Methylchlorosilanes, reaction

In a typical process, the chlorosilane blend is dissolved in a solvent such as toluene or xylene and then stirred with water. When the blend contains mainly methylchlorosilanes, reaction is very rapid and exothermic and cooling may be... 

The chemistry of silicones is summarized by following the steps necessary to produce a two-part, platinum-cured silicone containing vinyl-stopped polydimethylsiloxane, Si-H-on-chain siloxane, platinum catalyst and catalyst inhibitor. The process begins with silicon dioxide and follows the steps of conversion to sand to elemental silicon. Silicon is reacted with MeCl to make methylchlorosilanes in the methylchlorosilane reaction (MCS). The products from the MCS reaction are separated by distillation and then hydrolyzed and condensed to make the various siloxane polymers. Polymers with methyl, vinyl or Si-H functionality are made as required for the platinum addition-cured silicone product. 

In 1940 Rochow discovered the direct process, also cabed the methylchlorosilane (MCS) process, in which methyl chloride is passed over a bed of sibcon and copper to produce a variety of methylchlorosilanes, including dim ethyl dichi oro sil a n e [75-78-5] (CH2)2SiCl2. Working independently, Mbber made a similar discovery in Germany. Consequently, the process is frequently cabed the Rochow process and sometimes the Rochow-Mbber reaction. 

High quahty SAMs of alkyltrichlorosilane derivatives are not simple to produce, mainly because of the need to carefully control the amount of water in solution (126,143,144). Whereas incomplete monolayers are formed in the absence of water (127,128), excess water results in facile polymerization in solution and polysiloxane deposition of the surface (133). Extraction of surface moisture, followed by OTS hydrolysis and subsequent surface adsorption, may be the mechanism of SAM formation (145). A moisture quantity of 0.15 mg/100 mL solvent has been suggested as the optimum condition for the formation of closely packed monolayers. X-ray photoelectron spectroscopy (xps) studies confirm the complete surface reaction of the —SiCl groups, upon the formation of a complete SAM (146). Infrared spectroscopy has been used to provide direct evidence for the hiU hydrolysis of methylchlorosilanes to methylsdanoles at the soHd/gas interface, by surface water on a hydrated siUca (147). 

In this section, we will first demonstrate the formation of methylchlorosilanes from CH3 + a monolayers on CuaSi surfaces. The effects of promoters and the effect of surface segregation on the reaction rate and selectivity are scussed subsequently. 

The evolution of methylchlorosilanes between 450 and 600 K is consistent with the 550 - 600 K typical for the catalytic Rochow Process [3]. It is also reasonably consistent with the evolution of methylchlorosilanes at 500 - 750 K reported by Frank and Falconer for a temperature programmed reaction study of the monolayer remaining on a CuaSi surface after catalytic formation of methylchlorosilanes from CHaCl at higher pressures [5]. Both of these observations suggest that the monolayer formed by methyl and chlorine adsorption on pure CuaSi is similar to that present on active catalysts. For reference, methylchlorosilanes bond quite weakly to tiie surface and desorb at 180 - 220 K. It can thus be concluded that the rate-determining step in the evolution of methylchlorosilanes at 450 - 600 K is a surface reaction rather an product desorption. 

The reactions of CH3 radicals and CI2 alone with CujSi have also been investigated. On pure Cu3Si, the dominant silane product from CH3 adsorption is SiH(CH3>3 and the temperature at which the surface is sputtered prior to methyl adsorption has a dramatic effect on the reaction rate (see section 3.3). The CI2 reaction gives SiCU evolution, and the reaction temperature is close to that for methylchlorosilane formation. 

The products from the reaction of CH3 + Q monolayers on the promoted Cu3Si surface are the same as those for pure Cu3Si, but both the absolute rates and the selectivities are significantly different. In experiments analogous to those described in section 3.1, methylchlorosilanes are evolved from the promoted CusSi surface between 300 and 450 K. This temperature is 200 K lower than that from the pure Cu3Si surface. This 200 K difference in reaction temperature corresponds to a difference of six orders of magnitude in rate (if the rates are extrapolated to a common reaction temperature of 500 K assuming standard and equivalent pre exponential factors for the reactions on these two surfaces [10]). 

We have now tried to make new larger cyclosilanes by the reductive dehalogenation of mixtures of methylchlorosilanes and methylchlorodisilanes. After a separation of the reaction product mixture by means of GC/MS, we found some new cyclosilanes (Fig. 1) [12]. 

The existence of SiCl2 as an intermediate was indicated from an experiment in which the volatile product of a Si/CuCl reaction was allowed to react with CH3CI to form methylchlorosilanes. 

The example of the first category is the formation of alkyl- and arylchlorosilanes in the so-called direct process (DP). The process was discovered over 60 years ago by Rochow in the United States, and, independently, by Muller in Germany, and it is still the most important reaction in organosilicon chemistry. In fact, it is at the very basis of the silicone industry, being the primary source of organochlorosilane precursors (mostly methylchlorosilanes, comprising over 90% of the total) in the production of silicone oligomers and polymers. 

Methylbenzene halogen complex of, 3 122 iodine monochloridecomplese, 3 109 Methylchlorosilanes hydrolysis, 42 149-150, 157 pyrolysis products of, 7 356-363 Methylcobalamin, 19 151, 152 Methyl-coenzyme M reductase, 32 323-325 EPR spectra, 32 323, 325 F43 and, 32 323-324 function, 32 324-325 Methyl-CoM reductase, 32 329 Methyl cyanide, osmium carbonyl complexes, reaction, 30 198-201 Methylcyclophosphazene salts, 21 70 synthesis, 21 109... 

In view of the limited stability of the "carbenoid" LiCsCCP Cl, functionalization reactions have to be carried out a temperatures Lhat are as low as possible. Silylations of meiallated acetylenes are usually rather slow in Et20 at temperatures below -20 C. A small amount of HMPT appears to cause a considerable enhancement of the rates of silylatton with tri-methylchlorosilane. It is not known whether this effect is only due 10 the typical properties of HMPT as a dipolar aprotic solvent (also shown in alkylation with alkyl halides) or whether it is a result of active participation of this solvent in the reaction as depicted in the following equations ... 

Clogston(Ref 2) reported that a bomb contg a mixt of Al carbon tetrachloride(CCl ) exploded violently on heating for 53 min at 152°, The expl decompn of several chlorinated methyl-siloxanes Si chlorinated methylchlorosilanes when heated to ca 200° was reported by Zimmermann(Ref 3). A previously undescribed exothermic reaction of chlorinated rubber with zinc oxide was held responsible for an expln that leveled themanufg area of Dayton Chemical Products Laboratories(Ohio) in April... 

TFSA satisfies all these requirements for hydrophilic silicone surfaces. Using silica as a model for extensively oxidized silicone surfaces, we showed that silylation with vapor phase TFSA took place at room temperature under scrupulously dry conditions. In contrast, others have found for the more conventional silylating agents, the methylchlorosilanes and the methylmethoxy-silanes, that no reaction occurred at temperature below 200°C under similar dry conditions [38]. 

Not only octadecyltrichlorosilane is unreactive towards dry silica at room temperature. This is also the case for the chlorosilanes and the methylchlorosilanes. It was stated earlier that the vapour phase reaction occurs at elevated temperatures (> 473 K). This high-temperature constraint limits potential gas phase silanizing agents to those which have a high thermal stability and sufficient vapour pressure. 

Armistead and Hockey15 used the consecutive reaction path (D) to explain the difference in reactivity and selectivity of BX3 and methylchlorosilanes towards hydroxyl groups. 

Raw stock for the direct synthesis of methylchlorosilanes, methylchlo-ride, has such impurities as moisture, methyl alcohol, oxygen, sulfur dioxide, methylenechloride, dimethyl ether, carbon oxide and dioxide, etc. Most of them negatively affect the synthesis of methylchlorosilanes harmful impurities are chemisorbed on the active centres of contact mass and foul the copper catalyst, which naturally inhibits the reaction of methyl-chloride with contact mass. A similar situation is observed in the direct synthesis of ethylchlorosilanes. 

Selectivity of contact mass. Since the most important products in the synthesis of organochlorosilanes are diorganodichlorosilanes, it is natural that the increase of their yield receives much attention. The selective formation of diorganodichlorosilanes when organic chlorine derivatives interact with contact mass is connected with the purity of the reactants, silicon above all. High yield of dimethyldichlorosilane in the direct synthesis of methylchlorosilanes largely depends on the presence of noticeable quantities of aluminum in contact mass. The yield of dimethyldichlorosilane in the presence of aluminum as a rule decreases due to the formation of trimethylchlorosilane in the reaction with pure (semiconductor) silicon in the presence of copper trimethylchlorosilane is virtually not formed. 

Thus, the methylation of dimethyldichlorosilane becomes very significant in the processes of direct synthesis, whereas the total amount of trimethylchlorosilane, which is formed according to the reactions of dis-proportioning and methylation, may reach 60-65%. Thus, in the direct synthesis of methylchlorosilanes the introduction of significant amounts of AI or its compounds into contact mass reduces the yield of dimethyldichlorosilane and respectively increases the yield of trimethylchlorosilane. 

This example shows the importance of so-called activators, or promoters, for increasing the activity and selectivity of contact mass. These additives can sharply activate the reaction and shift it in a certain direction. Various substances have different effects on the activity of contact mass. For example, antimony has a positive effect on the direct synthesis of organochlorosilanes and increases the total yield of methylchlorosilanes, whereas lead and bismuth reduce the formation of these substances. How-ever, the positive effect of a promoter manifests itself only in a certain concentration, exceeding which transforms a positively acting additive into poison or an inhibitor of the reaction. For example, in a 0.002—0.005% concentration antimony is a promoter of the direct synthesis of methylchlorosilanes on the other hand, in a concentration higher than 0.005% it becomes poison. 

It follows from all the above-mentioned facts that the direct synthesis of methyl-, ethyl and phenylchlorosilanes is a complex heterophase process which depends on many factors and forms a compex reactive mixture. For example, in the direct synthesis of methylchlorosilanes there are about 130 compounds found and characterised. This does not mean, however, that in this or other definite synthesis all the 130 products are formed. The composition of the mixtures formed and the transformation degree of alkyl-chlorides and chlorobenzene in the synthesis of methyl-, ethyl and phenylchlorosilanes depend on the synthesis conditions, the type of the reactor used and many other factors. In spire of the complexity of the process and the variety of its products, the reaction of direct synthesis can nevertheless be directed (towards a preferential formation of a main product), changing the conditions for the preparation of contact mass, introducing various promoters into contact mass and changing the reaction conditions. 

Because direct synthesis in this case is very complex, the mechanism of this process has not been fully established. However, the following way of methylchlorosilane formation with the catalytic effect of copper on the reaction of methylchloride with silicon is the most probable. 

The chlorination of methylchlorosilanes is realised by free chlorine in the liquid or gaseous phase. The reaction takes place by the radical chain mechanism its initiators (substances capable of generating free radicals) can be peroxides (benzoyl, kumyl, etc.), the dinitrile of 2,2 -azobis(isobutyric) acid, fluorine, 60Co y-rays, as well as UV rays. 

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