Silanols conversion

Several enlightening comparisons can be made from the data of Table I. First an estimate of the vapor phase HMDS surface reaction efficiency vs that of the liquid phase can be obtained. The features of the vapor phase and liquid phase treatments are found in Tables II and III. From Table I, the values for Y58 substrates are 0.22 and 0.11, respectively, thus indicating an approximate 100% greater efficiency towards silanol conversion to trimethyl silyl labelled reaction product for the vapor treatment. An approximate 30% gain is obtained for the oxide substrate comparison. 

From the data reported in Fig. 8, it clearly emerges that the acidity of the silicalite-l/H20 and of the TS-I/H2O systems are remarkably different (compare open and full circles in Fig. 8). This difference can be explained as follows TS-1 has two main acidic sites, Ti(IV) Lewis sites and silanols, mainly located in the internal defective nests (see Sect. 3.8), while only the latter are present in silicalite-1. Addition of H2O2 to siUcaUte-l does not modify the titration curve (compare open circles with open squares in Fig. 8). This means that no additional acidic sites appear in the siUcaUte-l system upon adding H2O2, i.e., that hydrogen peroxide molecules coordinated to internal silanol do not modify their acidity. Conversely, addition of H2O2 to TS-1 moves the whole titration curve toward lower pH values, (compare full circles with full... 

A soluhon explored to definitely eliminate the problem of interachons with free silanol groups was the use of non-silica based stahonary phases. Many studies recently reviewed [9] were conducted on this class of stahonary phases to test their usefulness for UpophiUcity prediction. A few of these phases including polybutadiene-coated alumina [4] and octadecyl-bonded alumina show intereshng results. Conversely, several of them show poor correlahons or correlahons not better than those obtained on ODS stahonary phases between the retenhon parameter and log Pod-... 

Many other methods have been used to prepare bonded phases these include esterification of the surface silanol groups with alco-Tiols, or conversion of the silanol groups to Si—Cl using thionyl chloride, followed by reaction with an organometallic compound. If you are interested, there are details in the textbooks by Knox or by Hamilton and Sewell. 

In contrast, hydrolysis of the methyl derivative, Cp(OC)2Fe-SiMe(H)Cl (Id), yields the corresponding ferrio-silanol, Cp(OC)2Fe-SiMe(H)OH, as a short-lived intermediate identified by means of IR and NMR spectroscopy, which immediately reacts with Id to give the bis(ferrio)disiloxane 6. Conversion of 6 to the fluorine analogue [Cp(0C)2Fe-Si(Me)F]20, characterized by a linear Si-O-Si arrangement [6], is achieved via consecutive H/Cl- and Cl/F-exchange. 

Sears 189) and Heston et al. 190) used the adsorption of sodium hydroxide for the determination of the surface area of colloidal silica. An empirical factor was used for the conversion of alkali consumption into surface area. This is permissible provided the packing density of surface silanols is constant. The determination was performed in concentrated sodium chloride solution in order to keep down the dissolution of silica. Using the same technique, it was found in my laboratory that all surface silanol groups as determined by other methods are neutralized at pH 9.0. At higher pH, siloxane bonds in the surface were opened. A maximum in the sorption of Na+ ions occurred usually at pH 10.5-10.6 which corresponded to a packing density of ca. 5 OH/100 A. On further addition of alkali, silicate ions H3Si04 went into solution. 

The MTO-catalysed oxidation of silanes to silanols (data reported in Table 10) and epoxidation of olefins (data reported in Table 11) by aqueous H2O2 proceeds in high yields and excellent product chemoselectivities (no siloxane and no diol are observed as byproducts) in the presence of zeolite-Y [64], which are better than those obtained under homogeneous conditions (data in Table 11). For example, only 26% of PhMe2SiH is converted with as low as 20% selectivity towards silanol in 24 h when reacted with 85% H2O2 and catalysed by MTO (entry 5, Table 10). However, in the presence of zeolite-Y, 99% conversion is reached with 99% selectivity (entry 6, Table 10). The confinement of the oxidative species inside the 12 A supercages... 

Entry Silane Oxidant Nature Conversion % Selectivity silanol/ disiloxane % Refs. 

A series of novel styrene- and siloxane-based silanol polymers and copolymers were synthesized by a selective oxidation of the Si—H bond with a dimethyldioxirane solution in acetone from corresponding precursor polymers. The conversion of the Si—H to Si—OH in the polymer modification proceeded rapidly and selectively. The silanol polymers obtained in situ showed no tendency for self-condensation to form siloxane crosslinks in solution. Moreover, stable silanol polymers in the solid states were obtained by placing bulky substitute groups bonded directly to the silicon atom. It was found that the properties of these novel silanol polymers and copolymers depended largely on substituents bonded directly to the silicon atom and silanol composition in the copolymers as well. 

Polymer modification is of particular interest when the desired polymer is not readily available from its corresponding monomer by conventional polymerization methods. The primary challenge of polymer modification is to achieve a high conversion and selective modification of the appropriate functional group. In this paper, we describe a new convenient polymer modification to prepare novel silanol polymers by a rapid and selective oxidation of the Si—H bond with a dimethyldioxirane solution in acetone from their corresponding precursor polymers. 

The conventional methods for the synthesis of organosilanols can be accomplished by the hydrolysis of the appropriate substituted silane in the presence of catalysts such as an acid or a base.1 This synthetic route, however, had some difficulty when applied to the synthesis of silanol polymers which demanded not only high conversion of the functional groups for polymer modification but also resistance to the transformation of silanols to siloxane by self- or catalytic condensation during the preparation. 

A new convenient polymer modification for the conversion of the Si—H to Si—OH by the selective oxidation of the Si—H bond by dimethyldioxirane has been described. The oxyfunctionalization of the silane precursor polymers proceeded rapidly and quantitatively and can be applied to the synthesis of a wide variety of novel silanol polymers with specific properties from the corresponding precursor polymers containing Si—H functional groups. Control over the properties of these silanol polymers, such as reactivity and self-association of silanols, was realized through the placement of different substitute groups bonded directly to the silicon atom and by the variation of silanol composition in a copolymer. These novel silanol polymers with a... 

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