Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine–PIM-1 showed higher CO2 uptake and higher CO2/N2 sorption selectivity than the parent polymer, with very evident dual-mode sorption behavio...

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Published inMacromolecules Vol. 47; no. 3; pp. 1021 - 1029
Main Authors Mason, Christopher R, Maynard-Atem, Louise, Heard, Kane W. J, Satilmis, Bekir, Budd, Peter M, Friess, Karel, Lanc̆, Marek, Bernardo, Paola, Clarizia, Gabriele, Jansen, Johannes C
Format Journal Article
LanguageEnglish
Published Washington, DC American Chemical Society 11.02.2014
Subjects
adsorption
Applied sciences
carbon dioxide
Exact sciences and technology
gases
hydrogen
hydrogen bonding
Miscellaneous
Organic polymers
permeability
Physicochemistry of polymers
polymers
primary amines
Properties and characterization
solubility
Transport properties
Carbon dioxide
Adsorption isotherm
Adsorption capacity
Nitrogen
Experimental study
Porous material
Functional polymer
Heterocyclic polymer
Chemical reduction
Gas solid adsorption
Gas permeability
Chemical modification
Wettability
Amine polymer
Preparation
Surface properties
Selective permeability
Semiladder polymer
Spiran polymer
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Summary:Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine–PIM-1 showed higher CO2 uptake and higher CO2/N2 sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H2/CO2 gas pair, whereas PIM-1 favors CO2, amine–PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.
Bibliography:ObjectType-Article-1
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content type line 23
ISSN:0024-9297
1520-5835
1520-5835
DOI:10.1021/ma401869p