Diamines, sulfonated

Numerous diamines and aromatic dianhydrides have been investigated. WhoUy aromatic Pis have been stmctiirally modified by incorporating various functional groups, such as ether, carbonyl, sulfide, sulfone, methylene, isopropjlidene, perfluoroisopropyUdene, bipyridyls, sdoxane, methyl phosphine oxide, or various combinations of these, into the polymer backbone to achieve improved properties. The chemistry and apphcations of Pis have been described in several review articles (4). 

Dimethyl-6-t-butylphenol Hydrogen chloride Ethylene diamine p-Toluene sulfonic acid... 

Biocides Especially for controlling Clostridium and similar organisms found in water present in aviation kerosene and diesel tanks. Biocides include special grades of isothiazolines, polyquats, diamines, and sulfones. 

Carboxylic-sulfonic anhydrides, 80 Cardiovascular surgery, 27 Cardo diamines, 277, 278 Carothers, Wallace, 198 Carothers equation, 11, 59 Carothers group, 1 Carpet waste... 

A plugging material with 2-furaldehyde-acetone monomer and silicone oligomers has been described [1099]. The components for this material are shown in Table 18-1. The 2-furaldehyde-acetone monomer can contain mono-furfurylidene-acetone and difurfurylidene-acetone. The hardener can be iron chloride, benzene-sulfonic acid, hexamethylene diamine, or polyethylene polyamine. The plugging stone has improved strength, elastic-deformation, and anticorrosion and adhesion properties. 

The polyamines putrescine, cadaverine, spermidine, and spermine, which are seen at elevated levels in some victims of cancer, were separated on a Technicon (The Technicon Company Chauncey, NY) TSM Amino Acid Analyzer packed with an 8% divinylbenzene-co-polystyrene sulfonated resin with post-column ninhydrin detection.111 Amines such as ethanolamine, noradrenaline, hexamethylene diamine, methoxytryptamine, spermine, and spermidine were separated from amino acids on a DC-4A cation exchange resin.112 A similar approach, using a Beckman Model 121M amino acid analyzer equipped with an AA-20 column, was also successful.113 A Polyamin-pak strong cation exchange column (JASCO) was eluted with a citrate buffer for the detection of putrescene, spermine, cadaverine, and 1,5-diaminohex-ane from rat thymus.114 A post-column o-phthaldehyde detection system was used. 

One of the first examples of this type of blend was composed of SPEEK or SPES as the acidic component and diaminated PES, poly(4-vinylpyridine) (P4VP), poly(benzimidazole) (PBl), or poly(ethyleneimine) (PEI) as the basic component. " For blend lEC values of 1.0 meq/g, conductivity values were reported to be good, as was H2/O2 EC performance. Thermal stabilities for these blends was also demonstrated to be high (>270°C). Other examples of acid-base PEMs include blends of SPPO and PBI, sulfonated poly(phthalazinone ether ketone) and aminated SPES, SPIs and aminated Pls, and SPEEK with PES bearing benzimidazole side groups, ° as well as an unusual example in which the blend is composed of sulfonated, hyper-branched polyether and pyridine-functionalized polysulfone. ... 

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. 

Yin, Y, Fang, J. H., Watari, T., Tanaka, K., Kita, H. and Okamoto, K. 2004. Synthesis and properties of highly sulfonated proton conducting polyimides from bis(3-sulfopropoxy)benzidine diamines. Journal of Materials Chemistry 14 1062-1070. 

Figure 23. Sulfonated diamines for direct synthesis of sulfonated polyimides.

Principally, one commercially available sulfonated diamine (4,4 -diamino-2,2 -biphenyl disulfonic acid) has been used to synthesize sulfonated polyimides. In addition to the commercially available diamine, several novel sulfonated diamines incorporating flexible or kinked structures have been prepared in Okamoto s lab. " The chemical structures and names of all five diamines are shown in Figure 23. 

A comparison of the hydrolytic stability of several sulfonated six-membered ring polyimides was previously investigated. Membranes were placed in distilled water at 80 °C until a loss of mechanical properties was observed. Improvements in membrane stability were observed for polymers with lower degrees of sulfonation (lower lEC) and for random copolymers, as opposed to block or sequenced copolymers. Additionally, the flexibility of the sulfonated diamine in the polymer structure was shown to play an important role in stability. By simply changing the sulfonated diamine from the rigid 4,4 -diamino-... 

Figure 25. Sulfonated six-membered ring polyimides with novel sulfonated diamines.

Shobha et al. employed a novel sulfonated diamine containing a phosphine oxide moiety in the synthesis of a five—membered ring sulfonated poly-imide. The synthesis is shown in Figure 24. 

Use of the water-soluble analogues of complexes 90 and 91 were later reported by Williams and coworkers [83]. In this study, water solubility was achieved by replacing the chiral diamines TsDPEN and TsCYDN with the p-sulfonated derivatives TsDPEN-S03Na and TsCYDN-S03Na (Scheme 4.41). The ATH of aryl alkyl... 

Reduction of dibenzothiophene with sodium in liquid ammonia has been shown to be sensitive to the experimental methods employed however, the major product is usually 1,4-dihydrodibenzothiophene. 27 -28i The electrochemical reduction of dibenzothiophene in ethylene-diamine-lithium chloride solution has been shown to proceed via stepwise reduction of the aromatic nucleus followed by sulfur elimination. In contrast to the reduction of dibenzothiophene with sodium in liquid ammonia, lithium in ethylenediamine, or calcium hexamine in ether, electrolytic reduction produced no detectable thiophenol intermediates. Reduction of dibenzothiophene with calcium hexamine furnished o-cyclohexylthiophenol as the major product (77%). Polaro-graphic reduction of dibenzothiophene 5,5-dioxide has shown a four-electron transfer to occur corresponding to reduction of the sulfone group and a further site. ... 

The axial immobilization of chiral [Mn((S,S)-salen )j (where salen = (Si,Sj-NiN -bis(3,5-diR -salicylidene)-l,2-diRbethane-diamine R = Bu, R -R = -(CH2)4- R = Bu, R = Ph R = Pn, R R = -(CH2)4-) complexes was achieved by reaction of [Mn(salen )Cl] with sulfonic acid- or phenol-substituted crosslinked and insoluble polystyrene resins [45]. The resulting polymer-immobilized [Mn(salen )j complexes were active and enantioselective for the asymmetric epoxidation of... 

---