Abstract
The influence of hyper-crosslinked polystyrene (HCPS) MacronetTM MN200 on the gas transport properties and aging of the highly permeable glassy polymer poly(1-trimethylsilyl-1-propyne) (PTMSP) was studied and analyzed in detail. The gas transport characteristics of dense PTMSP membranes containing 0–10.0 wt % HCPS were studied. It was shown that the introduction of a small amount of HCPS into the PTMSP matrix led to a 50–60% increase of the permeability coefficients of the material for light gases (N2, O2, CO2) and slowed down the deterioration of polymer transport properties over time. The lowest reduction in gas permeability coefficients (50–57%) was found for PTMSP containing HCPS 5.0 wt % after annealing at 100 °C for 300 h. It was found that HCPS sorbed residues of tantalum-based polymerization catalyst from PTMSP. In order to investigate the influence of catalysts on transport and physical properties of PTMSP, we purified the latter from the polymerization catalyst by addition of 5 wt % HCPS into polymer/chloroform solution. It was shown that sorption on HCPS allowed for almost complete removal of tantalum compounds from PTMSP. The membrane made of PTMSP purified by HCPS demonstrated more stable transport characteristics compared to the membrane made of the initial polymer. HCPS has a complex effect on the aging process of PTMSP. The introduction of HCPS into the polymer matrix not only slowed down the physical aging of PTMSP, but also reduced chemical aging due to removal of active reagents.
Highlights
Membrane processes are among the most efficient technologies for the separation of gases and liquids due to low capital costs and small plant sizes compared to other separation methods that require solid or liquid adsorbents or processes such as distillation, which requires an energy-expensive phase transition [1,2,3,4]
Dense PTMSP membranes were fabricated by casting PTMSP solution in chloroform on cellophane and subsequent drying for 200 h under ambient conditions at room temperature
Hyper-crosslinked polymers were first produced by Davankov, Rogozhin, and TsyHyper-crosslinked polymers were first produced by Davankov, Rogozhin, and Tsyuurupa and are produced in volume by Purolite Corporation
Summary
Membrane processes are among the most efficient technologies for the separation of gases and liquids due to low capital costs and small plant sizes compared to other separation methods that require solid or liquid adsorbents or processes such as distillation, which requires an energy-expensive phase transition [1,2,3,4]. Hydrophobic glassy polymers with a large fractional free volume (FFV) or polymers of intrinsic microporosity, such as disubstituted polyacetylenes, polybenzodioxane (PIM-1), and polynorbornenes, are considered promising membrane and sorbing materials for the separation of gases and liquids [5,6,7,8,9,10,11,12,13,14]. A significant disadvantage of glassy polymers is physical aging over time and, as a result, a significant decrease in the permeability coefficients. This poses a serious problem for the commercial application of these polymers [15,16,17,18,19,20]. In the case of a poly[1-(trimethylsilyl)-1-propyne] (PTMSP) film with a thickness of 3 microns, nitrogen or helium permeability decreased more than twice during a 200 h test [20]
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