Salt complexation

With a large excess of sodium hydroxide solution, the salt complex is decomposed and the free amine is liberated ... 

Refractive Index. The effect of mol wt (1400-4000) on the refractive index (RI) increment of PPG in ben2ene has been measured (167). The RI increments of polyglycols containing aUphatic ether moieties are negative drj/dc (mL/g) = —0.055. A plot of RI vs 1/Af is linear and approaches the value for PO itself (109). The RI, density, and viscosity of PPG—salt complexes, which maybe useful as polymer electrolytes in batteries and fuel cells have been measured (168). The variation of RI with temperature and salt concentration was measured for complexes formed with PPG and some sodium and lithium salts. Generally, the RI decreases with temperature, with the rate of change increasing as the concentration increases. 

The existence of half-salt complex cations formed by the association of an ammonium cation B", with a neutral molecule, B, has also been postulated. 

Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of ethylene. Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstocks used in the production of ethylene, the yield of butadiene varies. Eor use in polymerization, the butadiene must be purified to 994-%. Cmde butadiene is separated from C and C components by distillation. Separation of butadiene from other C constituents is accomplished by salt complexing/solvent extraction. Among the solvents used commercially are acetonitrile, dimethyl acetamide, dimethylform amide, and /V-methylpyrrolidinone (13). Based on the available cmde C streams, the worldwide forecasted production is as follows 1995, 6,712,000 1996, 6,939,000 1997, 7,166,000 and 1998, 7,483,000 metric tons (14). As of January 1996, the 1995 actual total was 6,637,000 t. 

A second class of important electrolytes for rechargeable lithium batteries are soHd electrolytes. Of particular importance is the class known as soHd polymer electrolytes (SPEs). SPEs are polymers capable of forming complexes with lithium salts to yield ionic conductivity. The best known of the SPEs are the lithium salt complexes of poly(ethylene oxide) [25322-68-3] (PEO), —(CH2CH20) —, and poly(propylene oxide) [25322-69-4] (PPO) (11—13). Whereas a number of experimental battery systems have been constmcted using PEO and PPO electrolytes, these systems have not exhibited suitable conductivities at or near room temperature. Advances in the 1980s included a new class of SPE based on polyphosphazene complexes suggesting that room temperature SPE batteries may be achievable (14,15). 

As in the case of the salt complexation processes, the cryogenic systems require prepuriftcation of the feed gas. Bulk water, hydrogen sulfide, and carbon dioxide are removed by standard techniques. Final removal of these materials is accompHshed by adsorption. After prepuriftcation, the gases are ready for cryogenic processing. 

For colorimetric or gravimetric determination l-nitroso-2-naphthol can be used. For chromatographic ion exchange (qv), cobalt is isolated as the nitroso-(R)-salt complex. The cyanate complex is used for photometric determination and the thiocyanate for colorimetry. A rapid chemical analysis of... 

Nylon resins are made by numerous methods (53) ranging from ester amidation (54) to the Schotten-Baumann synthesis (55). The most commonly used method for making nylon-6,6 and related resins is the heat-induced condensation of monomeric salt complexes (56). In this process, stoichiometric amounts of diacid and diamine react in water to form salts. Water is removed and further heating converts the carboxylate functions to amide linkages. Chain lengths are controlled by small amounts of monofunctional reagents. The molten finished nylon resin can be dkectly extmded to pellets. 

The preparation of nylon resins from lactam precursors involves ring opening, which is facihtated by a controlled amount of water in the reaction mixture. The salt complex condenses internally to produce the polyamide (57). The synthesis of nylon-6 [25038-54-4] from S-caprolactam is as follows ... 

Today the sulphonation route is somewhat uneconomic and largely replaced by newer routes. Processes involving chlorination, such as the Raschig process, are used on a large scale commercially. A vapour phase reaction between benzene and hydrocholoric acid is carried out in the presence of catalysts such as an aluminium hydroxide-copper salt complex. Monochlorobenzene is formed and this is hydrolysed to phenol with water in the presence of catalysts at about 450°C, at the same time regenerating the hydrochloric acid. The phenol formed is extracted with benzene, separated from the latter by fractional distillation and purified by vacuum distillation. In recent years developments in this process have reduced the amount of by-product dichlorobenzene formed and also considerably increased the output rates. 

Frensch and Vdgtle have recently appended three crown ether units to the cyclo-triveratrylene unit . Note that Hyatt had previously prepared the open-chained relatives of this structure (see Sect. 7.3 and Eq. 7.6). Whereas Hyatt prepared the cyclo-triveratrylene skeleton and then appended polyethyleneoxy arms to it, Frensch and Vogtle conducted the condensation reaction (formaldehyde/HCl) on the preformed benzocrown. Thus benzo-15-crown-5 was converted into the corresponding tris-crown (IS) (mp 203.5—205.5°) in 4% yield. The yield was somewhat higher for the condensation of benzo-18-crown-6, but in both cases, yield ranges were observed. These species formed 1 3 (ligand/salt) complexes with sodium and potassium ions. 

The initiating radicals are assumed to be SCN, ONO or N3 free radicals. Tris oxalate-ferrate-amine anion salt complexes have been studied as photoinitiators (A = 436 nm) of acrylamide polymer [48]. In this initiating system it is proposed that the CO2 radical anion found in the primary photolytic process reacts with iodonium salt (usually diphenyl iodonium chloride salt) by an electron transfer mechanism to give photoactive initiating phenyl radicals by the following reaction machanism ... 

Figure 2. Vapor pressures of bromine/quaternary ammonium salt complexes elemental Br2, Me4N+ Br, MEMBr, Oct,MeN Cl. From Ref. [59J.

Complexed arenediazonium salts are stabilized against photochemical degradation (Bartsch et al., 1977). This effect was studied in the former German Democratic Republic in the context of research and development work on diazo copying processes (Israel, 1982 Becker et al., 1984) as well as in China (Liu et al., 1989). The comparison of diazonium ion complexation by 18-crown-6 and dibenzo-18-crown-6 is most interesting. Becker at al. (1984) found mainly the products of heterolytic dediazoniation when 18-crown-6 was present in photolyses with a medium pressure mercury lamp, but products of homolysis appeared in the presence of dibenzo-18-crown-6. The dibenzo host complex exhibited a charge-transfer absorption on the bathochromic slope of the diazonio band. Results on the photo-CIDNP effect in the 15N NMR spectra of isotopically labeled diazonium salts complexed by dibenzo-18-crown-6 indicate that the primary step is a single electron transfer. 

Changes to the active substance(s), such as use of different salts, complexes, isomers, or slightly different biological materials. 

The classical example of a soUd organic polymer electrolyte and the first one found is the poly(ethylene oxide) (PEO)/salt system [593]. It has been studied extensively as an ionically conducting material and the PEO/hthium salt complexes are considered as reference polymer electrolytes. However, their ambient temperature ionic conductivity is poor, on the order of 10 S cm, due to the presence of crystalUne domains in the polymer which, by restricting polymer chain motions, inhibit the transport of ions. Consequently, they must be heated above about 80 °C to obtain isotropic molten polymers and a significant increase in ionic conductivity. 

The mechanism of ion transport in the MEEP/metal salt complexes has been modelled on the PEO transport mechanism, that is to say in terms of jumps of the metal ion between the ether oxygen nuclei of the side groups, the nitrogen atoms of the backbone being not involved in the coordination [599]. 

To improve the dimensional stability of the oligoethyleneoxy phosphazene/ metal salt complexes, some attempts have been reported which concern the chemical modification of the parent polymers, their chemical or radiation cross-linking, or the use of blends. 

A chemical cross-hnking of MEEP was obtained by Shriver [606] by using polyethylene glycol (PEG) dialkoxide, which also forms polymer salt complexes. The cross-linked polymers were prepared by substituting a part (1 and 10 mole%) of the methoxyethoxyethoxy ethanol by PEG in the synthesis of MEEP. Contrary to the MEEP, the amorphous polymers obtained do not flow and are stable even at 140 °C. The maximum ionic conductivity at 30 °C, obtained after complexation with liSOjCFj, are 4.1x10" S cm for MEEP/PEG 1% complexed with 6.4 wt% salt and 3x10" S cm for MEEP/PEG 10% com-plexed with 8.9 wt% salt. These values are comparable with those obtained with the parent hnear polyphosphazenes. 

In conclusion, polymer electrolytes based on phosphazene backbone and containing ether side chains are, after complexation with alkali metal salts, among the highest ionically solvent-free polymer salt complexes, with conductivities in the order of 10" -10" S cm However, these conductivities are still below the value of 10 S cm" which is considered to be the minimum for practical applications. Therefore the design of new polyphosphazenes electrolytes with a higher conductivity and also a higher dimensional stability still remains a challenge for future researchers. 

In volume 7 reactions of metallic salts, complexes and organometallic compounds are covered. Isomerisation and group transfer reactions of inert metal complexes and certain organometallics (not involving a change in oxidation state) are considered first, followed by oxidation-reduction processes (a) between different valency states of the same metallic element (b) between salts of different... 

Reduction of Poly(2-cyano-l,3-phenylene arylene ether), 20 Twenty-five mL of a 1.0 M solution of lithium aluminum hydride (LAH) in THF was cooled to 0° C before adding a solution of 1.64 g (5.0 meg) of 20 in 120 mL of THF. The resultant slurry was stirred for 24 h at 0° C, refluxed for 1 h, recooled to 5° C, and the excess LAH decomposed with 2 mL of water. The volume of the solution was reduced to 25 mL before pouring the mixture into 500 mL of 5% HC1 to dissociate the amine aluminum salt complex and precipitate the polymer. The polymer was recovered by filtration, reslurried in 20 mL of water and the pH adjusted to 9.0 with NaOH. After recovery of the neutralized polymer was recovered, it was dried in vacuo redissolved in CHC13, and reprecipitated using water as the nonsolvent. Final drying in vacuo for 24 h at 35° C left 1.2 g (72.3%) of poly[oxy-l,4-phenylene-(l-methylethylidene)-l, 4 -phenylene-oxy-(2"-aminomethyl)-l",3"-phenylene], 21, [n] (CHCI3) 0.3 dl/g. 

Unique combinations of properties continue to be discovered in inorganic and organometallic macromolecules and serve to continue a high level of interest with regard to potential applications. Thus, Allcock describes his collaborative work with Shriver (p. 250) that led to ionically conducting polyphosphazene/salt complexes with the highest ambient temperature ionic conductivities known for polymer/salt electrolytes. Electronic conductivity is found via the partial oxidation of unusual phthalocyanine siloxanes (Marks, p. 224) which contain six-coordinate rather than the usual four-coordinate Si. 

Utilizing more reactive discrete palladium-N-heterocyclic carbene (NHC) complexes (for example, Pd(carb)2) or in situ generated palladium/imidazolium salt complexes (1 mol% ligand A), Caddick and coworkers were able to extend the rapid amination protocols described above to electron-rich aryl chlorides (Scheme 6.61) [128],... 

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