Solvent-impregnated resins hydrophobicity

The last two impregnation methods were proposed as alternatives to the dry impregnation method, because of the high hydrophobic balance showed by impregnated resins obtained by this method. In both cases it is necessary to add a third (solvent in the wet method or the modifier agent in the modifier addition method) or more components in the system. 

Ethyl silicate (tetraethoxysilane) is often used without modification as a water-repellent material for concrete and masonry in general. All, or nearly all. the ethoxyl groups are hydrolyzed by the moisture of the air to form cross-linked watcr-rcpcllcnt polymers. The material is applied in desirable thickness, dissolved in some volatile solvent which soon evaporates. Silicone resins which arc partially condensed before application, or even fully condensed, can also be used here. In the latter case, hardness is achieved on evaporation of the solvent. Certain silicone resins arc useful as hydrophobic agents for the impregnation of paper and fabrics. 

Aluminum chloride and its derivatives are the most familiar Lewis acids and are routinely employed in many Lewis acid-promoted synthetic transformations. The first polymer-supported metal Lewis acids to be studied were polymers attached by weak chemical or physical interactions to a Lewis acid. In the 1970s Neckers and coworkers reported the use of styrene-divinylbenzene copolymer-supported AlCl,- or BF3 as catalyst in condensations, esterifications, and acetalization of alcohols [11,12]. This type of polymer-supported AICI3 (1) is readily prepared by impregnation of a polystyrene resin with AICI3 in a suitable solvent. Subsequent removal of the solvent leaves a tightly bound complex of the resin and AICI3. The hydrophobic nature of polystyrene protects the moisture-sensitive Lewis acid from hydrolysis, and in this form the Lewis acid is considerably less sensitive to deactivation by hydrolysis. This polymer complex could be used as a mild Lewis acid catalyst for condensation of relatively acid-sensitive dicyclopropylcarbinol to an ether (Eq. 1) [13],... 

In comparison with the classical impregnation methods, this procedure has the advantage of polymeric supports with a high hydrophobic balance of the water affinity of the adsorbent that is not reduced by the impregnation of the extractant. As excess organic solvent is removed by water, the resulting resin swells with water. The SlRs prepared by this procedure are denser than water and sink in water. 

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