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DOI: 10.1002/ijch.201200081

Tuning Gas-Diffusion through Dynameric Membranes: Toward Rubbery Organic Frameworks (ROFs)
Gihane Nasr,[a] Arnauld Gilles,[a] Thomas Macron,[a] Christophe Charmette,[a] Jose Sanchez,[a] and Mihail Barboiu*[a]
Abstract : Obtaining high permeability whilst keeping a reasonable selectivity is the most important challenge in the development of membrane systems for gas separation. Satisfactory performance is usually obtained with polymeric membranes through which gas transport is controlled by gas-diffusivity in glassy polymers and by gas-solubility in rubbery polymers. During the last decade, important advances in this field have been made possible by molecular control of gas separation properties. The combination or replacement of classical glassy polymers with metal-organic crystalline frameworks (crystalline MOFs), such as zeolitic imidazolate frameworks (ZIFs) or other zeolites, provides reasonable permeability through the porous networks formed, and high selectivity, due to so-called selectivity centers, which interact specifically with the gas molecules. Despite impressive progress, difficulties in obtaining homogeneous, mechanically stable, thin layer MOFs on various supports have been encountered. Given the observed high permeabilities of rubbery polymers and their flexible casting properties, it should be very interesting to build rubbery organic frameworks (ROFs), as alternative materials for gas membrane separation systems. Here we use low macromolecular constituents and dialdehyde core connectors, in order to constitutionally generate ROFs. Distinct from rubbery polymeric membranes, the performance of the ROFs depends univocally on diffusional behaviors of gas molecules through the network. For all gases, a precise molecular composition of linear and star-type macromonomers generates an optimal free volume for a maximal diffusion through the matrix. These results should initiate new interdisciplinary discussions about highly competitive systems for gas separation, which are constitutionally controlled on a molecular scale.

Keywords: constitutional materials dynamers gas transport membranes self-assembly

Among the industrial methods used for capturing CO2 (absorption, distillation, etc.),[1] membrane technology,[211] which offers advantages such energy saving, simple design and scale-up, is becoming continually more prevalent. High permeability combined with reasonable selectivity is the most important goal in developing membranes for gas separation. This goal is usually achieved through the use of polymeric membranes, through which gas transport is controlled by gas-diffusivity in glassy polymers and by gas-solubility in rubbery polymers. De novo design of synthetic membrane materials like blockco-polymers,[25] polymeric composites,[6,7] mixed-matrix hybrids[8] and pseudo-microporous polymers[910] metal organic frameworks- MOFs[1,11] has been identified as an emerging area of interest. The combination or replacement of classical glassy polymers with crystalline MOFs, ZIFs, or zeolites provides molecularly controlled permeability and selectivity. However, attempts to obtain mechanically stable and homogeneous layers on various supports have been met with difficulty. Taking advantage of the high permeabilities and flexible casting properties observed for rubbery polymers, we decided to build ROFs as new membrane separation systems for gases. ROFs may provide premises for more fine structural interaction of diffusing gas molecules with moIsr. J. Chem. 2013, 53, 97 101

lecular addressable domains. Minimizing the size of ultradense addressable transporting domains[1215] would make it possible to improve the limits of interaction of gas molecules with percolated conductive domains with high diffusional behaviors.[1619] Such an improvement is specifically of interest to membrane scientists (Figure 1). Furthermore, the size of addressable elementary domains for the diffusion of gas molecules is reminiscent of the situation where pixel size determines the quality of resulting images in LCD devices. Within this context, we previously showed that dynamic covalent polymers,[15] or dynamers,[2023] generated from reversibly interacting monomers, offer the possibility to address these issues.[24,25] In dynamers, the components are reversibly connected, and they self-assemble in such a fashion that their overall morphology overrides defects during the for[a] G. Nasr, A. Gilles, T. Macron, C. Charmette, J. Sanchez, M. Barboiu Institut Europen des Membranes ENSCM-UMII-CNRS 5635 Place Eugne Bataillon CC 047 F-34095 Montpellier, Cedex 5 (France) e-mail: mihai.barboiu@iemm.univ-montp2.fr Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/ijch.201200081.

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Figure 1. Converging the structural behaviors of block co-polymers toward ultradense rubbery organic frameworks-block co-dynamers, controlled at the molecular level (see text for details).

mation and orientation of conductive domains, under the pressure of internal structural stabilization. Such behavior could mediate the self-assembly of low-size addressable domains, in which diffusional percolation pathways might be formed (Figure 1). For all these reasons, in this study, nanometric macromonomers and dialdehyde core connectors have been used to conceive dense ROFs for the preparation of dynameric membranes for selective gas transport.[2225] The isophthalaldehyde (1), the bis(3-aminopropyl)-polytetrahydrofuran (Mn ~ 1100 g mol1, polyTHF, 2), and the glyceroltris[poly(propylene glycol), amine terminated] ether, (Mn ~ 3000 g mol1, polyMePEG, 3) building blocks are the precursors of the dynamers 11-x 2 3x, used to cast stretchy membrane films (Figure 2). Compounds 11-x 2 3x (Figure 2 a) generate dynameric membranes based on three structural features: 1) The hydrophobic linear polyTHF (1) has been used to generate rigid crystalline phases considered to have low-permeability for gas transport. 2) The hydrophilic star-type polyMePEG (3) allows for high solubility of CO2, and thus contributes to the cross-linking of the dynameric network. The relative amount of 3 controls the free volume, and thus the permeability, of the membrane films. The presence of methyl (Me) groups induces a lack of tacticity in the macromonomeric chains, suppressing their crystallization. The network might be considered to contain combinations of linear and cross-linked arrays, resulting from the variable relative amounts of the linear polyTHF (1) and the star-type polyMePEG (3), which are interconnected with the core connectors via reversible imine bonds. 3) The macromonomers might have a protective effect against the hydrolysis of the imine bonds, favoring imine exchange. This would contribute to the implementation of dynamic adaptive reversible rearrangements of the components, leading, during membrane preparation, to a high level of correlativity of the nanodomains.[19,23] 1 H NMR analysis in CDCl3 allows easy identification of the peaks corresponding to total conversion to iminocompounds 11-x 2 3x (Figure 1S). The elastomeric behavior of compounds 11-x 2 3x is confirmed by their glass transition temperature, Tg ~ 69 to 628. Interestingly, 98
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the Tg values show a minimum at 33 % of 3 (Figure 3d), indicating a high free volume of the matrix around this composition, distinct from the compact matrix of linear 1 and the highly cross-linked matrix of 3. The increasing Tg values for high content of 3 follow the same pattern as the crystallization temperature, Tc, which cannot be detected for highly cross-linked polymers 11-x 2 3x, x = 0.7 or 1.0 (Figure 2S, Table 1S). The pure gases permeabilities for the 11-x 2 3x rubbery membranes as a function of % 3 mol/mol content are shown in Figure 3 a. As a general trend for all gases measured (He, O2, N2, and CO2), the permeability reaches a maximum around 33 % of 3. The rubbery blends allow high permeabilities for the CO2 and interesting CO2/light gas permselectivities (Figure 3 a, b). Generally, PEG-type materials exhibit very low permeability (~ 12 Barrers) due to their high degree of crystallinity,[26] which can be disrupted in the presence of non-PEG rubbery polymers, resulting in the formation of solubility-driven selective transport. To elaborate on this very sharp control of the permselectivity of such rubbery dynameric membranes, a detailed overview of their solubility/diffusivity selectivity is presented in Figure 3 c, d. First of all, a sorption analysis of CO2 was performed. The obtained sorption coefficients, 1.26 to 1.87 102 cm3(STP)cm3cmHg1, are in the same range as previously reported.[28] Amazingly, over a range of 6.550 % 3 the experimental sorption coefficients remain practically constant (Figure 3 c). Then, as the content of 3 increases, these values strongly decrease toward values at the method detection limit. These experiments confirm that the CO2 sorption is related to two opposite effects: with increasing concentration of 3 in the polymeric blend, the rivalry between an increase in the solubility of quadrupolar CO2 relative to the polar polyMePEG chains of 3, on the one hand, and the cross-linking behaviors of 3, on the other hand, keeps the sorption coefficients nearly constant. The values of diffusion coefficients D, obtained from permeability experiments, illustrate that the diffusivity of CO2, which reaches a maximum at ~ 33 % of 3, is correlated with the free volume of the dynameric network (Figure 3 d). The increase of the free volume of the dynamer is most likely caused by incorporation of 3, which causes the otherwise compact and low-diffusive matrix of linear polyTHF to become less compact (Figure 3 e, right). This structural behavior is certainly related to a critical amount of the cross-linker 3, which generates the optimal spacing of the linear polyTHF chains and allows gas molecules to diffuse through the film. More interestingly, the optimal performances are observed at 33 % molar ratio of 3. This means a molar ratio (1)/(3) of 2/1 mol/mol, for which the probable pseudo-porous geometry of a highly diffusive matrix is responsible for the observed maximum values (Figure 2 b, middle). The free volume generated correlates with Tg values (Figure 3 d), and is related to a strong
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Gas-Diffusion through Dynameric Membranes

Figure 2. a) Synthesis and b) schematic representation of chain packing of dynameric membranes combining polyTHF (1, red sticks) and polyMePEG, (3, green Y shapes), connected via isophthaldimine cores (2, blue circles). Structural diversity of matrices can be obtained: (left) linear compact (high content of 2), (center) free volume matrix (maximum value of diffusivity at % 3 = 33 %), and (right) highly crosslinked (high content of 3). c) Images of self-standing dynameric membrane films with elastomeric behavior.

increase in permeability, which can thus be mainly attributed to optimal gas diffusivity and not to an increase in solubility, which remains almost constant over a large concentration domain (Figure 3 c). Further addition of 3 generates a critical cross-linking of the matrix and prohibIsr. J. Chem. 2013, 53, 97 101

its diffusion/sorption of CO2 through the membrane. It may be concluded that CO2 permeation and selectivity are controlled by gas-diffusivity through rubbery dynameric membranes, which can be finely tuned at the nanometric level.
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Figure 3. Experimental profiles of a) pure gas permeabilities, b) pure CO2/N2 selectivities at 298 K and 1.0 105 Pa, c) solubilities of CO2, determined by absorption and d) diffusivity of CO2, calculated by using the time-lag method, as a function of the molar ratio % 3 = (1)/(3), mol/mol, of components. e) Mechanistic illustration of diffusive controlled transport of CO2 through membranes of variable composition: (left) linear compact (low content of 3), (center) mixed free volume composite (maximum value of diffusivity at % 3 = 33 %, and (right) highly cross-linked matrix (high content of 3).

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Gas-Diffusion through Dynameric Membranes

In conclusion, ROFs for dynameric membrane films can be rationally designed and synthesized for selective separation of CO2. This example shows that gas transport through ROF-based membrane films can be controlled by diffusion and mutual constitutional interactions between the gas molecules and the dynameric network, at molecular level. For all gases, the molar ratio (1)/(3) of 2/1 mol/ mol (33 %) generates the optimal free volume matrix for maximum diffusion. The cross-linking component 3 pushes back the macromonomeric chains of 1 and ensures a total free volume increase at 33 % mol/mol of 3 in the polymeric matrix, and thus the highest diffusion for all gases at this ratio. Moreover, due to structural behaviors and an increased CO2-philic character of 3, the transport of CO2 is strongly favored and is controlled by both increasing CO2 sorption (solubility) and diffusivity. Based on this discovery, one could imagine a fundamental transition from macromolecular design toward constitutional approaches,[2729] which might push the limits and achieve the molecular limit of gas permeable membranes. Finally, the rubbery dynameric membranes presented here allow a maximum permeability of 180 Barrers for CO2 and an interesting PCO2/PN2 = 16 permeselectivity. For industrial applications, higher CO2 permeability is most effective at reducing costs. Relying on higher selectivity, instead, would require large membrane areas. Membranes with high CO2 permeance (1000 Barrers) are required, while a selectivity of 2040 is enough for industrial purposes.[30] Within this context, the ROF-based membranes reported here show a strong potential. Prospects for the future include the development of these ROFs as an alternative to high performing MOFs in the design of novel dynamic systems presenting a greater degree of structural complexity. These results should initiate new interdisciplinary discussions about highly competitive systems for gas separation, which are constitutionally controlled at the molecular scale.

Acknowledgements
This work was conducted as part of DYNANO, PITNGA-2011-289033 (www.dynano.eu) and ANR 2010 BLAN 717 2.

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