Postmodification of PIM-1 and the effect on Gas Transport Properties (Abstract/Poster in atti di convegno)

Type
Label
  • Postmodification of PIM-1 and the effect on Gas Transport Properties (Abstract/Poster in atti di convegno) (literal)
Anno
  • 2012-01-01T00:00:00+01:00 (literal)
Alternative label
  • Christopher R. Mason1, Louise Maynard-Atem1, Nasser M. Al-Harbi1, Peter M. Budd1, Paola Bernardo2, Fabio Bazzarelli2, Gabriele Clarizia2, Johannes C. Jansen2 (2012)
    Postmodification of PIM-1 and the effect on Gas Transport Properties
    in DoubleNanoMem Workshop and Exhibition Nanostructured and Nanocomposite Membranes for Gas and Vapour Separations, Cetraro, Italy, 18-18 maggio 2012
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Christopher R. Mason1, Louise Maynard-Atem1, Nasser M. Al-Harbi1, Peter M. Budd1, Paola Bernardo2, Fabio Bazzarelli2, Gabriele Clarizia2, Johannes C. Jansen2 (literal)
Note
  • Abstract (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 1 School of Chemistry, University of Manchester, Manchester, M13 9PL, United Kingdom 2 Institute of Membrane Technology (ITM-CNR), Via P. Bucci, Cubo 17/C, c/o University of Calabria, 87036 Rende (CS), Italy (literal)
Titolo
  • Postmodification of PIM-1 and the effect on Gas Transport Properties (literal)
Abstract
  • Introduction PIM-1 (1) is well known for its high permeability and good selectivity, surpassing Robeson's 1991 upper bound [1] and defining the 2008 upper bound [2] for several important gas pairs [3,4]. Since its discovery there have been numerous publications concerned with preparing novel PIMs with a view to improving or tuning the gas transport properties by incorporation of different moieties and functionalities. Postmodification of PIMs also presents a novel route to new polymers. Currently there are only a few examples of PIM-1 postmodification, where the nitrile has been converted to a carboxylic acid [5], a tetrazole [6] and more recently a thioamide functionality (2) [7]. The preparation of PIM-1 containing the thioamide functionality will be presented along with that of the amine (3) and amide (4) containing polymer. Scheme 1. Reagents and conditions: The modification of PIM-1 leads to a loss free volume for all polymers, as seen by a reduction in surface area. This is due to the ability of the new functional groups to hydrogen bond as well as them generally being bulkier than the nitrile. The solubility of the polymer changes on modification, losing its solubility in chloroform and dichloromethane. However, thioamide-PIM-1 remains soluble in the volatile solvent THF, as well as having improved solubility in high boiling polar aprotic solvents such as dimethyl sulphoxide, so can easily be solution processed into membranes. So far a suitable solvent for amine-PIM-1 has not been found, so membranes were prepared by reaction on as prepared PIM-1 membranes. Figure 1. Double logarithmic plot of selectivity for CO2/N2 for postfunctionalised PIM-1 polymers. The gas transport properties of postfunctionalised PIM-1s showed a reduction in permeabilities with increased selectivities compared to that of PIM-1, with the exception of CO2 for aminePIM-1. This showed a significant decrease in permeability and thus CO2/selectivites (Fig. 1), possibly due to strong sorption of the penetrant CO2. As for PIM-1, treatment of the membranes with lower alcohols results in increased permeabilities with a general modest decreases in selectivity. For example for thioamide-PIM-1 this shows a five to ten fold increase in permeabilities due to removal of occluded casting solvent as well as the introduction of extra free volume from swelling of the structure [7]. As a consequence, for the gas pair CO2/N2 thioamide-PIM-1 lies very close to the Robeson 2008 upper bound (Fig. 1). References [1] L.M. Robeson, Correlation of separation factor versus permeability for polymeric membranes, J. Membr. Sci. 62 (1991) 165-85. [2] L. M. Robeson, The upper bound revisited, J. Membr. Sci. 320 (2008) 390-400. [3] P.M. Budd, K.J. Myasib, C.E. Tattershall, B.S. Ghanem, K. J. Reynolds, N.B. McKeown, D. Fritsch, Gas separation membranes from polymers of intrinsic microporosity, J. Membr. Sci. 251 (2005) 263-269. [4] P.M. Budd, N.B. McKeown, B.S. Ghanem, K.J. Myasib, D. Fritsch, L. Starannikova, N. Belov, O. Sanfirova, Y. Yampolskii, V. Shantarovich, Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: Polybenzodioxane PIM-1, J. Membr. Sci. 325 (2008) 851-860. [5] N. Du, G.P. Robertson, J. Song, I. Pinnau, M.D. Guiver, High-performance carboxylated polymers of intrinsic microporosity (PIMs) with tunable gas transport properties, Macromolecules 42 (2009) 6038-6043. [6] N. Du, H.B. Park, G.P. Robertson, M.M. Dal-Cin, T. Visser, L. Scoles, M.D. Guiver, Polymer nanosieve membranes for CO2-capture applications, Nat. Mater. 10 (2011) 372-375. [7] C.R. Mason, L. Maynard-Atem, N.M. Al-Harbi, P.M. Budd, P. Bernardo, F. Bazzarelli, G. Clarizia, J.C. Jansen, Polymer of intrinsic microporosity incorporating the thioamide functionality: Preparation and gas transport properties, Macromolecules 44 (2011) 6471-6479. (literal)
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