiO-66-NH2 (≈10 nm)/carboxylated PIM-1 (cPIM-1) as the composite filler. Unlike conventional fillers, which interact with the polymer only via the surface, the UiO-66-NH2 /cPIM-1 forms a stable three-dimensional (3D) network intertwining with the polymer chains, being very effective to impede chain relaxation, and thus physical aging. Nanosizing of UiO-66-NH2 was achieved by regulating the nucleation kinetics using carbon quantum dots (CQD) during the synthesis. This led to increased surface area, and hence more functional groups to bond with cPIM-1 (via hydrogen bonding between -NH2 and -COOH groups), which also improved interfacial compatibility between the 3D network and polymer chains avoiding defect formation. As a result, the novel TFN showed significantly improved performance in gas separation along with reduced aging (i.e. ≈6 % loss in CO2 permeability over 63 days); the aged membranes had a CO2 permeance of 2504 GPU and ideal selectivity values of 37.2 and 23.8 for CO2 /N2 and CO2 /CH4 , respectively.

Crosslinking of Branched PIM-1 and PIM-Py Membranes for Recovery of Toluene from Dimethyl Sulfoxide by Pervaporation.

Branched forms of the archetypal polymer of intrinsic microporosity PIM-1 and the pyridinecarbonitrile-containing PIM-Py may be crosslinked under ambient conditions by palladium(II) acetate. Branched PIM-1 can arise in polymerizations of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane with tetrafluoroterephthalonitrile conducted at a high set temperature (160 °C) under conditions, such as high dilution, that lead to a lower-temperature profile over the course of the reaction. Membranes of PIM-1 and PIM-Py crosslinked with palladium acetate are sufficiently stable in organic solvents for use in the recovery of toluene from its mixture with dimethyl sulfoxide (DMSO) by pervaporation at 65 °C. With both PIM-1 and PIM-Py membranes, pervaporation gives high toluene/DMSO separation factors (around 10 with a 77 vol % toluene feed). Detailed analysis shows that the membranes themselves are slightly selective for DMSO and it is the high driving force for toluene evaporation that drives the separation.

Methanol Vapor Retards Aging of PIM-1 Thin Film Composite Membranes in Storage.

Physical aging of glassy polymers leads to a decrease in permeability over time when they are used in membranes. This hinders the industrial application of high free volume polymers, such as the archetypal polymer of intrinsic microporosity PIM-1, for membrane gas separation. In thin film composite (TFC) membranes, aging is much more rapid than in thicker self-standing membranes, as rearrangement within the thin active layer is relatively fast. Liquid alcohol treatment, which swells the membrane, is often used in the laboratory to rejuvenate aged self-standing membranes, but this is not easily applied on an industrial scale and is not suitable to refresh TFC membranes because of the risk of membrane delamination. In this work, it is demonstrated that a simple method of storage in an atmosphere of methanol vapor effectively retards physical aging of PIM-1 TFC membranes. The same method can also be utilized to refresh aged PIM-1 TFC membranes, and one-week methanol vapor storage is sufficient to recover most of the original CO2 permeance.

Sieving gases with twisty polymers.

Ladder polymers in three dimensions show promise as gas-separation membranes.

PIM-1/Holey Graphene Oxide Mixed Matrix Membranes for Gas Separation: Unveiling the Role of Holes.

PIM-1/holey graphene oxide (GO) mixed matrix membranes (MMMs) have been prepared and their gas separation performance for CO2/CH4 mixtures assessed. Nanopores have been created in the basal plane of gas-impermeable GO by chemical etching reactions, and the resulting holey flakes have been further chemically functionalized, either with octadecylamine (ODA) or with PIM-1 moieties, to aid their dispersion in PIM-1. It is found that nanopores barely promote gas transport through the graphene-like nanofiller for fresh membranes (tested right after preparation); however, the prepared hybrid PIM-1/holey GO membranes exhibit higher CO2 permeability and CO2/CH4 selectivity than the pure polymer membrane 150 days after preparation and 13 and 15% higher CO2 permeability for filler contents of 0.1% of octadecylamine-functionalized holey GO and 1% of (PIM-1)-functionalized holey GO, respectively. The most significant improvement is observed for the mitigation of physical aging, as MMMs using 10% of (PIM-1)-functionalized holey GO nanofillers are capable of maintaining up to 70% of their initial CO2 permeability after 150 days, whereas only 53% is kept for pure PIM-1 after the same period. The gas permeability of the nanofiller has been rationalized with the aid of the Maxwell-Wagner-Sillars equation.

High-Flux Thin Film Composite PIM-1 Membranes for Butanol Recovery: Experimental Study and Process Simulations.

Thin film composite (TFC) membranes of the prototypical polymer of intrinsic microporosity (PIM-1) have been prepared by dip-coating on a highly porous electrospun polyvinylidene fluoride (PVDF) nanofibrous support. Prior to coating, the support was impregnated in a non-solvent to avoid the penetration of PIM-1 inside the PVDF network. Different non-solvents were considered and the results were compared with those of the dry support. When applied for the separation of n-butanol/water mixtures by pervaporation (PV), the developed membranes exhibited very high permeate fluxes, in the range of 16.1-35.4 kg m-2 h-1, with an acceptable n-butanol/water separation factor of about 8. The PV separation index (PSI) of the prepared membranes is around 115, which is among the highest PSI values that have been reported so far. Hybrid PV-distillation systems have been designed and modeled in Aspen HYSYS using Aspen Custom Modeler for setting up the PIM-1 TFC and commercial PDMS membranes as a benchmark. The butanol recovery cost for the hybrid systems is compared with a conventional stand-alone distillation process used for n-butanol/water separation, and a 10% reduction in recovery cost was obtained.

Superglassy Polymers to Treat Natural Gas by Hybrid Membrane/Amine Processes: Can Fillers Help?

Superglassy polymers have emerged as potential membrane materials for several gas separation applications, including acid gas removal from natural gas. Despite the superior performance shown at laboratory scale, their use at industrial scale is hampered by their large drop in gas permeability over time due to physical aging. Several strategies are proposed in the literature to prevent loss of performance, the incorporation of fillers being a successful approach. In this work, we provide a comprehensive economic study on the application of superglassy membranes in a hybrid membrane/amine process for natural gas sweetening. The hybrid process is compared with the more traditional stand-alone amine-absorption technique for a range of membrane gas separation properties (CO2 permeance and CO2/CH4 selectivity), and recommendations for long-term membrane performance are made. These recommendations can drive future research on producing mixed matrix membranes (MMMs) of superglassy polymers with anti-aging properties (i.e., target permeance and selectivity is maintained over time), as thin film nanocomposite membranes (TFNs). For the selected natural gas composition of 28% of acid gas content (8% CO2 and 20% H2S), we have found that a CO2 permeance of 200 GPU and a CO2/CH4 selectivity of 16 is an optimal target.

Boosting gas separation performance and suppressing the physical aging of polymers of intrinsic microporosity (PIM-1) by nanomaterial blending.

In recent decades, polymers of intrinsic microporosity (PIMs), especially the firstly introduced PIM-1, have been actively explored for various membrane-based separation purposes and widely recognized as the next generation membrane materials of choice for gas separation due to their ultra-permeable characteristics. Unfortunately, the polymers suffer substantially the negative impacts of physical aging, a phenomenon that is primarily noticeable in high free volume polymers. The phenomenon occurs at the molecular level, which leads to changes in the physical properties, and consequently the separation performance and membrane durability. This review discusses the strategies that have been employed to manage the physical aging issue, with a focus on the approach of blending with nanomaterials to give mixed matrix membranes. A detailed discussion is provided on the types of materials used, their inherent properties, the effects on gas separation performance, and their benefits in the suppression of the aging problem.

Mitigation of Physical Aging with Mixed Matrix Membranes Based on Cross-Linked PIM-1 Fillers and PIM-1.

A low cross-link density (LCD) network-PIM-1, which offers high compatibility with the polymer of intrinsic microporosity PIM-1, is synthesized by a modified PIM-1 polycondensation that combines both a tetrafluoro- and an octafluoro-monomer. To maximize the advantages of utilizing such cross-linked PIM-1 fillers in PIM-1-based mixed matrix membranes (MMMs), a grafting route is used to decorate the LCD-network-PIM-1 (dispersed phase) with PIM-1 chains, to further enhance compatibility with the PIM-1 matrix. Mixed-gas CO2/CH4 (1:1, v/v) separation results over 160 days of membrane aging confirm the success of a relatively short (24 h) grafting reaction in improving the initial CO2 separation performance, as well as hindering the aging of PIM-1/grafted-LCD-network-PIM-1 MMMs. For MMMs based on a 24 h grafting route, all the gas separation data surpass the 2008 Robeson upper bound by a significant margin, and the 160-day aged membranes show only 29% reduction from the initial CO2 permeability, which is substantially less than the equivalent losses of nearly 70% and 48% for PIM-1 and traditionally fabricated MMMs counterparts, respectively. These results demonstrate the potential of network-PIM components for obtaining much more stable gas separation performance over extended periods of time.

Intrinsically Microporous Polymer Nanosheets for High-Performance Gas Separation Membranes.

Microporous polymer nanosheets with thicknesses in the range 3-5 nm and with high apparent surface area (Brunauer-Emmett-Teller surface area 940 m2 g-1 ) are formed when the effectively bifunctional (tetrafluoro) monomer used in the preparation of the prototypical polymer of intrinsic microporosity PIM-1 is replaced with an effectively tetrafunctional (octafluoro) monomer to give a tightly crosslinked network structure. When employed as a filler in mixed-matrix membranes based on PIM-1, a low loading of 0.5 wt% network-PIM-1 nanosheets gives rise to enhanced CO2 permeability and CO2 /CH4 selectivity, compared to pure PIM-1.

Effect of Backbone Rigidity on the Glass Transition of Polymers of Intrinsic Microporosity Probed by Fast Scanning Calorimetry.

Polymers of Intrinsic Microporosity (PIMs) of high performance have developed as materials with a wide application range in gas separation and other energy-related fields. Further optimization and long-term behavior of devices with PIMs require an understanding of the structure-property relationships, including physical aging. In this context, the glass transition plays a central role, but with conventional thermal analysis a glass transition is usually not detectable for PIMs before their thermal decomposition. Fast scanning calorimetry provides evidence of the glass transition for a series of PIMs, as the time scales responsible for thermal degradation and for the glass transition are decoupled by employing ultrafast heating rates of tens of thousands K s-1. The investigated PIMs were chosen considering the chain rigidity. The estimated glass transition temperatures follow the order of the rigidity of the backbone of the PIMs.

Gas Permeation Properties, Physical Aging, and Its Mitigation in High Free Volume Glassy Polymers.

Hundreds of polymers have been evaluated as membrane materials for gas separations, but fewer than 10 have made it into current commercial applications, mainly due to the effects of physical aging and plasticization. Efforts to overcome these two problems are a significant focus in gas separation membrane research, in conjunction with improving membrane separation performance to surpass the Robeson upper bounds of selectivity versus permeability for commercially important gas pairs. While there has been extensive research, ranging from manipulating the chemistry of existing polymers (e.g., thermally rearranged or cross-linked polyimides) to synthesizing new polymers such as polymers of intrinsic microporosity (PIMs), there have been three major oversights that this review addresses: (1) the need to compare the approaches to achieving the best performance in order to identify their effectiveness in improving gas transport properties and in mitigating aging, (2) a common standardized aging protocol that allows rapid determination of the success (or not) of these approaches, and (3) standard techniques that can be used to characterize aging and plasticization across all studies to enable them to be robustly and equally compared. In this review, we also provide our perspectives on a few key aspects of research related to high free volume polymer membranes: (1) the importance of Robeson plots for membrane aging studies, (2) eliminating thermal history, (3) measurement and reporting of gas permeability and aging rate, (4) aging and storing conditions, and (5) promising approaches to mitigate aging.

First Clear-Cut Experimental Evidence of a Glass Transition in a Polymer with Intrinsic Microporosity: PIM-1.

Polymers with intrinsic microporosity (PIMs) represent a novel, innovative class of materials with great potential in various applications from high-performance gas-separation membranes to electronic devices. Here, for the first time, for PIM-1, as the archetypal PIM, fast scanning calorimetry provides definitive evidence of a glass transition ( Tg = 715 K, heating rate 3 × 104 K/s) by decoupling the time scales responsible for glass transition and decomposition. Because the rigid molecular structure of PIM-1 prevents any conformational changes, small-scale bend and flex fluctuations must be considered the origin of its glass transition. This result has strong implications for the fundamental understanding of the glass transition and for the physical aging of PIMs and other complex polymers, both topical problems of materials science.

The unique calcium chelation property of poly(vinyl phosphonic acid-co-acrylic acid) and effects on osteogenesis in vitro.

There is a clear clinical need for a bioactive bone graft substitute. Poly(vinyl phosphonic acid-co-acrylic acid) (PVPA-co-AA) has been identified as a promising candidate for bone regeneration but there is little evidence to show its direct osteogenic effect on progenitor or mature cells. In this study mature osteoblast-like cells (SaOS-2) and human bone marrow-derived mesenchymal stem cells (hBM-MSCs) were cultured with PVPA-co-AA polymers with different VPA:AA ratio and at different concentrations in vitro. We are the first to report the direct osteogenic effect of PVPA-co-AA polymer on bone cells and, more importantly, this effect was dependent on VPA:AA ratio and concentration. Under the optimized conditions, PVPA-co-AA polymer not only has an osteoconductive effect, enhancing SaOS-2 cell mineralization, but also has an osteoinductive effect to promote hBM-MSCs' osteogenic differentiation. Notably, the same PVPA-co-AA polymer at different concentrations could lead to differential osteogenic effects on both SaOS-2 and hBM-MSCs in vitro. This study furthers knowledge of the PVPA-co-AA polymer in osteogenic studies, which is critical when utilizing the PVPA-co-AA polymer for the design of novel bioactive polymeric tissue engineering scaffolds for future clinical applications. © 2017 The Authors Journal of Biomedical Materials Research Part A Published by Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 168-179, 2018.

Poly(vinylphosphonic acid-co-acrylic acid) hydrogels: The effect of copolymer composition on osteoblast adhesion and proliferation.

There is a clinical need for a synthetic bone graft substitute that can be used at sites of surgical intervention to promote bone regeneration. Poly(vinylphosphonic acid-co-acrylic acid) (PVPA-co-AA) has recently been identified as a potential candidate for use in bone tissue scaffolds. It is hypothesized that PVPA-co-AA can bind to divalent calcium ions on bone mineral surfaces to control matrix mineralization and promote bone formation. In this study, hydrogels of PVPA-co-AA have been produced and the effect of copolymer composition on the structure and properties of the gels was investigated. It was found that an increase in VPA content led to the production of hydrogels with high porosities and greater swelling capacities. Consequently, improved cell adhesion and proliferation was observed on these hydrogels, as well as superior cell spreading morphologies. Furthermore, whereas poly(acrylic acid) gels were shown to be relatively brittle, an increase in VPA content created more flexible hydrogels that can be more easily molded into bone defect sites. Therefore, this work demonstrates that the mechanical and cell adhesion properties of PVPA-co-AA hydrogels can be tuned for the specific application by altering the copolymer composition. © 2017 The Authors Journal of Biomedical Materials Research Part A Published by Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 255-264, 2018.

Anomalies in the low frequency vibrational density of states for a polymer with intrinsic microporosity - the Boson peak of PIM-1.

Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering.

Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation.

Metal-organic frameworks (MOFs) were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1). Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8) and Copper benzene tricarboxylate ((HKUST-1), were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA) -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability.

Selective dye adsorption by chemically-modified and thermally-treated polymers of intrinsic microporosity.

Nitrile groups in the polymer of intrinsic microporosity PIM-1 were modified by base-catalysed hydrolysis, by reaction with ethanolamine and diethanolamine, and by reduction to amine, and the products investigated for their ability to take up a range of dyes from aqueous or ethanolic solution. Hydrolysed products exhibited selectivity for cationic over anionic species, while other products showed the reverse selectivity. At low pH, amine-PIM-1 adsorbed more than its own weight of the anionic dyes Orange II and Acid Red I from aqueous solution. It was demonstrated that adsorbed Orange II can be removed with basic ethanol. Mixtures of oppositely charged dyes undergo precipitation, but selective adsorption of one dye leads to dissolution of the other from the precipitate. Thermal treatment of the chemically modified polymers at 300°C for 48h in an inert atmosphere led to structural changes that reduced the dye adsorption capacity. On the basis of a combination of thermogravimetric and elemental analysis with ATR-IR and NMR spectroscopy, feasible structures are suggested for the thermally-treated polymers.

PIM-1 mixed matrix membranes for gas separations using cost-effective hypercrosslinked nanoparticle fillers.

High-free-volume glassy polymers, such as polymers of intrinsic microporosity (PIMs) and poly(trimethylsilylpropyne), have attracted attention as membrane materials due to their high permeability. However, loss of free volume over time, or aging, limits their applicability. Introduction of a secondary filler phase can reduce this aging but either cost or instability rules out scale up for many fillers. Here, we report a cheap, acid-tolerant, nanoparticulate hypercrosslinked polymer 'sponge' as an alternative filler. On adding the filler, permeability is enhanced and aging is strongly retarded. This is accompanied by a CO2/N2 selectivity that increases over time, surpassing the Robeson upper bound.