No abstract

Prior work has suggested simple guidelines for matching transport characteristics of materials to form high-performance mixed-matrix materials for gas separation. Such materials comprise a dispersion of molecular sieving particles in a properly selected matrix polymer phase. Recent work has shown that these simple criteria are necessary but not sufficient to achieve the desired properties. The analysis presented here shows the need to optimize the transport properties of the interfacial region, i.e., the region between the bulk polymer and dispersed sieve phases. Guided by the need to optimize both the transport properties of the interfacial region and the matrix material selection criteria noted above, a new paradigm is recommended for matrix phase selection. The practicality of the paradigm is validated by the formation of mixed-matrix membranes with an appropriate polymer and sieve. These materials lead to the attractive predicted performances at low loading. For success at higher loading a zeolite "priming" protocol based on polymer-solvent sieve interactions is shown to be necessary. This modified protocol leads to success at intermediate and high dispersed-phase loading.

Mixed matrix materials comprised of molecular sieve domains embedded in processable polymer matrices have the potential to provide membranes with higher permselectivity and equivalent productivity compared to existing membrane materials. It has been shown that successful mixed matrix materials can be formed using relatively low glass transition (T g ) polymers that have a favorable interaction with the sieves. This article extends this earlier work to include the use of more practical rigid matrix polymers with high T g s that can ultimately be used in forming high-performance mixed matrix layers for composite membranes. Initial attempts to form mixed matrix materials based on high T g polymers with a type 4A zeolite resulted in poor adhesion between the polymer and sieve. Correcting this problem was pursued in this study by forming the composite material close to the T g of the polymer by addition of a plasticizer to match the matrix T g with the solvent volatility. Forming the films at elevated temperatures presented substantial challenges, and this work discusses overcoming these challenges in detail. With some modifications in the film casting procedure, successful materials were achieved. Promising oxygen/nitrogen transport results are presented for these zeolite 4A-Matrimid/plasticizer membranes, and this data compares favorably with predictions of the well-known Maxwell model for composite systems.

Mixed matrix materials comprising molecular sieve entities embedded in a polymer matrix can economically increase membrane permselectivity, thereby addressing a key challenge hindering the widespread use of membrane‐based gas separations. Prior work has clarified the importance of proper selection of the dispersed sieve phase and the continuous matrix phase based on their intrinsic transport properties. Proper material selection for the two components, while necessary, is not sufficient since the interfacial contact zone appears to be equally important to achieve optimum transport properties. Specifically, it was found that chemical coupling of the sieve to the polymer can lead to better macroscopic adhesion but to even poorer transport properties than in the absence of the adhesion promoter. This counterintuitive behavior may be attributed to a nanometric region of disturbed packing at the polymer sieve interphase. The poor properties are believed to result from “leakage” of gas molecules along this nanometric interface. The Maxwell model was modified to take into account these complexities and to provide a first order quantification of the nanometric interphase. The analysis indicates that optimization of the transport properties of the interfacial region is key to the formation of ideal mixed matrix materials. This approach is used in the second part of this paper to form successful mixed matrix membrane materials.

Analysis presented in Part 1 of this paper indicated the importance of optimization of the transport properties of the interfacial region to achieve ideal mixed matrix materials. This insight is used in this paper to guide mixed matrix material formation with more conventional gas separation polymers. Conventional gas separation materials are rigid, and, as seen earlier, lead to the formation of an undesirable interphase under conventional casting techniques. We show in this study that if flexibility can be maintained during membrane formation with a polymer that interacts favorably with the sieve, successful mixed matrix materials result, even with rigid polymeric materials. Flexibility during membrane formation can be achieved by formation of films at temperatures close to the glass transition temperature of the polymer. Moreover, combination of chemical coupling and flexibility during membrane formation produces even more significant improvements in membrane performance. This approach leads to the formation of mixed matrix material with transport properties exceeding the upper bound currently achieved by conventional membrane materials. Another approach to form successful mixed matrix materials involves tailoring the interface by use of integral chemical linkages that are intrinsically part of the chain backbone. Such linkages appear to tighten the interface sufficiently to prevent “nonselective leakage” along the interface. This approach is demonstrated by directly bonding a reactive polymer onto the sieve surface under proper processing conditions.