Polyaramide

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). 

For example, there is a dramatic improvement in modulus, tensile strength, and thermal stability when the aliphatic components in polyamides (nylons) are replaced by aromatic components, resulting in polyaramides such as Kevlar (29). Likewise, poly(ether ether ketone) (PEEK), one of the mechanically strongest condensation... 

Kragl and Dreisbach (1996) have carried out the enantioselective addition of diethyl zinc to benzaldehyde in a continuous asymmetric membrane reactor using a homogeneous soluble catalyst, described in their paper. Here a,a-diphenyl-L-proline was used as a chiral ligand, coupled to a copolymer made from 2-hydroxy ethyl methacrylate and octadecyl methacrylate, which had a sufficiently high molecular weight to allow separation by ultra-filtration (U/F). The solvent-stable polyaramide U/F Hoechst Nadir UF PA20 retained more than 99.8% of the catalyst. The ee was 80 %, compared to 98 % for a noncoupled catalyst. 

Membrane filtration using a polyaramide membrane [56] showed a retention of more than 99.8%. Application of this catalyst in a continuously operated membrane reactor showed conversion for more than 150 h. The ee dropped from 80% in the beginning (non-bonded analogue 97%) to about 20% after 150 h. The average ee for the first 80 h was 50%. 

If degradation is due to sequential or synergistic mechanisms, then a simple extrapolation may not be reasonable. For example, in accelerating the rate of oxidation of polyethylene it may be necessary to identify the induction time and subsequent degradation time separately and to produce Arrhenius diagrams for each. The total time to failure is the sum of the two times. Figure 9.3 shows an instance of where unknowing extrapolation of the short-term results in tests on polyaramid fibres could have led to overestimates of lifetime and premature failure. 

Figure 9.3 Illustration of the optimistic prediction of the rupture lifetime of a polyaramid from short-term data, if the presence of a transition is not taken into account (curve shape based on data from [7])...

Allred, R.E., Merrill, E.W. and Roylance, D.K. (1985). Surface chemical modification of polyaramid filaments with amine plasma. In Molecular characterization of compo.site interfaces (H. Ishida and G. Kumar, eds.). Plenum Press, New York, pp. 333-375. 

The most extensive research on furanic polyamides is recent (33) and deals essentially with furanic-aromatic structures, although an important effort was also devoted to all-fiiranic compositions. The reaction of the diacid 11a with various aromatic diamines leads to high-molecular weight polymers with good thermal stability and ciystallinity. Structure 23, obtained with p-phenylenediamine, exhibited features resembling closely those of polyaramides ... 

Kragl 13) pioneered the use of membranes to recycle dendritic catalysts. Initially, he used soluble polymeric catalysts in a CFMR for the enantioselective addition of Et2Zn to benzaldehyde. The ligand a,a-diphenyl-(L)-prolinol was coupled to a copolymer prepared from 2-hydroxyethyl methyl acrylate and octadecyl methyl acrylate (molecular weight 96,000 Da). The polymer was retained with a retention factor > 0.998 when a polyaramide ultrafiltration membrane (Hoechst Nadir UF PA20) was used. The enantioselectivity obtained with the polymer-supported catalyst was lower than that obtained with the monomeric ligand (80% ee vs 97% ee), but the activity of the catalyst was similar to that of the monomeric catalyst. This result is in contrast to observations with catalysts in which the ligand was coupled to an insoluble support, which led to a 20% reduction of the catalytic activity. 

The special properties and differences between all-mefa linked and all-pflra linked polyaramides have three reasons ... 

Allred, R. E. Surface Chemical Modification of Polyaramid Filaments with Amine Plasmas, Ph.D. Dissertation, Mass. Inst. Tech., Dept, of Mater. Sci., (1983)... 

Removal of carbon dioxide is the only membrane-based natural gas separation process currently practiced on a large scale—more than 200 plants have been installed, some very large. Most were installed by Grace (now Kvaerner-GMS), Separex (UOP) and Cynara and all use cellulose acetate membranes in hollow fiber or spiral-wound module form. More recently, hollow fiber polyaramide (Medal) membranes have been introduced because of their higher selectivity. 

Ammonia plants Medal Polyaramide/fine fiber ... 

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