Water-organic interfacial synthesis

Environmental Rationale for an Organic-Water Interfacial Synthesis... 

The feasibility and some of the advantages of a novel organic-water interfacial synthesis technique have been demonstrated on several reactions of commercial and scientific interests. The new technique is based on the use of a surface-active... 

The previous extension of solvent mixtures involved solvent interfaces. This organic-water interfacial technique has been successfully extended to the synthesis of phenylacetic and phenylenediacetic acids based on the use of surface-active palla-dium-(4-dimethylaminophenyl)diphenylphosphine complex in conjunction with dode-cyl sodium sulfate to effect the carbonylation of benzyl chloride and dichloro-p-xylene in a toluene-aqueous sodium hydroxide mixture. The product yields at 60°C and 1 atm are essentially quantitative based on the substrate conversions, although carbon monoxide also undergoes a slow hydrolysis reaction along with the carbonylation reactions. The side reaction produces formic acid and is catalyzed by aqueous base but not by palladium. The phosphine ligand is stable to the carbonylation reactions and the palladium can be recovered quantitatively as a compact emulsion between the organic and aqueous phases after the reaction, but the catalytic activity of the recovered palladium is about a third of its initial activity due to product inhibition (Zhong et al., 1996). 

The interfacial synthesis of bisphenol-A carbonate oligomers is conducted by passing phosgene into an agitated, two-phase mixture of a water-insoluble organic solvent and an alkaline solution of bisphenol-A. Reactions 1-4 shown on p. 260 illustrate some of the reactions believed to occur in the interfacial system. 

One of the main problems in modern nanotechnology is the preparation and stabilization of nanoparticles of different nature semiconductors, metals, organic compounds, etc. Nowadays there are a number of methods for nanoparticle synthesis [1]. Among them water-in-oil reverse micelles (RMs) are the successful technique for the controlled preparation of very small and monosized nanoparticles. Water-in-oil RMs are thermodynamically stable dispersion of nanosized water drops in organic solvent, stabilized by surfactants. RMs are formed spontaneously due to the surfactants, which diminish the interface tension down to ultralow values, and as a result the free energy decreases when the total oil-water interfacial area increases. Thermodynamically stable water-in-oil microemulsions can be produced at strictly defined conditions. It is possible to change the size of the water pool of RMs by variation of the ratio between water and surfactant concentrations. This allows changing the size of nanoparticles, which are stabilized in such microemulsions. 

Till date, liquid-crystalline phases [51], colloidal particles [52], and structure-directing molecules [53[ as the soft-template have been employed to synthesize PANI nanostructures. Based on the traditional synthesis method of PANI, in particular, some simple approaches such as interfacial polymerization [54], mixed reactions [55], dilute polymerization [56] and ultrasonic irradiation [57] have also been employed to synthesize PANI. The interfacial polymerization method only allows the oxidative polymerization of aniline to take place at the interface of the organic/water phases and the product directly enters into the water phase, which could facilitate environmentally friendly processing. 

On the other hand, Ishizu et al. [58] reported the synthesis of cyclic polystyrene using interfacial condensation reaction of a/o-dibromopolyslyrcnc prepared from living polystyrene initiated with sodium naphthalene and terminated with 1,4-dibromobutane and then tetramethylenediamine as depicted in Fig. 11. The reaction was carried out in organic solvent/water to yield in more than 90%. The effect of solvent on the yield of cycUc polymer was observed, and the yield of cyclic product obtained in DMSO was higher than that in toluene. Since DMSO dissolves in both water and toluene, the reaction proceeded faster than that in toluene. 

Interfacial polymerization has become a very important and useful technique for the synthesis of thin-film composite RO and NF membranes [5, 13]. Polymerization occurs at the interface between two immiscible solvents that contain the reactants (Fig. 3.6-8). For instance, a UF membrane is immersed in an aqueous diamine solution. The excess of water is removed, and the saturated support is put in contact with an organic phase that contains an acyl chloride. As a consequence, the two monomers react to form a thin layer (1 to 0.1 pm) of PA on top of the U F membrane. 

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