Microporous polymers

M. Valero, B. Zomoza, C. Tellez, J. Coronas, Mixed matrix membranes for gas separation by combination of silica MCM l and MOF NH2-MIL-53(A1) in glassy polymers, Microporous Mesoporous Materials 192 (2014) 23-28. 

Separator structures fall into four main categories microporous films, nonwovens, gel polymers, and solid polymers. Microporous films contain small pores (5 to 10 nm in diameter) and are often used for low temperature applications. They are made from nonwoven fibers such as cotton, polyester, glass, polyolefins (PP and PE), PTFE, and PVC. Microporous separators are commonly used with organic electrolytes and in acidic systems. Nonwovens are manufactured as mats of fibers and bind through frictional forces. They exhibit consistent weight, thickness, and degradation resistance but they show inadequate pore order and are difficult to make thinner than 25 pm. Nonwovens are generally made from cellulose, PTFE, PVC, PVdF, or a combination of polyolefins and receive preference in alkaline systems [114]. 

Huang L, Wang H, Chen J, Wang Z, Sun J, Zhao D, et al. Synthesis, morphology controL and properties of porous metal-organic coordination polymers. Micropor Mesopor Mater 2003 58 105-14. 

Figure 1 Examples of ions introduced into polymers microporous poly(vinylidene fluoride) swollen with a solution of lithium perchlorate in propylene carbonate (b) Nafion (c) poly(ethylene oxide) plus lithium salt...

Wynne-Jones and Marshfound somewhat similar results with a number of carbons made by pyrolysis of eight organic polymers at a series of temperatures. The isotherms of Nj at 77 K and of COj at 195 K were measured, and the apparent surface area calculated by the usual BET procedure. (Owing to the microporous nature of the solids, these figures for area will be roughly proportional to the uptake at saturation and therefore... 

Phase Separation. Microporous polymer systems consisting of essentially spherical, intercoimected voids, with a narrow range of pore and ceU-size distribution have been produced from a variety of thermoplastic resins by the phase-separation technique (127). If a polyolefin or polystyrene is insoluble in a solvent at low temperature but soluble at high temperatures, the solvent can be used to prepare a microporous polymer. When the solutions, containing 10—70% polymer, are cooled to ambient temperatures, the polymer separates as a second phase. The remaining nonsolvent can then be extracted from the solid material with common organic solvents. These microporous polymers may be useful in microfiltrations or as controlled-release carriers for a variety of chemicals. 

Ceramic, Metal, and Liquid Membranes. The discussion so far implies that membrane materials are organic polymers and, in fact, the vast majority of membranes used commercially are polymer based. However, interest in membranes formed from less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafHtration and microfiltration appHcations, for which solvent resistance and thermal stabHity are required. Dense metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported or emulsified Hquid films are being developed for coupled and facHitated transport processes. 

Fig. 8. Equipment to prepare microporous membranes by the polymer precipitation by cooling technique (23).

Fig. 10. Schematic of casting machine used to make microporous membranes by watervapor imbibition. A casting solution is deposited as a thin film on a moving stainless steel belt. The film passes through a series of humid and dry chambers, where the solvent evaporates from the solution, and water vapor is absorbed from the air. This precipitates the polymer, forming a microporous membrane that is taken up on a collection roU (25).

Cellulose acetate Loeb-Sourirajan reverse osmosis membranes were introduced commercially in the 1960s. Since then, many other polymers have been made into asymmetric membranes in attempts to improve membrane properties. In the reverse osmosis area, these attempts have had limited success, the only significant example being Du Font s polyamide membrane. For gas separation and ultrafUtration, a number of membranes with useful properties have been made. However, the early work on asymmetric membranes has spawned numerous other techniques in which a microporous membrane is used as a support to carry another thin, dense separating layer. 

Fig. 15. Schematic of the interfacial polymerization process. The microporous film is first impregnated with an aqueous amine solution. The film is then treated with a multivalent cross-linking agent dissolved in a water-immiscible organic fluid, such as hexane or Freon-113. An extremely thin polymer film...

Most solution-cast composite membranes are prepared by a technique pioneered at UOP (35). In this technique, a polymer solution is cast directly onto the microporous support film. The support film must be clean, defect-free, and very finely microporous, to prevent penetration of the coating solution into the pores. If these conditions are met, the support can be coated with a Hquid layer 50—100 p.m thick, which after evaporation leaves a thin permselective film, 0.5—2 pm thick. This technique was used to form the Monsanto Prism gas separation membranes (6) and at Membrane Technology and Research to form pervaporation and organic vapor—air separation membranes (36,37) (Fig. 16). 

Although microporous membranes are a topic of research interest, all current commercial gas separations are based on the fourth type of mechanism shown in Figure 36, namely diffusion through dense polymer films. Gas transport through dense polymer membranes is governed by equation 8 where is the flux of component /,andare the partial pressure of the component i on either side of the membrane, /is the membrane thickness, and is a constant called the membrane permeability, which is a measure of the membrane s ability to permeate gas. The ability of a membrane to separate two gases, i and is the ratio of their permeabilities,a, called the membrane selectivity (eq. 9). 

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