Atomistic packing model and free volume distribution of a polymer with intrinsic microporosity (PIM-1)

Heuchel, Matthias; Fritsch, Detlev; Budd, Peter M.; McKeown, Neil B.; Hofmann, Dieter

doi:10.1016/j.memsci.2008.02.038

Cited by 228 publications

(205 citation statements)

References 30 publications

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“…Early work required the accurate experimental measurement of the density of the PIM, which is difficult to achieve as a film and almost impossible as a powder [97]. However, subsequent studies using a series of simulated high pressure compression and relaxation achieve a realistic packing without the need for density measurements [98,99].…”

Section: Computer Simulationmentioning

confidence: 99%

“…However, for PIMs it appears that the rigid and contorted macromolecular structures help to reduce intermolecular cohesive interactions by limiting the amount of close contacts between polymer chains. The relative flexibility of the spirobisindane unit may also assist in solubility [97]. It is notable that the PIM prepared from the ethanoanthracene monomer A4 and tetrafluoroterephthalonitrile B1 is insoluble [75], and this may be due to the greater rigidity of the bridged bicyclic ethanoanthracene unit.…”

Section: Solubilitymentioning

confidence: 99%

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Polymers of Intrinsic Microporosity

McKeown

2012

ISRN Materials Science

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This paper focuses on polymers that demonstrate microporosity without possessing a network of covalent bonds-the so-called polymers of intrinsic microporosity (PIM). PIMs combine solution processability and microporosity with structural diversity and have proven utility for making membranes and sensors. After a historical account of the development of PIMs, their synthesis is described along with a comprehensive review of the PIMs that have been prepared to date. The important methods of characterising intrinsic microporosity, such as gas absorption, are outlined and structure-property relationships explained. Finally, the applications of PIMs as sensors and membranes for gas and vapour separations, organic nanofiltration, and pervaporation are described.

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Section: Computer Simulationmentioning

confidence: 99%

Section: Solubilitymentioning

confidence: 99%

Polymers of Intrinsic Microporosity

McKeown

2012

ISRN Materials Science

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179

136

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“…Linear polymer chains interacting by relatively weak van der Waals forces or entanglements could easily slide over each other. In addition, molecular modelling of PIM-1 indicates that the spirobisindane unit and dioxane linkages are relatively flexible 30 . This amorphous and flexible nature of PIMs polymer chains results in a broad size distribution of free volume elements (for example, 4-10 Å), which compromises their separation performance, for example, poor molecular selectivity, physical aging and plasticization.…”

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confidence: 99%

Controlled thermal oxidative crosslinking of polymers of intrinsic microporosity towards tunable molecular sieve membranes

et al. 2014

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Organic open frameworks with well-defined micropore (pore dimensions below 2 nm) structure are attractive next-generation materials for gas sorption, storage, catalysis and molecular level separations. Polymers of intrinsic microporosity (PIMs) represent a paradigm shift in conceptualizing molecular sieves from conventional ordered frameworks to disordered frameworks with heterogeneous distributions of microporosity. PIMs contain interconnected regions of micropores with high gas permeability but with a level of heterogeneity that compromises their molecular selectivity. Here we report controllable thermal oxidative crosslinking of PIMs by heat treatment in the presence of trace amounts of oxygen. The resulting covalently crosslinked networks are thermally and chemically stable, mechanically flexible and have remarkable selectivity at permeability that is three orders of magnitude higher than commercial polymeric membranes. This study demonstrates that controlled thermochemical reactions can delicately tune the topological structure of channels and pores within microporous polymers and their molecular sieving properties.

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“…The first group of nanoporous materials in Table I (1) is formed by polymer powders (used for membrane preparation), silicon-containing tricyclonanens, perfluorinated polymers, or rigid polymers having a ladder structure and spiro-centers, formed by single C-C bonds (PIM-1, polymers of intrinsic microporosity) [5]. Remarkably, the most probable micropore size ≈ 0.8 nm, according to LTGS (HK,SF), Fig.…”

Section: Micropore Powders and Membranesmentioning

confidence: 99%

Nanoporosity of Polymer Sorbents and Membrane Materials as Seen by PALS and Low Temperature Gas Sorption

Shantarovich

Bekeshev²,

Kevdina³

et al. 2017

Acta Phys. Pol. A

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The limits of application of positron annihilation lifetime spectroscopy and low temperature gas sorption for studying nanoporosity of polymer sorbents and membrane materials are discussed relying on the results previously obtained by the authors. For the two methods, limitations are determined by different factors: the dispersion of the material is essential for low temperature gas sorption, while concentration of nanopores of given size is important for positron annihilation lifetime spectroscopy. The both methods came out to be a useful addition to each other in the studies of micropores and mesopores.

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Atomistic packing model and free volume distribution of a polymer with intrinsic microporosity (PIM-1)

Cited by 228 publications

References 30 publications

Polymers of Intrinsic Microporosity

Polymers of Intrinsic Microporosity

Controlled thermal oxidative crosslinking of polymers of intrinsic microporosity towards tunable molecular sieve membranes

Nanoporosity of Polymer Sorbents and Membrane Materials as Seen by PALS and Low Temperature Gas Sorption

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