Importance of small loops within PIM-1 topology on gas separation selectivity in thin film composite membranes

Foster, Andrew B.; Beal, Joseph L.; Tamaddondar, Marzieh; Luque-Alled, José Miguel; Robertson, Ben; Mathias, Michael; Gorgojo, Patricia; Budd, Peter M.

doi:10.1039/d1ta03712a

Cited by 42 publications

(33 citation statements)

References 62 publications

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“…All films cast from polymer samples containing more than 10 wt % colloidal network material exhibited nontypical aging behavior between 1 and 143 days: both permeability and selectivity decreased upon aging. This negative aging behavior has been previously observed in thin film composite membranes cast from blends of PIM-1, which contained high amounts of colloidal network material, after a couple of months . The presence of a second colloidal network phase in the bulk presents at the very least a second mode of aging within the overall films.…”

Section: Resultssupporting

confidence: 71%

Influence of Polymer Topology on Gas Separation Membrane Performance of the Polymer of Intrinsic Microporosity PIM-Py

Devarajan

Asuquo²,

Ahmad³

et al. 2021

ACS Appl. Polym. Mater.

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The polymer synthesis of 2,3,5,6-tetrafluoro-4-pyridinecarbonitrile-3,3,3′,3′-tetramethyl-1,1′-spirobisindane-5,5′,6,6′-tetrol copolymer, termed PIM-Py, was investigated under different solvent (dimethylformamide (DMF) and dimethylacetamide/dichlorobenzene) and temperature (65–160 °C) conditions to produce a range of topologically different polymer samples. Characterization of the polymers, particularly with proton NMR spectroscopy and multiple detector SEC analysis, indicated that, like PIM-1, the polymerizations proceeded with a degree of polymer chain branching. This is attributed to the occurrence of monosubstitution reactions, instead of disubstitution, which eventually leads to a significant proportion of colloidal network formation. However, all polymer samples remained soluble/dispersible in chloroform at the concentration required to cast self-standing films. This work reports the first examination of PIM-Py as a membrane for gas separation applications. The most structurally diverse PIM-Py samples produced films that exhibited selectivity/permeability balances in single gas permeation studies above the 2008 Robeson upper bound for the CO2/N2 gas pair. Indeed, a film cast from the highest colloidal network content sample surpassed the recently introduced 2019 CO2/N2 upper bound. After 143 days of aging, a 40 μm self-standing membrane still exhibited a single gas CO2 permeability of 4480 barrer and an ideal CO2/N2 selectivity of 45. The polymers produced in lower temperature reactions in DMF exhibited gas separation performances very similar to a structurally regular “normal” PIM-1 polymer, sitting on or around the 2008 Robeson upper bound line. Single gas permeation measurements to determine CO2/CH4 selectivity showed similar trends across the range of polymer samples, without generally reaching high selectivities as for the CO2/N2 pair. Mixed gas CO2/CH4 permeation measurements with aging were also completed for PIM-Py membranes, which indicated similar gas separation performance to a structurally regular PIM-1 polymer. This study would suggest that, like PIM-1, gas separation performance of PIM-Py is greatly influenced by the topological balance toward branched and network material within the polymer sample.

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Section: Resultssupporting

confidence: 71%

Influence of Polymer Topology on Gas Separation Membrane Performance of the Polymer of Intrinsic Microporosity PIM-Py

Devarajan

Asuquo²,

Ahmad³

et al. 2021

ACS Appl. Polym. Mater.

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“…However, the pristine PIM-1 membranes in our previous work suffer a larger extent of physical aging than the ones used in this work over the same period (Table ); it is worth noting that two different PIM-1 batches were used, and the observed higher gas permeabilities for MMMs containing ODA-HGO-4h may be related to the polymer itself. Foster et al , found that the presence of branched PIM-1 chains (formed during the polymer synthesis as a consequence of incomplete disubstitutions) results in slower physical aging as compared to linear polymeric structures. NMR characterization (Figure S8) suggests the presence of branched polymer structures within the PIM-1 sample employed in this manuscript, which accounts for the slower physical aging as compared to the PIM-1 sample reported in our previous publication.…”

Section: Results and Discussionmentioning

confidence: 99%

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

Luque-Alled

Tamaddondar

Foster

et al. 2021

ACS Appl. Mater. Interfaces

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PIM-1/holey graphene oxide (GO) mixed matrix membranes (MMMs) have been prepared and their gas separation performance for CO 2 /CH 4 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 CO 2 permeability and CO 2 /CH 4 selectivity than the pure polymer membrane 150 days after preparation and 13 and 15% higher CO 2 permeability for filler contents of 0.1% of octadecylaminefunctionalized 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 CO 2 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.

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Section: Resultsmentioning

confidence: 96%

“…41 More recently, Foster et al reported the effect of blending topologically distinct samples of PIM-1 on the performance and aging behaviour of TFCs. 42 Those containing a multi-loop polymeric structure (with 3 small loops) and very few chain ends (0-1 max) showed the best aging behaviour, with CO 2 permeance of 671 GPU aer 120 days. Some of the prepared TFN membranes with aminefunctionalised-rHGO were able to reduce the physical aging of the PIM-1 polymer, for example the membrane containing 0.25 wt% of tetrakis (TFN-0.25rHGO-tetrakis) experienced a loss of CO 2 permeance of only 14% (from (1265 AE 70) to (1092 AE 108) GPU) over a period of 66 days.…”

Section: Resultsmentioning

confidence: 97%

Thin film nanocomposite membranes of superglassy PIM-1 and amine-functionalised 2D fillers for gas separation

et al. 2022

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Importance of small loops within PIM-1 topology on gas separation selectivity in thin film composite membranes

Abstract: Studies of blends of topologically distinct samples of the polymer of intrinsic microporosity PIM-1 provide, for the CO2/N2 gas pair, insight into the optimum loop topology required for high selectivity and permeance of thin film composite (TFC) membranes.

Cited by 42 publications

References 62 publications

Influence of Polymer Topology on Gas Separation Membrane Performance of the Polymer of Intrinsic Microporosity PIM-Py

Influence of Polymer Topology on Gas Separation Membrane Performance of the Polymer of Intrinsic Microporosity PIM-Py

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

Thin film nanocomposite membranes of superglassy PIM-1 and amine-functionalised 2D fillers for gas separation

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