Polyimide membranes aromatic polyimides

Miscellaneous Applications. Ben2otrifluoride derivatives have been incorporated into polymers for different appHcations. 2,4-Dichloroben2otrifluoride or 2,3,5,6-tetrafluoroben2otrifluoride [651-80-9] have been condensed with bisphenol A [80-05-7] to give ben2otrifluoride aryl ether semipermeable gas membranes (336,337). 3,5-Diaminoben2otrifluoride [368-53-6] and aromatic dianhydrides form polyimide resins for high temperature composites (qv) and adhesives (qv), as well as in the electronics industry (338,339). 

Membrane modules have found extensive commercial appHcation in areas where medium purity hydrogen is required, as in ammonia purge streams (191). The first polymer membrane system was developed by Du Pont in the early 1970s. The membranes are typically made of aromatic polyaramide, polyimide, polysulfone, and cellulose acetate supported as spiral-wound hoUow-ftber modules (see Hollow-FIBERMEMBRANEs). 

Makino, H., Y. Kusuki, H. Yoshida, and A. Nakamura, Process for Preparing Aromatic Polyimide Semipermeable Membranes, U.S. Patent No. 4,378,324, March 1983. 

Another concern for polystyrene- and some aromatic-based PEMs is hydrolysis of fhe sulfonic acid group from aromatic rings as well as hydrolytic cleavage of polymer backbone under fuel cell conditions for aromafic polymers including polyimides, poly(arylene ethers), poly(ether ketones), and poly(ether sulfones). It is well known that the sulfonation of aromafic rings is a reversible process especially at low pH and at elevated temperature (Scheme 3.3). The reversibility of sulfonation, for example, is used in fhe preparafion of trinitrotoluene or picric acid. Por the simplest membrane of the class of arylsulfonic acids (i.e., benzenesulfonic acid), fhe reacfion occurs upon freatment with a stream of superheated steam at 180°C.i ... 

Shobha, H. K., Sankarapandian, M., Glass, T. E. and McGrath, J. E. 2000. Sulfonated aromatic diamines as precursors for polyimides for proton exchange membranes. Abstracts of Papers of the Americttn Chemical Society 220 11278-11278. 

Asano, N., Aoki, M., Suzuki, S., Miyatake, K., Uchida, H. and Watanabe, M. 2006. Aliphatic/aromatic polyimide ionomers as a proton conductive membrane for fuel cell applications. Journal of the American Chemical Society 128 1762-1769. 

Y. Kusuki, T. Yoshinaga and H. Shimazaki, Aromatic Polyimide Double Layered Hollow Filamentary Membrane and Process for Producing Same, US Patent 5,141, 642 (August, 1992). 

The membrane used depends on the nature of the organics. Poly(vinyl alcohol) and cellulose acetate [14] have been used to separate alcohols from ethers. Polyurethane-polyimide block copolymers have been used for aromatic/aliphatic separations [17]... 

Fluorinated polyimides have achieved great importance as barrier materials during the last few years. Many experimental polyimides prepared from fluorine-containing monomers, mainly novel diamines, show an advantageous balance of permeability and selectivity for technical gases and vapours, which makes them very attractive for the fabrication of permselective membranes [119]. This is an application field showing very rapid expansion, where there exists a strong demand for new polymeric materials, and where soluble aromatic polyimides are considered as a real alternative [136-146]. 

A nonporous aromatic polyimide membrane that is selectively permeable to H2, H, and H O has also been used for water vapor removal before the sample enters the ICP-MS [32]. Molecular analyte oxide ion signals were reduced approximately two orders of magnitude and O-containing polyatomic ions, such as ArO+ and C10+, were reduced by one to two orders of magnitude. 

Monsanto and Ube (Japan) developed membrane processes for purification of hydrogen gas mixtures. This process is based on the selective diffusion of hydrogen through semi-permeable membranes in the form of hollow fibers. The Monsanto PRISM separator process (owned by Air Products as of 2004) uses a polysulfone fiber whereas Ube uses an aromatic polyimide fiber.46... 

Specialty polymers achieve very high performance and find limited but critical use in aerospace composites, in electronic industries, as membranes for gas and liquid separations, as fire-retardant textile fabrics for firefighters and race-car drivers, and for biomedical applications (as sutures and surgical implants). The most important class of specialty plastics is polyimides. Other specialty polymers include polyetherimide, poly(amide-imide), polybismaleimides, ionic polymers, polyphosphazenes, poly(aryl ether ketones), polyarylates and related aromatic polyesters, and ultrahigh-molecular-weight polyethylene (Fig. 14.9). 

According to literary data, the following mixtures of aromatic/aliphatic-aromatic hydrocarbons were separated toluene/ n-hexane, toluene/n-heptane, toluene/n-octane, toluene/f-octane, benzene/w-hexane, benzene/w-heptane, benzene/toluene, and styrene/ethylbenzene [10,82,83,109-129]. As membrane media, various polymers were used polyetherurethane, poly-esterurethane, polyetherimide, sulfonyl-containing polyimide, ionicaUy cross-linked copolymers of methyl, ethyl, n-butyl acrylate with acrilic acid. For example, when a composite polyetherimide-based membrane was used to separate a toluene (50 wt%)/n-octane mixture, the flux Q of 10 kg pm/m h and the separation factor of 70 were achieved [121]. When a composite mebrane based on sulfonyl-containing polyimide was used to separate a toluene (1 wt%)/ -octane mixture, the flux 2 of 1.1 kg pm/m h and the separation factor of 155 were achieved [10]. When a composite membrane based on ionically cross-linked copolymers of methyl, ethyl, w-butyl acrylate with acrilic acid was used to separate toluene (50 wt%)//-octane mixture, the flux Q of 20-1000 kg pm/m h and the separation factor of 2.5-13 were achieved [126,127]. 

In oil processing, separation of aromatic isomers Cg (ethylbenzene 7b= 136°C,p-xylene 7b= 138.3°C, m-xylene Ty, = 139.1°C, >-xylene T], = 144.4°C) is required. According to the literary data, the following isomers of hydrocarbons are separated p-xylene/m-xylene, p-xylene/o-xylene, -hexane/2,2-dimethylbutane, -hexane/3-methylpentane, and n-butane/f-butane [8,83,130-137]. Pervaporation method is the most effective for this purpose. To separate the isomers, membranes based on various polymers were used. Good separation for aU isomer mixtures was attained by the polyimide Kapton film (fip = 1.43-2.18) but parylene films and cellulose acetate also exhibited a relatively high separation factor (fip = 1.22-1.56 and /3p = 1.23-1.56, respectively). Temperatures >200°C were required to obtain a reasonable flux through the polyimide film and a pressure of about 20 atm was necessary to keep the feed stream liquid [8]. 

The polymer materials mainly used for the membranes are glassy polymers, the first and foremost polyimides. The use of glassy polymers having a rigid ensemble of macromolecules results in high separation effectiveness. Separation effectiveness in pervaporation processes is characterized by the separation factor, /3p, which is determined by the diffusion component, /3d, and the sorption component, /3s [8,55]. Let us consider the effect of chemical composition of polymer membranes on their transport properties with respect to aromatic, alicyclic, aliphatic hydrocarbons and analyze ways to improve these properties. 

To increase the sorption component of the separation factor, homogeneously distributed tetracyanoethylene, a strong electron acceptor having high affinity for electron donors, was added to the polyimide matrix [77]. It can be seen from data presented in Table 9.12 that this is accompanied by an increase in the sorption component /3s (benzene/cyclohexane) by a factor of 1.5 probably as a result of selective sorption of aromatic compounds by tetracyanoethylene with a simultaneous increase in the diffusion component /3d. The prepared membranes showed good pervaporation properties with respect to benzene/cyclohexane, toluene/isooctane mixtures. For example, for a two-component 50/50 wt% benzene/cyclohexane mixture at 343 K, the flux was 2 = 0.44 kg p,m/m h, and /3p (benzene/cyclohexane) = 48 and for a two-component toluene/isooctane mixture, 45/55 wt%, at 343 K the flux was 2 = 1-1 kg p-m/m h, and /3p (toluene/wo-octane) = 330. 

Okamoto K, Wang H, Ijyuin T, Fujiwara S, Tanaka K, and Kita H. Pervaporation of aromatic/non-aromatic hydrocarbon mixtures through crosslinked membranes of polyimide with pendant phosphonate ester groups. J Membr Sci 1999 157 97-105. 

Wang YC, Li CL, Huang J, Lin C, Lee KR, Liaw DJ, and Lai JY. Pervaporation of benzene/cyclohexane mixtures through aromatic polyimide membranes. J Membr Sci 2001 185 193-200. 

Figure 10.5 Development of the H-bond network in a sulfonated polyimide (homo)polymer made of chains of aromatic and polyaromatic substituted cycles. Three repeat units of a chain are represented. Structure of the dried membrane in the upper drawing, of the membrane in equilibrium with an atmosphere with hygrometry 15% (middle page drawing) and 65% (lower drawing).

The aromatic polyimides, cited earlier, separate carbon dioxide over methane with a-valves of 150-160. Aromatic polyoxadiazoles have a-valves of 100-2 00.157 The permeability of one aromatic polyimide was improved by two to four orders of magnitude by carbonizing it on porous alumina,158 the final a-valve being 100. In this case, the final actual membrane was probably a porous carbon molecular sieve. Facilitated transport has also been used to increase the separation factor. A porous poly(vinylidene difluoride) membrane with ethanolamine or diethanolamine in the pores gave a separation factor of carbon dioxide over methane of 2000.159 Such a method is less energy-intensive than when an amine is used in the usual solvent method. 

Aromatic polyimides, containing trifluoromethyl groups, have been used to separate hydrogen over carbon monoxide, with a-values of 26-66 and hydrogen over methane with a-valves of 73-380.160 An a-valve of 22 was obtained with a membrane of a copolymer of methyl methacrylate and tris (trimethylsiloxy) y (met ha cry loxy)propyl] silane, in a process estimated to cost only 40% of the cost of the present cryogenic distillation.161... 

Ho W., Sartori G., Thaler W. A., Dalrymple D. C. 1997. Separating aromatics from non aromatics by polyimide-polyester membrane. US Patent 5.670.052. 

Ribeiro C. P., Freeman B. D., Kalika D. S., Kalakkunnath S. 2012. Aromatic polyimide and polybenzoxazole membranes for the fractionation of aromatic/aliphatic hydrocarbons by pervaporation. Journal of Membrane Science 390-391 182-193. 

White [25] investigated the transport properties of a series of asymmetric poly-imide OSN membranes with normal and branched alkanes, and aromatic compounds. His experimental results were consistent with the solution-diffusion model presented in [35]. Since polyimides are reported to swell by less than 15%, and usually considerably less, in common solvents this simple solution-diffusion model is appropriate. However, the solution-diffusion model assumes a discontinuity in pressure profile at the downstream side of the separating layer. When the separating layer is not a rubbery polymer coated onto a support material, but is a dense top layer formed by phase inversion, as in the polyi-mide membranes reported by White, it is not clear where this discontinuity is located, or whether it wiU actually exist The fact that the model is based on an abstract representation of the membrane that may not correspond well to the physical reality should be borne in mind when using either modelling approach. 

C. Linder, M. Nemas, M. Perry, R. Ka-TRARO, Silicone-derived solvent stable membranes, US Patent 5205934 (1993). L. S. White, Polyimide membranes for hyperfiltration recovery of aromatic solvents, US Patent 6180008 (2001). 

A suitable polymer material for preparation of carbon membranes should not cause pore holes or any defects after the carbonization. Up to now, various precursor materials such as polyimide, polyacrylonitrile (PAN), poly(phthalazinone ether sulfone ketone) and poly(phenylene oxide) have been used for the fabrication of carbon molecular sieve membranes. Likewise, aromatic polyimide and its derivatives have been extensively used as precursor for carbon membranes due to their rigid structure and high carbon yields. The membrane morphology of polyimide could be well maintained during the high temperature carbonization process. A commercially available and cheap polymeric material is cellulose acetate (CA, MW 100 000, DS = 2.45) this was also used as the precursor material for preparation of carbon membranes by He et al They reported that cellulose acetate can be easily dissolved in many solvents to form the dope solution for spinning the hollow fibers, and the hollow fiber carbon membranes prepared showed good separation performances. 

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