DD288152A5 - DIRECT SYNTHESIS PROCESS FOR THE SELECTIVE PRODUCTION OF ORGANOHALOGENHYDROSILONES - Google Patents

Abstract

The invention relates to a direct synthesis process for the selective production of organohalohydrosilane by catalytic reaction of activated silicon with mixtures of organohalides and hydrogen in the presence of controlled concentrations of selected metal atoms. This process is characterized by the general formula RaHbSiXc by the reaction of activated silicon with a mixture of an organohalide of the general formula RX and hydrogen in contact with a catalytic amount of catalyst at elevated temperature, in which R is a hydrocarbon group of up to about 20 carbon atoms X is a halogen atom and a, b and c are integers having a value from 1 to 2, with the proviso that the sum of abc4 is {activated silicon; Mixture of an organohalide; catalytic amount; Catalyst; Hydrocarbon group; Carbon atom; Halogen atom}

Description

Field of application of the invention This invention relates to a direct synthesis process for the production of organohalohydrosilanes by catalytic Reaction of activated silicon with a mixture of organohalides and hydrogen and the activated Silicon catalysts themselves. In particular, it relates to a direct synthesis process which has increased reaction rates

and show selectivities by controlling the concentration of trace metals present in the reaction mixture and the type of reactor used, as well as the improved rate, stability and selectivity of the reaction by the proper addition of selected metal additives, adequate addition of halo-silanes and / or

Organohalosilanes during the course of the reaction from the outside. In the following description, various terms and abbreviations are used repeatedly. To one

understanding their meaning in a timely manner is followed by their definitions:

Direct Synthesis = the one-step synthesis method of this invention whereby organohalohydrosilanes are selectively and directly produced by the reaction of activated silicon with a mixture of an organohalide and hydrogen in the presence of controlled amounts of specific metal atoms and under specific reaction conditions (both as defined below) and in contact with a catalyst in a fixed bed, stirred bed, fluidized bed or slurry phase reactor;

Organohalogen = one or more compounds of the general formula R, H _b SiX _c , as defined in more detail below,

hydrosilanes as they are applicable in the particular situation given;

MeSiH = one or more organosilane compounds of the methylchlorohydrosilanes of the formulas CH ₃ SiHCl ₂ ,

(CH ₃ I ₂ SiHCl and CH ₃ SiH ₂ Cl;

DH = CH ₃ SiH ₂ Cl;

DM = (CH ₃ I ₂ SiHCl;

MD = CH ₃ SiHCl;

Organohalogen = one or more of the organosilane compounds of the general formula R _d SiX _<K) , as described below

silanes are defined in more detail as they are applicable in the particular, given situation;

M = (CH ₃ I ₃ SiCl;

T = CH ₃ SiCl ₃ ;

D = (CH ₃ J ₂ SiCl ₂ ;

Halogen- = one or more compounds of the general formula HdSiX ^, as described in more detail below

silanes are defined as they are applicable in the particular, given situation;

TC = HSiCl ₃ ;

HVS = the higher boiling fraction, uppermost about 70 ° C at atmospheric pressure, generally predominantly methylchlorodisilanes;

tr - trace (trace), less than - 05 Gow .-% by gas chromatography;

GC = gas chromatography; GC / MS = gas chromatography / mass spectrometer; GC / FTIR = Gas Chromatography / Fourier Transform Infrared Spectroscopy;

o.d. = Outer diameter;

i.d. "Internal diameter;

MVg = square meters per gram; BET = Braunnaueer-Emmet plate; NA '= not analyzed; ND = not determined;

Me = methyl.

Characteristic of the known state of the art

The production of silanes, whether halosilanes or organohalosilanes or organohalohydrosilanes, have long been known. The organohalohydrosilanes have found many applications and are generally useful intermediates for the synthesis of organosilicon coupling agents, silicone surfactants, and hydrosilation and redistribution reactions. In fact, there has been such a demand for these compounds that the supply of organohalohydrosilanes obtainable by the conventional methods has often been insufficient. The direct reaction method described in U.S. Patent 2,380,995 issued to Rochow indicates the reaction of silicon with a methyl halide in the presence of a catalyst. However, this process produces a mixture of silicon products wherein the methyl halohydrosilanes are formed only in minor amounts and only a small portion of the mixture, generally less than about 5 weight percent CH ₃ SiHCl ₂ and less than about 1 weight percent (CH ₃ I ₂ SiHCI and no CH ₃ SiH ₂ CI, if the methyl halide is methyl chloride, make up. the bulk of the products formed is composed of HSiCl _3, SiCl, (CH ₃ I ₃ SiCl, CH ₃ SiCl _3, (CH ₃ I ₂ SiCl ₂ and disilanes of the structure (CH ₃ I _x Si ₂ Cl _{6- x} and a number of disilamethanes, siloxanes and hydrocarbons as shown in U.S. Patents 2,598,435, 2,651,355 and 2,709,176, which require complex ones Distillation process to isolate and purify the minor amounts of methylchlorohydrosilanes that have been formed from hydrocarbon by-products having similar boiling points, as described in US Pat. Nos. 3,704,260 issued November 28, 1972 to MJWynn, and 4,181,673 , granted H. Schumann et al., Can be seen.

Voorhoeve (Organohalosilanes: Precursors to Silicones, Elsevier, NY, 1967, pp. 190-201) describes C ₂ Hs-SiHCl ₂ as the major product of the direct reaction of ethyl chloride with copper-activated silicon. The more desirable compounds (C ₂ He) ₂ SiHCI and C ₂ Hs-SiH ₂ CI do not arise, even if hydrogen is added together with the ethyl chloride under pressure, as further described in German Offenlegungsschrift 859 164, published on December 11, 1952 and in Turetskaya et al., Khim. Prom., P. 18 (1963). These methods are incapable of producing all three desired organohalohydrosilanes in sufficiently high yield and / or selectivity.

Although various methods for the preparation of silanes using hydrogen, hydrogen chloride or metal hydrides have been published, none are able to meet the growing demand for organohalohydrosilant.i. Catalytic hydrogenation processes for the synthesis of (CH ₃ I ₂ SiHCl and CH ₃ SiHCl ₂ from methylchlorodisilanes are disclosed in US Pat. Nos. 3,639,105, issued February 1, 1972 to WHAtwell et al., And 4,059,608 issued November 22, Calas et al., And 4,079,071 issued to Mar Neale on March 14, 1978. These processes require the use of disilanes as the starting material, but the disilanes represent only a fraction of the product, usually in a direct reaction process For example, the disilanes obtained in U.S. Patent 4,500,724, issued February 19, 1985 to Ward et al., constitute about 1 to 6 weight percent of the silanes produced CI (CH ₃ ) ₂ Si / ₂ , resulting in high yields of (CH ₃ I ₂ SiHCl.) The hydroboration of disilanes results as described in U.S. Patents 2,709,176, loc Calas et al., J. Organomet. Chem., 225, 117-130 (1982), esp typically more CH ₃ SiCl ₃ , CH ₃ SiHCl ₂ and (CH ₃ I ₂ SiCl ₂ and not to (CH ₃ I ₂ SiHCl or CH ₃ SiH ₂ Cl.

Attempts to directly hydrogenate alkylhalosilanes to alkylhalohydrosilanes have also been unsuccessful. The reaction is slow, even at temperatures of more than about 1000 ⁰ C and pressures of about 1500psig when using a Pd catalyst (Japanese Patent 82-47917, U.S. Patent 2,585,620). This reaction leads to a further complication since the organohalohydrosilanes of the formulas R ₂ SiHCl and RSiH ₂ Cl are not sufficiently stable to withstand such high temperatures.

Syntheses of alkylchlorohydrosilanes vi j the metal hydride reduction of alkylchlorosilanes with NaH, Chalk, J. Organomet. Chem., Vol.21, 95101 (1970); Antipin et al., Russ. J. Gen. Chem., Vol. 40, p.789 (1970; U.S. Patent 3,704,261, issued November 28, 1972 to Berger et al., CaH ₂ (Simon et al., J. Organomet. Chem., Vol. S.279 [1981]); NaBH ₄ (U.S. Patent 4,115,426, issued September 19, 1978 to Hillrod et al.) And LiAlH ₄ (Eaborn et al., J. Organomet. Chem., Vol , P.371 [1969]) are also described and are not practiced commercially because of the relatively high cost of the metal hydrides and the need to rely on stoichiometric amounts of metal chlorides that form during the course of the reduction.

The yield of organohalohydrosilanes of the formula RHSiX ₂ is determined by using mixtures of organochlorides (for example CH ₃ Cl) and hydrogen halide (for example HCl) in the Rochow direct reaction synthesis (see Gorbunow et al., Dokl. Akad. Nauk SSR, Vol 194, page 92 [1970]). However, even large amounts of the less desirable RSiX ₃ are formed simultaneously, and the method is uneconomical. The use of hydrogen-organohalide (for example CH ₃ Cl, C ₂ H ₆ Cl) mixtures in the Rochow direct reaction synthesis is described in the following references: US Patent 2,380,998 issued August 7, 1945 to Sprung et al. ; British Patent 590,654 and 575,674; German Patent 859,164; Turetskaya et al., Khim. Prom., P. 18 (1963). These publications describe the increased formation of RHSiCl ₂ , but not of R ₂ SiHCl or RSiH ₂ Cl.

DeCooker et al. [J. Organomet. Chem., Vol. 99, p.371 [1975]; Ph.D. Diss. Univ. Delft, The Netherlands, 1976, Chapters 5 and 6) that the addition of Zn, Cd and Al is used to copper-activated silicon, as in the Direktroaktionssynthese with mixtures of CH ₃ CI and H ₂ at 300-370 ⁰ C, decreases the selectivity to CH ₃ SiHCI ₂ and (CH ₃ SiHCI I _2. A summary of results is shown in Table The data show that selectivity to methylchlorohydrosilanes is favored by high water partial pressures and high temperatures Reaction rates are slow and erratic, and stable contact mass activity is not achieved (DeCooker, 1976, Ph.D.D Dis3. Chapter 5, pp. 57-63, Chapter 6, pp. 64-73), even when using 10 to 15% by weight of Cu catalyst In addition, the Reaktionsleistungsparametor such as the ratio of CH ₃ SiHCI ₂ au ( CH ₃ I ₂ SiHCl and the overall predominance of methylchlorohydrosilanes (for example, CH ₃ SiHCl ₂ + (CH ₃ I ₂ SiHCI) variable even when the experiments are repeated. The dissertation presents kinetic data (Chapter 6) of the direct synthesis reaction of CH ₃ SiHCl ₂ and (CH ₃ I ₂ SiHCl on a contact mass (for example, intimate mixture of Si, Cu, and a copper-silicon alloy) containing 0.1 wt. However, the maximum tolerable Zn, Cd and At levels result in high selectivity of the desired compounds, and a high bulk activity is not defined. "Ee is noteworthy (Chapter 6, P. 64) that the authors associate low selectivity for methyl chlorohydrosilanes with low CuCl concentrates, and there are no comments on working at superatmospheric pressures.

French Patent 1,523,912 describes the direct reaction synthesis of CH ₃ SiHCl ₂ and (CH ₃ I ₂ SiHCl with CH ₃ Cl-H ₂ mixtures at 350-380 ⁰ C and 0-2.5at in which the selectivity for methylchlorohydrosilane Addition of Group VIII metal salts (for example, chlorides, oxalates and formates of Fe, Co, Ni) in amounts of 0.3-10 wt.%, Preferably 1.3-2 wt.%, Of the silicon contact mass The formation of (CH ₃ I ₂ SiHCl and CH ₃ SiHCl ₂ under the conditions illustrated in the examples of the patent is shown in Table 2. '

In contrast to the findings of DeCooker (loc.cit.), This French patent (Examples 5 and 8, claim 6) describes that 0.25-0.5 wt% ZnCl ₂ (equivalent to 0.12-0, 25 wt% Zn) advantageously included in the composition which improves selectivity for methylchlorohydrosilanes. However, there are no comments regarding the control of the ratio of CH ₃ SiHCl ₂ to (CH ₃ I ₂ SiHCl or the most favorable range of hydrogen partial pressures or maximum tolerance levels of other metals such as Cd, Al or Sn. Examples 8 uses 15% by weight. The performance of the crude reaction in the absence of salts of the Group VIII metals is also not described, and the execution of the synthesis at 2.5 atm ⁰ C with 2,5Gew .-% NiCl ₂ as an additive for the selectivity (CHj) ₂ SiHCI (cf. · ie Examples 1 and 3 of Table 2).

As can be seen, the literature does not provide a suitable DirdVtsyn ^ eprozeß that would be suitable to meet the requirements for Organohalogenhydrosilanen. None of the references disclose or suggest process conditions that result in stable, reproducible formation of organochlorohydrosilanes, particularly alkylchlorohydrosilanes, which give both high rates of reaction and high selectivity to organohalohydro-silanes with good reproducibility and process stability.

In the following description, various terms and abbreviations are used repeatedly. In order to facilitate a timely understanding of their meaning, their definitions follow:

Direct Synchtese = the one-step synthesis process of this invention, thereby organohalohydrosilanes selectively produced directly by the reaction of activated silicon with a mixture of an organohalide and hydrogen in the presence of controlled ¹ · amounts of specific metal atoms and (under specific reaction conditions defined both as described below ) and in contact with a catalyst in a fixed bed, stirred bed, fluidized bed or slurry phase reactor;

Organohalogeno = one or more compounds of general formula R ₁ HbSiXc, as defined in more detail below, hydrosilanes as applicable in the particular situation given;

MeSiH - one or more organosilane compounds of the methylchlorohydrosilanes of the formulas CH ₃ SiHCl ₂ ,

(CH ₃ SiHCI ₂ J and CH ₃ SiH ₂ CI; DH = CH ₃ SiH ₂ CI;

DM = (CHr ₂ SiHCi;

MD = CH ₃ SiHCl;

Organohalogeno = one or more of the organosilane compounds of the general formula R ₁ JSiX ₄ _ <j, as defined below in more detail silanes, as applicable in the particular, given situation;

M = (CH ₃ I ₃ SiCl;

T = CH ₃ SiCl ₃ ;

D = (CH ₃ I ₂ SiCl ₂ ;

Halogen = one or more compounds of the general formula H ₁₁ SiX ₄ _ _d , as described in more detail below

silanes are defined as they are applicable in the particular, given situation;

TC = HSiCl ₃ ;

HVS = the higher boiling fraction, above about 70 ⁰ C at atmospheric pressure, generally mainly methylchlorodisilanes;

tr = trace, less than =, 05% by weight by gas chromatography;

GC - gas chromatography; GC / MS = gas chromatography / mass spectrometer; GC / FTIR = Gas Chromatography / Fourier Transform Infrared Spectroscopy;

o.d. = Outer diameter;

i.d. = Inner diameter;

MVg = square meters per gram; BET = Braunnaueer-Emmet plate; NA = not analyzed; ND = not determined;

Me = methyl.

Object of the invention

The aim of the invention is to avoid the aforementioned disadvantages.

Explanation of the essence of the invention

The invention has for its object to provide a direct synthesis process for the selective production of Organohalogenhydnsilan available.

Erfindüngsgemäß the object is characterized by a direct synthesis process for the selective production of Organohalogenhydrosilanon, by the general formula

by reaction of activated silicon with a mixture of an organohalide of the general formula RX

and hydrogen in contact with a catalytic amount of catalyst at elevated temperature, wherein R is a hydrocarbyl group having up to about 20 carbon atoms; X is a halogen atom and a, b and c are integers of 1 or 2, with the proviso that the sum of a + b + c = 4.

Among the objects described in this invention, a simple process for the direct synthesis of organohalohydrosilanes can be mentioned in a continuous, reproducible manner. Another is the direct synthesis of organohalogenohydrosilanes in which the rate is generally high and reproducible without, on the other hand, affecting selectivity for compounds having silicon-to-hydrogen bonds and the overall conversion of silicon. Other items will be apparent from the following.

Table 1: Direct Synthesis of CH ₃ SiHCl ₂ and (CH ₃ I ₂ SiHCI According to DeCooker

Si Conv., Temp. Cu Zn al DM MD T D rate H ₂ partial Wt. % ⁰ C Wt. % Wt. % Wt. % mole% mole% mole% mole% gm CH ₃ CI / Press, (atom) 20 332 10 _ - 32.7 37.6 3.4 23.4 kg Si, Hr 12:55 40 332 10 _ _ 30.8 23.8 9.9 33.1 75 12:55 55 332 10 - - 33.1 45.7 6.9 12.5 100 0.75 65 332 10 - - 24.4 51.1 4.8 17.3 75 12:55 25 332 10 0.1 12:05 17.5 30.8 4.7 45.8 85 12:55 50 332 10 0.1 12:05 28.5 56.7 2.7 10.3 40 0.75 60 332 10 0.1 12:05 17.5 70.3 2.7 5.0 40 0.75 20 370 10 0.1 12:05 23.0 26.6 5.3 42.1 50 12:58 50 370 10 0.1 12:05 31.6 39.5 3.2 23.9 180 12:58 20 334 15 0.1 12:05 13.4 29.5 3.2 49.5 290 12:55 40 334 15 0.1 12:05 17.4 36.0 4.1 39.6 65 12:55 70 334 15 0.1 12:05 8.0 62.4 12.7 5.4 75 12:55 50

'Data from Ph. D. Dissertation, Univ. Delft (1976). Chp. 5 and 6

DM = (CH ₃ ) ₂ SiHCl, MD = CH ₃ SiHCl ₂ , T = CHjSiCl ₃ , D = (CH ₃ J ₂ SiCl ₂ .

Table 2: Direct Synthesis of (CH ₃ I ₂ SiHCl and CH ₃ SiHCl ₂ Accordiag to Fr. Pat. 1,523,912

Example H ₂ DM MD T D rate MD / DM D / T additives 1 % Vol. Wt. % Wt. % Wt. % Wt. % gm / kgSi, Mr. 3:41 1.94 2.5 wt.% NiCl ₂ 2 35.7 8.0 27.3 20.8 40.4 149 9.25 0.68 2.5 wt.% CoCl ₂ 4 7.1 4.0 37.0 33.0 22.5 75 2.86 1:39 2 wt.% Ni (C ₂ O ₄ ) 6 35.7 7.0 27.0 26.7 37.2 128.5 3.5 2:09 2 wt.% Co (C ₂ O ₄ ) 35.7 8.8 30.8 17.6 36.8 97.6 2 wt.% Fe (C ₂ O ₄ ) 5 2.12 2:59 + 35.7 15.5 32.9 13.2 34.2 145.8 0.25 wt.% ZnCl ₂ 2 wt.% Fe (HCOO) ₂ 8th 8.27 0.96 + 35.7 6.3 52.1 17.9 17.2 8.6 0.5 wt.% ZnCl ₂ 3 _ 0.76 2 wt.% NiCl ₂ 27.3 - 42.9 25.1 19.1 164

All experiments at 380 ¹ C, O atom, gauge except Example 3, which was run at 350'C, 2.6 atom, gauge

DM = (CH ₃ ) jSiHCl, MD = CH ₃ SiHCl j, T = CH ₃ SiCl ₃ , D = (CH ₃ IjSiCl ₂ .

This invention relates to direct synthesis processes for the preparation of organohalohydrosilanes that exhibit increased reaction rates, reproducibility and selectivity to such silanes, as well as overall conversion of the silicon. The methods determine the control of the amount of trace metals present, the type of reactor system used, and the addition of certain additives to the system. The critical aspects of the direct synthesis process

of this invention require that the primary objects of said process include the control of the concentrations of certain particular metal atoms in the activated silicon bed, particular adjuvants used, and their concentrations, the influence of the addition of calcium chloride on the activated silicon the reaction and the ability to directly produce organohalohydrosilanes of the formula RH ₂ SiX by performing the direct synthesis in a fixed bed reactor at high selectivity and speed, a hitherto unprecedented matter. The direct reaction process for the production of silanes, disclosed by Rochow, are conventionally carried out in a gas-solids reactor, such as a fed bed, stirred bed, fluidized bed reactor, all of which are known. In this conventional process, an organohalide with activated silicon in contact with a catalyst, promoters and auxiliaries is converted to mixtures of silanes. However, the processes described so far do not produce sufficiently significant amounts of orgimohalocene hydrosilanes of the general formula R, H _b SiX _c , since the formation of organohalosilanes of the general formula RdSiX _{4- d is} favored to a considerable extent. In view of the commercial demand and the demand for organohalohydrosilanes, many attempts have been made to increase the formation of these compounds, none of them was sufficiently required. The direct synthesis methods of this invention have been successful in this reaction; they have allowed the production of organohalogenohydrosilanes in a continuous and reproducible manner at higher reaction rates, yields, and selectivities than heretofore. The means by which these benefits were achieved were completely unpredictable and unexpected. In the processes of this invention, organohalogenohydrosilanes of the general formula

R ₁ HbSiXe, (I)

produced by the direct synthesis process in increased amount and selectivity. In this formula, R is an aliphatic or aromatic, saturated or unsaturated hydrocarbyl radical having up to about 20 carbon atoms, for example alkyl or alkenyl of up to about 10 carbon atoms, preferably up to about 6 carbon atoms; Aryl, alkaryl, aralkyl having 6 or 10 ring carbon atoms and wherein the alkyl group is as defined above; Cycloalkyl having 4-7 ring carbon atoms which may be substituted with alkyl or alkenyl groups as defined above; X is a halogen atom, for example, chlorine, bromine, iodine and fluorine; a, b and c are integers having a value of 1 or 2, with the proviso that the sum of a + b + c is four. Subtypes of the formula are compounds of the formulas RH ₂ SiX, RHSiX ₂ and R ₂ HSiX. Illustrative of such compounds are those listed below, where the components and values for R, X, a, b and c of the compounds having the above formulas are shown.

Table A R X a b C methyl Cl 1 2 1 methyl Cl 1 1 2 methyl Cl 2 1 1 ethyl Cl 1 2 1 ethyl Cl 1 1 2 ethyl Cl 2 1 1 methyl br 1 2 1 methyl br 2 1 1 methyl I 1 2 I ethyl br 1 2 1 ethyl br 2 1 1 pentyl Cl 1 2 1 phenyl Cl 1 2 1 phenyl Cl 1 1 2 phenyl Cl 2 1 1 phenyl br 1 2 1 phenyl br 1 1 2 phenyl br 2 1 1

The improved direct synthesis methods of this invention are the reaction of an organohalide of the formula RX, wherein R and X are as defined above, with activated silicon. Examples of suitable organohalogens are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, phenyl chloride, vinyl bromide and the like. Any organohalide known to react with activated silicon may be used, with those being preferred which evaporate under the reaction conditions employed; these compounds are well known to those skilled in the art. Methyl chloride is preferred.

Methyl chloride with the standard commercial purity of at least about 99.6% by weight is a preferably suitable starting material. However, there are means to remove trace contaminants or to avoid the introduction of vaporous inhibitors and poisons (for example CO, CO ₂ , O ₂ , H ₂ O, SO ₂ ), if desired.

The term activated silicon has a specific meaning in this technology. It refers to silicon in which a catalyst, one or more promoters and one or more adjuvants have been incorporated.

In this invention, the activation may be carried out by any suitable known method, for example, by solidifying a melt containing the catalyst (for example, copper) and silicon and crushing the solid; or by heating a mixture of silicon and catalyst as described in U.S. Patent 2,380,996; or by heating mixtures of silicon, catalyst and promoters in the presence of hydrogen and / or hydrogen chloride as described in U.S. Patent 2,380,997 and 4,314,908 issued February 9, 1982 to Downing et al .; or by heating a mixture of a salt of the catalyst (for example, copper (I) chloride) and silicon, as described in U.S. Patent 2,119,808, to higher temperature. These and many other activation methods, catalysts, promoters and auxiliaries are known in the art.

Activation, as known to those skilled in the art, is the process of incorporating certain amounts of catalyst, promoter and excipient into the silicon. This may be done in the same reactor used for the reaction of the organohalide-hydrogen mixture or in a separate reactor. In the latter case, transport will normally be to the organohalide-water reactor in an anhydrous, non-oxidizing atmosphere.

A preferred method of activation for the direct synthesis of the present invention utilizes copper (I) chloride and chlorosilane (HSiCl ₃ , SiCl ₄ ), methylchlorosilane (CH ₃ SiCl ₃ , (CH ₃ I ₂ SiCl ₂ ) or their mixtures Methylchlorosilanes are vaporized and transported in amounts into the reactor sufficient to fluidize the mixture of silicon and cupric chloride Other gases such as hydrogen, nitrogen, argon and helium, which interfere with the subsequent performance of the active silicon, may combine with the vaporous chlorosilanes and methylchlorosilanes to aid in fluidization, temperatures above 200 ° C are required for this activation, values between 280 and 38O ⁰ C are preferred.

The catalyst used in this invention is a metallic element, for example, copper or silver, or their compounds. The suitable catalysts, including the above, are well known and fully described in the literature. The literature does not, however, provide any insights into the significant effects of the presence of traces of other elements on the reaction. The accepted theory is that the metal atom fuses with and diffuses into the silicon to form an alloy or a solid solution, which is the phase that reacts with the organohalide. The preferred catalysts for the direct synthesis process of the present invention are metallic copper powder, any anhydrous copper compound, or mixtures thereof. However, metallic silver, its compounds and their mixtures are also known as effective catalysts. Examples of copper compounds suitable for use, singly or in admixture, are cuprous oxide, copper (I) chloride, cuprous D-chloride, copper nitride, copper hydroxide and copper carboxylates such as copper formate. However, this is not a restrictive or exclusive list.

Copper compounds having a direct opposite effect are those such as copper sulfides and lead and copper intermetallics which introduce into the reaction intolerant amounts of compounds or elements which are known to have a negative impact on their rate and / or selectivity and / or stability exercise. In addition, Zn, Sn, Cd, or other promoters of dialkyldihalosilane formation that limit selectivity to alkylhalohydrosilanes should be avoided, or their concentrations maintained at c'a prescribed level, as discussed below.

A preferred copper catalyst is copper (I) chloride. Another preferred catalyst is a powdered mixture of copper, copper chloride, and cupric oxide as produced by comminution and partial oxidation of molten copper, by partial oxidation of electrolytically or chemically produced copper metal, or by incomplete reduction of copper (II) oxide. Mixtures of copper and copper oxides produced by precipitation generally contain amounts of Zn, Cd, and Sn which reduce the selectivity for alkyl halohydrosilanes, as shown below. During the precipitation, an aqueous copper-containing solution is contacted with Al, Fe, Zn, or another metal that is higher in the electrochemical series than copper. The copper precipitates and the metals dissolve. As a result of the partial air oxidation, the precipitate is a mixture of copper, copper (I) oxide and cupric oxide. Copper catalysts represented in this way are known as precipitation catalysts. Those partially oxidized copper catalysts that were not prepared were called non-precipitated catalysts. Copper formate is another preferred catalyst, in particular, copper formate having a layered or cell-like crystal structure is particularly preferred. This crystal structure is characterized by intense reflections in the X-ray powder pattern of copper formate at d-spacings of 3.0-3.1 Angstroms and 5.0-6.5 Angstroms. The preferred copper formate catalysts are also subject to a complete thermal decomposition at atwater 170 to about 200 ⁰ C. The copper formate may be hydrated or anhydrous, but it is desirable that remain in the image represented by bekennte methods solids the lamellar structures.

In order to achieve the selectivity and speed values characterizing the present invention, the Cd and Zn concentrations in the catalyst should be below 0.07% by weight, preferably below 0.01% by weight. The Sn content should be less than 0.002 wt%. The Pb content should be 0.07 wt% maximum, preferably less than 0.005 wt%. The iron and aluminum content of the catalyst is preferably at most 0.3 wt .-%. The reported concentrations of Zn, Cd and Sn are critical to this invention.

Catalyst particles up to a maximum size of 100 microns are useful for the process of this invention. However, it is preferred that the particles are smaller than 50 microns and most preferably 2-25 microns. A minimum BET surface area of 0.1 m '/ gm is generally acceptable. Values of more than 1 mVgm are preferred for good catalyst dispersion. The amount of copper required to activate the silicon is usually less than about 10% by weight of the silicon used. In general, copper levels in the range 0.05-3 wt% have been found to be optimal. Earlier (see DeCooker et al., Morozov ot al., Loc.cit.), The use of copper in the range of 10-15% by weight was reported for the direct synthesis of alkyl halohydrosilanes. However, the present invention can use copper concentrations of 0.5-1.5% by weight and can achieve performance benefits for the top teats.

The silicon used in the direct synthesis process of this invention is a engineering material that preferably contains at least about 98.5 wt% Si. Trace metals found in engineering silicon used in the conventional direct synthesis process are described by NP Lobusevich et al., Russ. Jour. Appl. Chem., Vol. 49, No. 10, pp. 2168-2174 (1976). In general, the silicon used in the conventional synthesis can also be used in the present invention, provided that the following specifications are satisfied: Si> 98.5 wt%, Al = 0.1-0.4 wt%, Fe = 0 , 3-0.6 wt%, Ca = 0.01-0.15 wt%, Ti = 0.03-0.6 wt%, Mn = 0.005-0.01 wt% , Zn <0.005wt%, Sn <0.0005wt%, Pb <0.001wt%, Bi <0.005wt%, Sb <0.005wt%, Ni = 0.001-0.2wt. %, Cr = 0.0005-0.02 wt%, Co £ 0.005 wt%, Cd <; 0.005 .-%. The levels of Al, Bi, Cd, Cr, Ni, Pb, Sb, Sn and Zn are particularly critical for the selectivity of R ₂ SiHX and RSiHX ₂ . For example, Al values in excess of 0.4 wt% can result in <10 wt% Me ₂ SiHCl in the reaction product. Values of less than 0.1% by weight of Al can limit the reactivity of the silicon. Promoters of dimethyldichlorosilane formation and conventional adjuvants, for example, Zn, Cd, Bi, Sb, Sn, when present in concentrations exceeding the ranges shown above, inhibit formation of the organohalohydrosilane compounds. The Pb is especially critical. Values less than 0.005 wt% can cause significant loss of reactivity. A particularly preferred silicon for this invention is that containing 0.004-0.02 wt% Ni and 0.002-0.01 wt% Cr.

A wide range of silicon particulates, for example 28 XD mesh (that is, no larger than 500 microns) can be used in the synthesis. However, it is preferred that the silicon particles be less than about 48 mesh (that is less than 300 microns) and greater than about 325 mesh (that is more than 45 microns). Smaller particle sizes contribute to a good Fluidisierun 3 of the bed and support the exchange of heat. The range of particle size used in a given reaction depends on the reactor size and synthesis scale. In laboratory experiments, the preferred particle size range is 65 x 150 mesh (that is 104-208 microns), but this distribution is not considered essential to the success of our process.

Preformed metal silicides such as those of calcium, magnesium and copper may also be present in the synthesis, either as an individual phase or mixed with elemental silicon. The presence of calcium silicides (for example CaSi ₂ ) is particularly favorable for the formation of R ₂ SiHX compounds, even if they are only present in relatively small amounts of 1-10% by weight. The preferred amount is 2-8% by weight. This is dictated by the need to keep both the reaction temperature and the fluidization of the particles within controllable limits. The reaction of calcium silicides with alkyl halides is highly exothermic. Consequently, the presence of more than 10% by weight of calcium silicides in silicon has undesirable effects. It is also important that the calcium silicide contain no amounts of Al, Fe, Zn, Sn and other metals that exert negative influences on the rate of formation of the organohalohydrosilane compounds and on the selectivity for R ₂ SiHX In particular.

In the direct synthesis method of this invention, the concentrations of the various metal atoms present in the activated silicon bottoms subjected to reaction with the organohalide are critical. It is an important aspect of this direct synthesis that the activated silicon bed contains the metal atoms in the following wt% values. The amount of zinc, antimony and cadmium, either singly or together, should be less than about 0.05% by weight, preferably less than about 0.01% by weight, most preferably less than 0.005% by weight. The tin concentration should be less than about 0.01 weight percent, preferably less than 0.005 weight percent, most preferably less than 0.0005 weight percent. The nickel concentration should be from about 0.001 to about 0.02 wt.%, Preferably from about 0.002 to about 0.01 wt.%, Most preferably from about 0.004 to about 0.008 wt.%. The chromium concentration should be from about 0.001 to about 0.06 weight percent, most preferably from about 0.0005 to about 0.01 weight percent. The aluminum concentration can range from about 0.1 to about 0.4 weight percent, preferably from about 0.1 to about 0.2 weight percent.

In the prior conventional direct reaction processes, promoters have been used in significant concentrations to potentiate the formation of diorganodihalosilanes of the formula R ₂ SiX ₂ where R and X are as defined above. These conventional promoters are elements such as Zn, Cd, Hg, As, Sb, Bi and their compounds. However, in the direct synthesis methods of the present invention, the presence of any significant amount of one or more such conventional promoters is detrimental and results in a decrease in selectivity for organohalohydrosilane formation; therefore their quantities must be controlled to the critical values defined here. In the direct synthesis method of the present invention, the term promoter refers to the elements Ni, Cr, Rh, Pd and their compounds. These promoters are those which have been found to increase the formation of organohalohydrosilanes of Formula I.

The promoters used in the processes of this invention provide satisfactory rate and selectivity in the direct synthesis of organohalohydrosilanes. The promoters of this invention, when used in effective amounts, favor the increasing formation of RHSiX ₂ , R ₂ SiHX and / or RSiH ₂ X in the direct synthesis process of this invention. The promoter is preferably in powder form as an element, oxide, halide or silicide having a particle size distribution similar to that of the catalyst. For good and sufficient speed and selectivity, it is desirable to use the activated silicon, represented by silicon, containing the promoter (s) homogeneously distributed throughout the particle mass. An inhomogeneous distribution only leads to a temporary realization of the advantages. French Patent 1,523,912 describes the use of salts of Group VIII elements (for example Fo, Co, Ni) in amounts of 0.3-10% by weight to give the total selectivity (for example MeSiH or MeSiH / D). for Organohalogenhydrosilane increase. However, there are no teachings or suggestions as to the choice of promoters to favor RSiHCl ₂ over R ₂ SiHCl or vice versa (for example, MD / DM). The present invention teaches the control of the ratio MD / DM by both the choice of promoter and its concentration. In French Patent 1,523,912, nickel salts (for example, nickel chloride, nickel oxalate, and nickel formate) are used at 0.3-10 wt% in the activated silicon. The lower limit of the nickel salt concentration (e.g., 0.3 wt%) is equivalent to 0.12-0.14 wt% Ni. The present invention is characterized by the advantageous use of nickel concentrations below 0.1 wt%, preferably 0.002-D, 08 wt%, most preferably 0.004-0.0; Wt .-%. At concentrations in these ranges, nickel increases the rate of reaction between the activated silicon and the organohalide-hydrogen mixture. Contrary to the teachings of French Patent 1,523,912, selectivity to organohalohydrosilanes of the general formula, R ₂ SiHCl (for example, (CH ₃ ) ₂ SiHCl) is maintained at these low nickel concentrations when the reaction is conducted at greater than atmospheric pressure , Nickel concentrations in excess of 0.1% by weight favor the increased formation of organotrihalosilanes, RSiXa (for example CHaSiCl ₃ ), at the expense of the organohalohydrosilanes. The application of the preferred Ni values generally gives MD / DM = 2-5, MeSiH / D> 1.0, rate> 1 wt% Si / hr when the reaction is at 290-325 ^e C and 0- 30psig in a fluidized bed with a volume ratio H ₂ -CH ₃ CI of 50:50 or 60:40 is performed.

? Chrome lashing ^u «n of <O, 5Gow .-% to the activated silicon give improved selectivity to R ₂ SiHX (for example, (CH ₃ I _2; '.1 / In ratio iu RSiHX ₂ (e.g. CH ₃ SiHCI ₂ ) Additions equal to or less than 0.1% by weight are particularly advantageous The concentrations maintained in the activated silica gel should preferably be 0.0005-0.006% by weight. Thus, the use of silicon with 0 , 005wt% CrMD / DM = 2 = 3 and MeSiH / D = 6-8 when the reaction was conducted at a volume ratio of H ₂ : CH ₃ CI 60:40 at 32O ⁰ C and 30 psig in a fluidized bed.

Rhodium also increases selectivity for organohalohydrosilanes of the general formula R ₂ SiXH (for example, (CH ₃ I ₂ SiHCl)) when introduced at concentrations below 1% by weight In contrast, the inclusion of palladium increases to 0, 5Gow .-% selectivity for the compounds RSiHX ₂ (for example CH ₃ SiHCl ₂ ) Both Rh and Pd are elements of Group VIII, but their use for controlling the content of R ₂ SiHX and / or RSiHX ₂ is in the French patent 1,523,912 not mentioned.

The adjuvants used in the past have generally been elements such as Sn and Cs and their compounds. They were added to improve the reaction rate and / or selectivity for diorganodihalosilanes R ₂ SiX ₂ and / or to reduce the formation of higher boiling compounds than the disilanes; precondition is that both catalyst and promoter are present in equal amounts.

In the direct synthesis method of the present invention, the auxiliaries are the halosilanes of the formula H _d SiX, and the organohalosilanes of the formula R'fSiX *, where R 'is an alkyl of 1-6 carbon atoms, preferably 1 or 2 carbon atoms, or phenyl, on the the best methyl is; X is halogen; d has a value of 0-3; e has a value of 1-4; the sum of d + e is 4; and f has a value of 1-3. In addition, the organohalohydrosilanes of the formula I are also suitable auxiliaries. The adjuvants are those compounds of the above formulas which, when added to the bed, activate the mixture of silicon and catalyst particles and increase the selectivity to organohalohydrosilanes. They serve to increase speed and selectivity, a double benefit that was completely unexpected and unpredictable.

The auxiliaries used in the direct synthesis process of the present invention are halosilanes (for example HSiCl ₃ , SiCl ₄ ), organohalogenohydrosilanes, organohalosilanes (for example CH ₃ SiCl ₃ ) as defined above, and their mixtures which exert their main effect on the rate of direct synthesis of the organohalogenated hydrosilanes thereof Invention. They can be applied in two different ways. First, the adjuvants can be used to activate the catalyst mixture, along with promoter and silicon. In this case, the tool is usually evaporated and the steam is used to fluidize the mixture of the solids in the active esterification temperature (for example 280-350 ⁰ C). The vapor can also be mixed with inert gases such as nitrogen, argon, helium and hydrogen. In this second mode, the adjuvant can be added for a short (e.g., less than one hour) or long period during the course of the direct synthesis of this invention to improve reaction rate and selectivity. Normally, the speed increase is observed after completion of the auxiliary agent addition. When used in the activation step, the adjuvant should be present in at least about 10% by volume of the gases used to fluidize the bed. Lower values may also be effective, but the reaction performance may become unstable. It is preferred to use more than 50% by volume of the fluidizing gas as auxiliary, most preferably 90-100% by volume. The aid is recovered from activation by condensation of the vapors in a substantially unaltered form. It can be recovered and reused for subsequent activations.

When the halosilane or organohalosilane or organohalohydrosilane is injected in the course of the direct synthesis of this invention, it is important that the injection be made rapidly if the full benefit of the application of the adjuvant is to occur. During the injection time, the overall rate of synthesis is slowed down. As a result, it is desirable to limit this time to at most 6 hours, preferably one hour or less. Times of about 1-20 minutes have been found to be advantageous on a laboratory scale. However, shorter periods may be used if the benefits are not lost.

The amount of additive injected should be a minimum of 0.0001 wt% per minute, based on the weight of activated silicon in the reactor. The maximum amount should not be so great that the total gas volume (for example, organohalide, hydrogen and auxiliaries) is capable of driving the solid particles out of the reactor. A value of about 10% by weight per minute is practically the upper limit. The preferred range is about 0.02-3 wt% per minute. With respect to the organohalide, the aids should be about 0.002-2 times as much, preferably about 0.2-2 times as much on a weight basis.

In order to avoid contamination of the products, it is desirable to use as an aid the halosilanes, organohalohydrosilanes and organohalosilanes which have the same halo and organic groups as the direct synthesis to be carried out by the process of the invention. For example, CH ₃ SiCl ₃ is preferred as an aid in the Direct Synthesis of methylchlorohydrosilanes compared with C ₂ H ₆ SiBr. ₃

The use of the auxiliary during silicon activation improves the dispersion of copper catalyst on the silicon surface. Prolonged use of hydrogen (for example, in the water-i-organohalide mixture) causes sintering of the copper particles and reduces the reaction rate. The sintering can be reversed or stopped, the dispersion increased and the reaction rate improved by interval injection of the adjuvant.

. J. earlier (Russ App Chem, Vol.38, No. 12, pp 7 ^ 36 (1965);... A number of articles of Lobusevich et al, Russ J. Gen. Chem, Vol.48... No. 12, pp.2055-2060 [1978], Vol.48, No., p.2290-2307 [1978]), it has been taught that methylchlorosilanes and chlorosilanes can be recovered in a conventional reaction between methyl chloride and activated silicon. With the injection of methyltrichlorosilane, their additional formation during the reaction was suppressed, the selectivity for dimethyldichlorosilane was increased. However, during the recovery experiment, the overall rate of reaction was also reduced. In addition, conventional promoters including Zn, Cd, Sb or Al and their mixtures with alkali metal salts such as KCl were required for high selectivity to dimethyldichlorosilane. The present invention is directed to the direct synthesis of methylchlorohydrosilanes and requires methyl chloride and hydrogen as co-reactants. Conventional promoters are particularly well suited as activated silicon additions of the present invention. Moreover, an increase in velocity after injection is observed only with simultaneous use of methyl chloride-hydrogen mixtures and activated silicon having the already defined composition. The hydrogen content of the organohalide-hydrogen mixture influences both the rate and selectivity of the direct synthesis of the present invention. The speed decreases with increasing hydrogen partial pressure. In contrast, the selectivity for the Organohalogenhydrosilane increases with the hydrogen partial pressure. The relationship between selectivity, expressed as the total percentage of organohalohydrosilanes in the product (for example,% of MeSiH) and hydrogen partial pressure (or% by volume of H ₂ in the organohalide-hydrogen mixture) is sigmoidal. Hydrogen concentrations below 20% by volume of the mixture give lower selectivities (for example MeSiH <20% by weight, MeSiH / D <1). Concentrations above 8 bVol .-% resulted in very high selectivities (for example MeSiH> 75% by weight, MeSiH / D> 3). The best balance of selectivity and rate is achieved by working with about 40-75 vol% hydrogen, most preferably about 45-60 vol%. In this preferred range, the velocities are greater than 1.5% Si / hour and MeSiH / Ds 1.5 under the preferred conditions of this invention.

The total amount of gaseous reactant (e.g., halogen halide hydrogen mixtures and occasional adjuncts) employed in this invention must be at a minimum sufficient to fluidize the activated silica particles and, of course, must be less than the activated mass stream completely removed from the reactor, before the silicon particles have reacted. The minimum flow for fluidization may be calculated from a knowledge of the gas density, the density and particle size distribution of the activated silicon and the reaction temperature, for example as described in the monograph "Fluidization Engineering" by D. Kuni !, and O. Levenspiel (John Willey & Sons, NY, 1969.) It is possible to treat the bed several times with this minimum flow and to keep the reacting, activated silicon particles contained in the reactor in a still fluidized state, for example, in a laboratory glass reactor at atmospheric pressure and 325 ⁰ C is the minimum ignore fluidization velocity of silicon particles averaging 149 microns in size to about 1.5cr.i / s (rrvr., Nral linear fluidization velocity of the particles in a coal / tetrafluoride reagent at 3. <psig and 30O ⁰ C was found to be 1.73 cm / s Voorhoeve (loc cit p 154) described 1.8 cm / s and Lobu: ·. ··: it: fr, (Soviet Chem. Ind., No.2, p.83 (1974)) 2.0 cm / s as experimentally determined values for silicon particles of Ί05-2 · ^ 'K with an average of 150 Micron

... τ 2-5 times of this minimum are preferred fil- the direct synthesis of RSiHX ₃ and R ₂ SiHX by the Verfelfhren this egg lindung. The direct synthesis of RSiH ₂ X by the process of this invention is best done in a fixed bed reactor.

The minimum temperature of the direct synthesis of this invention for the production of organoholactiv. osilanone is determined by the initial temperature of the reaction between the organohalide and the activated silicon. These temperatures v. in the above-cited monograph by Voc'oeve and Petrov et al., Synthesis of Organosilicone Monomers, published by Consultants Bureau, NY (1976). Lashing, iispiel at atmospheric pressure, the minimum temperature for the Mothylchlorid reaction is about 290 ⁰ C. The maximum temperature may akzeptieicar been ieslimmt by the onset of organohalide pyrolysis. Such pyrolysis is usually accompanied by a marked increase in the formation of the less desirable organotrihalosilanes RSiX ₃ and hydrocarbon by-products. Temperatures above 380 ° C lead to low R ₂ SiHX formation and / or RjSiHX decomposition.

Optimal temperatures are those which allow easy reaction and evaporation of the products without the complexities of organohalide pyrolysis or the thermal stability of the organohalohydrosilanes. When the organohalide is methyl chloride and the water content is 50% by volume, in the optimum temperature range, the content of methylchlorohydrosilanes in the condensed reaction product is generally at least about 50% by weight. The range comprises temperatures of about 300-370 ⁰ C, preferably about 320-340 ° C at atmospheric pressure. At 2-0 atmospheres pressure of this range is wider, about 260-330 ⁰ C, preferably from about 280-33O ⁰ C. Within this preferred range, there is no statistically significant changes in the product composition with temperature for Reakt'i ones as in Fluidized bed reactors occur.

As apparent from the foregoing, the direct synthesis process of this invention can be carried out for the production of organohalogonohydrosilanes at atmospheric or higher pressure. It is recommended to stir the synthesis under pressure as this increases the reaction rate and makes better use of hydrogen, organohalide and the activated silicon. A maximum pressure (measured at the top of the fluidized bed reactor) of about 6 or more atmospheres ensures controllable reaction rates. An optimum pressure range of about 2-4 atmospheres allows the process to be carried out uniformly and in a controlled manner with acceptable selectivity for a longer time. In its preferred form, the direct synthesis process of the present invention is carried out in a fluidized bed reactor using copper-activated silicon, a nickel promoter, a gaseous organohalosilane-hydrogen mixture, and an organohalosilane gaseous auxiliary. The reactor may have a single or multiple nozzle for continuous introduction of the gas mixture. Devices for the continuous or batchwise addition of copper-activated silicon, promoters and auxiliaries are also provided. Devices for the continuous removal of gaseous reaction products, unreacted organohalide and hydrogen, and finely divided particles are also supplied on request. The conventional techniques and devices are known and can be used. As shown in Example 11, the synthesis of RSiH ₂ Cl is preferably carried out in a fixed bed reactor.

Conventional means are available for separating the solid particles from the hot gases (for example, cyclones and / or filters) as well as for cooling of the hot URT condensation i. Product mixture ii a vessel separate from the fluidized bed reactor, if desired. Other work details relevant to the fluid bed reactor and the separation and recovery of the reaction products are known to those skilled in the art and, therefore, will not be described in detail here.

Uniform operation is typically defined as the condition in a direct reaction wherein the speed and selectivity parameters have assumed stable values following an initial entry or unstable period. Provided that the supply of activated silicon, promoter and reactive chromium halide or their mixture with other gas is continued at their preferred rates, the steady state condition can be maintained for a very long time, for example from less than 10% SiConversion to more than 50% Si conversion, to be extended. Diorganodihalosilanes are the preferred products of the prior conventional Rochow direct reduction process. A quantitative measure of this preference is the gravimetric ratio, wt% R ₂ SiX ₂ / wt% RSiX ₃ , usually abbreviated D / T, and referred to as the selectivity of the direct synthesis; these values of our process are described here. The present invention relates to the preferred synthesis of organohalohydrosilanes. Consequently, other quantitative measures of reaction selectivity are required. These performance parameters are defined below for the case where the organohalide is methyl chloride. (MeCl).

In the examples and tables, the term MeSiH refers to the total content of methylchlorohydrosilane in the reaction product. So

MeSiH = MeHSiCl ₂ + Me ₂ SiHCl + MeSiH ₂ Cl.

E r is expressed either as a gravimetric or molar percentage The predominance of MeHSICI ₂ over Me ₂ SIHCI is shown by the molar or gravimetric etch, MeHSiCI ₂ / Me ₂ SiHCl, abbreviated MD / DM. The expression

(MeHSiCl ₂ + Me ₂ SiHCl + MeSiH ₂ Cl)

Me ₂ SiCl ₂

is a measure of the total selectivity of SiH compounds in relation to the main conventional product,

Dimethyldichlorosilane. It can be either a gravimetric or a molar ratio. The overall rate of the direct synthesis method of this invention is defined as the amount of raw material per Time unit, for example grams of Si reacted per kilogram of Si in the reactor per hour, or% Si,

which is reacted per hour, or grams of MeCl reacted per gram of Si in the reactor per hour. These definitions are used in the present invention. In addition, there are other definitions for the present synthesis, specifically the weight or volume or molar (or percentage) of hydrogen reacted per unit time, and the molar or gravimetric amount of organohalohydrosilanes formed per gram of Si per unit time. The high selectivity for

Organohalohydrosilanes ensure that the overall silicon conversion rate at which all these reaction products

not much larger than the sum of the specific formation rates of

RSiHX ₂ + R ₂ SiHX + RSiH ₂ X. According to the direct synthesis method of the present invention, the use of the preferred and defined

activated silicon both a high reaction rate and a high selectivity for Organohalogenhydrosilane.

For the specific case of methylene chloride-hydrogen as a gaseous reaction mixture is with Reaction rates by our invention of more than 1 wt .-% Si conversion per hour and selectivities of MeSiH> 50Gew .-% of the reaction product, MD / DM s 5.0, MeSiH / D> 1.0 simultaneously reached the equilibrium state. In our invention, reaction rates of more than 2% by weight of Si conversion per hour are preferred. MeSiH> 70% by weight, MD / DM s 3.0 and MeSiH / D> 2.0 at equilibrium. These equilibrium speeds

and selectivities can at a temperature of about 290-330 ⁰ C and achieved a pressure up to about 4 atmospheres.

Most importantly, however, this invention teaches controlling the rate and selectivity parameters of ours Direct synthesis of methylchlorohydrosilanes. The values of the parameters depend on the trace metal content of the activated one Siliciums as well as the special injected chlorosilanes or methylchlorosilanes. This flexibility is in the

illustrated below.

As stated above, the main products of the previous conventional processes are methyl chloride as Organohi logenid is used, HSiCI ₃ , Me ₂ SiHCl, MeHSiCI ₂ , Me ₃ SiCl, SiCl ₄ , MeSiCl ₃ , Me ₂ SiCl ₂ , Me _x Si ₂ CI ₈ _ _x (0 <χ <6, χ is

an integer), various methylchlorosilamethanes, methylthiordisilox / jno and methylchlorotrisilanes. In this list, all compounds that follow Me ₂ SiCl _{2 have} normal boiling points above VO ⁰ C and include the heavy or higher boiling fraction. Normally, Me ₂ SiCl _{2 is} at least 80% by weight, MeSiCl _{3 is} 1-5% by weight and the higher boiling

Fraction to 1-6Gew .-% contained in the reaction products. The compounds formed by the process of the invention using methyl chloride and hydrogen are the

with the exception that in addition MeSiH ₂ CI is formed. The preferred compounds of the present invention

Invention are MeSiH ₂ Cl, Me ₂ SiHCl and MeHSiCl ₂ . According to this invention, the total content of these Compounds in the reaction product at least 50% by weight and preferably at least 70% by weight. MeSiH ₂ CI makes

at least 1% by weight; Me ₂ SiHCl is at least 10% by weight and preferably at least 20% by weight; MeHSiCl ₂ at least 40% by weight and preferably at least 50% by weight. That these organohalohydrosilanes could be directly synthesized in such high selectivity was completely unexpected and unpredictable.

When using this invention, the levels of certain by-products were normally as follows: MeSiCl ₃ makes

at most 20% by weight, Me ₂ SiCl ₂ is in the range of 20-50% by weight, Me ₃ SiCl is at least 1% by weight and the higher-boiling fraction is at most 1% by weight. In fact, the process of the present invention can generally reduce the level of higher boiling fraction to undetectable (eg, <0.05 wt% by gas chromatography) levels.

The following examples serve to further illustrate this invention. In the examples, certain catalysts

and silicon materials used; for convenience, these are summarized in Tables 3 and 4.

Table 3 summarizes the analyzes of the copper catalysts used in the examples. Table 3: Composition of copper catalysts Element C-1 C-2 C-3 (M C-5 C-6

Cu (a) 64.1 64 65 01.8 87.9 64.2

Al ppm 90 <1 2 2070 <24 5

As ppm N.A. <1 N.A. 892 <20 4

Cd ppm <20 <1 <1 <10 <10 <1

Cr ppm <12 <12 <12 44 <23 <12

Fe ppm <20 396<\ 16400 190 12

Ni ppm <20 <1 <1 165 <23 <1

Pb ppm <50 95 <1 358 106 <1

Sb ppm <20 <20. <1 <25 <23 <1

Sn ppm <20 <20 <10 1200 126 <10

Zn ppm <100 750 300 987 42 300 (a) wt% copper

The silicon used in the examples was obtained from commercial sources and all materials had particle sizes from about 100 microns to about 208 microns. Table 4 presents the analyzes of a number of trace elements of the silicon material used in the examples.

In the examples, two different reactors were used. Reactor A was used only at atmospheric pressure, Reactor B was of a construction which permitted its use at overpressure; These are described below.

Table 4: Content of trace elements of the silicon samples

Element Si-I Si-2 Si-3 Si-4 Si-5 Si-6

Al wt .-% (Ui QM 0 ^ 23 Ö25 Ö7i4 0.18

Ca ppm 149 176 244 317 196 318

Cd ppm <1 <2.5 17 <2.5 <1.0 <2

Cr ppm 60 46 22 7.9 66 181

Cu ppm 86 24 34 12 24 45

Fe% by weight 0.44 0.39 0.18 0.27 0.36 0.26

Mnppm 80 111 12 16 105 252

Ni ppm 16 20 13 81 53 20

Pb ppm <2 <2.5 <7 <2.5 <2.5 <2

Sb ppm <2 <2.5 <3, <2.5 <2.5 <2

Sn ppm <2 <2.5 <3 '<2.5 <2.5 <3

Ti ppm 365 339 254 386 321 546

V ppm 23 33 10 10 92 56

Zn ppm 3 4 3 <3 <2 8

Zr ppm 46 49 22 23 23 43

Reactor A

This was a conventional Vycor * fluid bed reactor with a total length of 91 cm and an id of 3.5 cm. A sintered glass frit at the reactor base supports the bed of silicon or activated silicon particles and disperses the reacting gas (e.g., organohalide-hydrogen mixture) as it enters the bed. A Vycor * reservoir vented with nitrogen is connected to the reactor near its base, just above the frit, to allow intermittent addition of catalyst, promoter, and / or additional silicon or activated silicon. The connection between reservoir and reactor is normally kept closed by a valve. Two thermocouples are placed vertically through the reactor head into the bed of silicon or activated silicon particles. A thermocouple is connected to a digital thermometer. The other provides the feedback signal to the heater / controller. Electric heating wire and fiberglass insulation run the length of the reactor. The two ends of the heating wire are connected to the heater / controller. The top of the reactor is through a Vycor® sidearm of 2.5 cm i. D. and 20cm length connected to the condensing chamber. The Krndensierkammer is kept at -63 to -78 ⁰ C with solid carbon dioxide and isopropanol. Condensed samples of the reaction product are withdrawn into weighed containers, usually hourly. Unreacted The organohalide was distilled off at 23-3O ⁰ C, the residue analyzed by GC, GC / MS and / or GC / FTIR.

Reactor B

This was a carbon steel fluid bed reactor 183 cm long and 5.08 cm high. d. A sintered metal frit at its base carries the silicon or activated silicon bed and distributes the gaseous reactant as it enters the bed. A flanged carbon steel reservoir vented with nitrogen is located near the base, just above the frit, and allows for the discontinuous addition of catalyst, promoter, and / or additional silicon or activated silicon to the reactor. The connection between reservoir and reactor is normally kept closed by a valve. Two thermocouples are mounted in the silicon or activated silicon bed. One provides the feedback to the heater / controller; the other is connected to a digital thermometer. The electrical heaters with insulation on the outer surface extend over the entire reactor length. The heaters are connected to the heater / controller. A measuring element at the head of the reactor measures the reactor pressure. The reactor outlet is connected to a carbon steel cyclone which connects the downflow with a sintered metal filter. The separation of the fluidized solid from gaseous reactor effluent occurs in the cyclone and the filter. A backpressure control valve mounted behind the condenser exit allows reactor B to operate at pressures up to 100 psig. Sampling and analysis are performed as described above for Reactor A.

For both reactors, gaseous organohalide, hydrogen and nitrogen are transported from their commercial cylinders through stainless steel tubes to the usual reactor unit. All gases, each by themselves, were treated for oxygen traces (for example with OXICLEAR®, Labclear, Oakland, CA) and moisture (for example with Drierite® and / or Lind's 4 A molecular sieve) before entering the reactor to remove. The liquid auxiliary (for example CH ₃ SiCl ₃ ) is additionally fed by means of an injection pump, metering pump or gas pressure (N ₂ , H ₂ or organohalide) into the usual inlet. The normal inlet is heated to temperatures well above the boiling point of the adjuvant, so that a full stream of gas enters the reactor. All flow meters are calibrated and control valves are installed in the transport lines to prevent inadvertent contamination of the feed sources. All gas flow rates mentioned in the examples refer to 21 ⁰ C and constant reaction pressure.

AusfOhrungsbelsplele

example 1

This example illustrates the detrimental effect of zinc on selectivity for all methylchlorohyrosilanes (MeSiH).

Run 1A was carried out without further addition of zinc to the reactants while Run B contained an increased zinc content by the addition of ZnCO ₃ . In both runs were 246,9g silicon, SM and 3.1 g of cement copper catalyst, C-4 A mixed in the reactor and heated under nitrogen fluidization in a nitrogen flow of one liter per minute to 325 ⁰ C. Thereafter, hydrogen chloride gas was supplied at a flow of one liter per minute through the bottom of the reactor for 30 minutes to activate the silicon. During this time a warming to 10-2O ⁰ C was observed. During this activation, about 1-2% of the silicon was converted to chlorosilanes, mainly trichlorosilane, which were removed, condensed, collected and weighed.

Run 1A After completion of the hydrogen chloride flow to activate the silicon were introduced 472 ml / min of hydrogen and 1,013ml / min methylene chloride (32Vol .-% of hydrogen) through the frit in the reactor bed, and the reaction was conducted at 325 ⁰ C for 8 hours Fluidization continued. At the beginning, the total zinc concentration of the activated silicon was 15.2 ppm; at the end of the reaction, it was less than 5ppm.

Run 1B - After completion of the hydrogen chloride stream to activate the silicon, 0.5 g of zinc carbonate was mixed with 2.8 g of silicon, Si-I, and added just prior to the introduction of the hydrogen-methyl chloride mixture through the reservoir. The flow of the gaseous mixture was continued for eight hours at a reaction temperature of 325 ° C. At the onset of the reaction, the total zinc concentration of the activated silicon was 1.046 ppm; in the end, it was less than about 70 ± 20 ppm.

in both runs, samples were taken hourly and analyzed by gas chromatography after removal of unreacted methyl chloride. The average composition of the hourly samples is given in Table 5.

The data allow the following conclusions:

(1) Reduced total zinc concentration in the activated silicon at the beginning causes the average hourly concentration of methylchlorohydrosilanes (DM + MD) to increase by about 91.4%. From 15.1% by weight in runs 1B to 28 , 9% by weight in Run 1A.

(2) The selectivity for methylchlorohydrosilanes was greater when the activated silicon contained less than 50 ppm zinc.

(3) Although the higher zinc content in Run 1B was associated with a higher reaction rate of the silicon and the formation of a greater total weight of the product mixture over the eight hour reaction time as compared to Run 1A, the selectivity suppression for the methylchlorohydrosilanes was in Run 1B so great that the absolute total weight of methylchlorohydrosilanes of 33.78 g formed in Run 1A far exceeded that of 17.84 g formed in Run 1B.

Example 2

This example shows the influence of the tin content on the selectivity for methylchlorohydrosilanes (MeSiH).

Lauf2A, 2B, 2C

They were carried out in reactor A and yielded 300g of silicon Si-5 and a single copper catalyst selected from the list in Table 3.7.5g of cement copper catalyst C-4 was used in Figure 2A; 7.5g of non-cemented copper catalyst C-5 was shown in Figure 2B and 24g of copper (I) chloride catalyst C-1 in 2C. The procedure used to activate the silicon with HCI was that described in Example 1. The reaction was carried out at 325 ° C. for eight hours with a mixture of 615.8 ml / min of CH ₃ Cl and 653.3 ml / min of H ₂ (51.5% by volume of H ₂ ). Sampling and analysis of the reaction product were carried out every hour as described in Example 1.

Table 5: Average of Hourly Compositions of Samples Collected in Runs 1A and 1B

DM MD M T D HVS MD / DM Mt) SiH MeSiH / D Rate, " ¹ run Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 2,974 ± Wt. % 0.53 + % Si / hr 1A 7.44 ± 21.45 ± 2.87 ± 11.97 ± 55.17 ± 0.58 ± 0.70 28.90 ± 12:05 13.1 ± 1.22 1.79 12:41 1.78 2:52 12:27 1.59 ± 1:57 0.22 ± 12:46 1B 6.10 ± 9.01 ± 4.42 ± 7.96 ± 71.48 ± 0.94 ± 12:51 10.15 ± 12:08 1.78 + 1.92 2.99 12:40 0.82 3.97 0.61 4:00 12:46

(a) Average rate of silicon per hour.

Note: Each entry in this and subsequent tables should read as follows: e.g. 7.44 ± 7.44 ± 1.22 1.22

Lauf2D

In the experiment of Run 2D reactor was charged with B a mixture of 1400 g silicon Si 1.75 g of cuprous chloride and 1.5 g of C-2 SnCl ₂ and under a flow of 2.6 liters / min and 1 atm of nitrogen at ⁰ C 33P heated. Then 2.3 liters / min HCl at 1 atm 1 hour, taken long, during which time the temperature rose to 348 ⁰ C. The weight of crude trichlorosilane formed was 360,4g. After completion of the HCI stream, a mixture of 1.84 liters / min. CH ₃ CI and 1.56 liters / min H ₂ (46 vol .-% H ₂ ) initiated. The gas streams relate to 30psig and was 21 ⁰ C. The reactive η for 20 hours at 335 ⁰ C and continued psig 30th During the first hours of reaction, heating to 30-40 ⁰ C. The sample was wurrden in the amounts shown in Table 8 intervals removed. The samples were analyzed by gas chromatography. The initial concentrations of Cu, 3n and Zn in the activated silicon coupon of the four experiments are summarized in Table 6. Note that the initial concentrations of Zn were all less than 50ppm. Table 7 shows that the reaction of Run 2 A, in which the initial Sn concentration was 29.3 ppm, was significantly less selective for the metr ylchlorohydrosilanes and provided more methylchlorodisilanes (HVS) than the Run 2B and 2C reactions.

Table 6: Concentration of critical trace elements and copper in the activated silicon of runs 2 A-2 D

sn Zn Cu run (Ppm) (Ppm) (Wt .-%) 2A 29.3 24.1 1.97 2 B 3.1 1.0 2.14 2C <1.5 <7 4.94 2D 671 40 3.53

Table 8 contains the composition of the samples collected periodically during the 20 hour reaction of Run 2 D. The data show that a constant rate and composition was not detectable during the 20 hour reaction. The high Sn concentration in the activated silicon resulted in a very low selectivity (MeSiH and MeSiH / D) for methylchlorohydrosllanes and a considerable formation of methylchlorodisilanes (HVS) and methyltrichlorosilane (T). Taken together, the four runs of this example demonstrate that the total concentration (MeSiH) of the methylchlorohydrosilanes in the product mixture can exceed 500% by weight and the MeSiH / D ratio can be greater than 1.0 when the Sn concentration in the activated silicon is less than 1 ppm and at Zn is less than 50ppm, preferably less than 2Gppm.

Example 3

This example illustrates the advantages in terms of reaction rate and selectivity for methylchlorohydrosilanes (MeSiH) using a silicon containing 40-100ppm nickel distributed throughout all activated silicon particles.

Table 7: Average Hourly Composition of Samples Collected in Runs 2 A-2 C

DM MD M T D HVS MD / DM MeSiH MeSiH / D Rate, run Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 6.59 ± Wt. % 0.33 ± % Si / hr 2A 2.52 ± 17:38 ± 2.66 ± 16.05 ± 58.48 ± 3.12 ± 12:25 19.06 ± 12:06 0.27 ± 12:19 1.60 12:49 6:56 9.26 1.27 2.75 ± 0.82 1.45 ± 12:03 2 B 14.22 ± 39.07 ± 3.0-1 ± 6.57 ± 36.81 ± 0.21 ± 12:11 53.29 ± 12:13 0.57 ± 0.78 1:35 12:28 12:47 1:52 12:14 2.18 ± 1.96 0.86 ± 12:07 2C 12.70 ± 27.64 ± 5.38 ± 6.46 ± 47.66 ± 0.03 ± 12:06 40.33 ± 12:19 0.62 ± 1.89 3.97 0.81 1:45 3.69 12:03 5.85 12:12

Table 8: Composition of Cumulative Samples Collected During Run 2 D

TC DM MD M T D HVS MeSiH MeSiH / D Rate, Time (hr) Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 12:19 % Si / hr 0-2 2:09 _ 7:52 6.64 35.10 40.52 8.13 7:52 12:13 7:58 2-6 12:12 12:09 7.25 2.27 24.24 57.18 8.89 7:34 12:11 3:47 6-8 - _ 5.73 2:00 25.82 54.10 12:35 5.73 12:09 2:34 8-12 - 12:24 5.93 1.79 22.91 65.51 3.62 6.17 12:13 2:03 12-16 0.93 12:32 7:57 30.2 22.90 59.95 4.85 7.89 12:35 1.75 16-20 6.65 12:53 15:25 1:04 30.73 44.54 1.27 15.78 1.22

Lauf3A, 3B, 3C

Three different silicon samples (Si-I, Si-4, Si-5) were used in three separate runs and summarized in this example; Reactor B was used in all three cases. The amounts of silicon and catalyst used in these experiments are summarized in Table 9. The table also shows reaction temperature, pressure, hydrogen and methyl chloride flow rates, duration of each experiment and the concentrations of Cu, Sn, Zn and Ni initially present in the activated silicon.

The activation of the silicon-catalyst mixture was carried out as in Run 2 D, described with gaseous HCl, except that the duration of the HCI stream was 60 min in Run 3 A and 30 min in Runs 3B and 3C, respectively. Table 10 shows the total weights of the crude (e.g., the product still contains dissolved methyl chloride) product mixture obtained in each run, the composition of each product mixture, converted to methyl chloride content, and the speed and selectivity percentage of the synthesis. The data show that nickel concentrations of about 10-lOOppm in activated silicon cause high selectivity for methylchlorohydrosilanes. The MeSiH / D ratio was greater than 1) 0 and the MeSiH accumulation was greater than 50 weight% in each of the three runs of this example. However, a comparison of the rate in Run 3 A, in which the initial concentration of Ni in the silicon particles was 16 ppm, with the rates of Runs 3B and 3C, in which the initial concentrations of Ni were 53 and 83 ppm respectively, indicated that the rates at nickel concentrations of about 40-100 ppm higher. In addition, the nickel promoter must have been present in the silicon samples Si-4 and Si-5 in a catalytically active state.

Si Catalyst Temp. Press. H ₂ Vol .-% Weight of TC DM MD M CH ₃ CI Duration Cu -16- 288 152 % Si / hr 1,492.4 g 74.6 g ⁰ C psig lit / min H ₂ Crude Wt. % Wt. % Wt. % Wt. % lit / min Mr. Wt. % 12:32 SM C-2 315 ± 3 30 1:57 61.1 81.3 0.11 16.26 43.52 3:37 1:00 4 3.3 sn Zn Ni 1.96 1,382.Og 73 g 63.0 554 3.34 14.82 50.50 1:59 ppm ppm ppm 1.30 Si-5 C-1 307 ± 3 30 2:03 50.C 356.6 1.55 16.84 37.96 4.68 1.19 8th 3.0 <5 41 16 ., 0Og 45 g , Si-4 C-O 312 ± 2 30 2.17 2.17 8th 3.3 <5 7 53 Table 9: Reaction Conditions and Activated Mass Composition in the Runs 3A-3C Table 10: Composition of the Reaction Products of Runs 3A-3C <3 18 83 run T D MeSiH 3A run Wt. % Wt. % MD / DM Wt. % 3A 5.70 31.03 2.68 59.78 Rate, 3B 3B 12.42 17.43 3:41 65.32 MeSiH / D 3C 9.16 29.81 2.25 54.80 1.93 3C 3.77 1.84

Example 4

This example shows that a silicon sample with low or inactive nickel content (and thus low reactivity in the direct synthesis of methylchlorohydrosilanes, MeSiH) can be made to be faster by the addition of nickel powder. Speed to respond, since the effective nickel concentration is kept high in the activated silicon. This sample also shows the effects of nickel addition on the composition of the reaction product. The three runs of this example were carried out separately in reactor B.

Run 4A: In this example, silicon sample Si-1 was used. In Run 3 A, it was shown (Tables 9 and 10) that this silicon had a low nickel content.

A mixture of 900 g silicon, Si-1, und45,1 g of copper (l) chloride catalyst, C-6 was heated under nitrogen fluidization to 330 ^c C, and then described for 30 minutes as in Run 2 D 2 , 3 liters / min of gaseous HCI activated. During activation, 9.0 g nickel powder (1 micron particle size from Alpha Inorganics, Andover, Mass., Lot # 100675) mixed with 30 g silicon, Si-1, was added to the reactor. Upon completion of the HCI flow, hydrogen (2.2 liters / min) was used for 30 minutes to desorb the chlorosilanes from the activated silicon.

For the reaction, CH ₃ Cl and H _{2 were used} at 1.25 liter / min, the reaction pressure was 30 psig, the temperature was 280 ° C. The samples were taken hourly for 5 hours. Thereafter, the reaction temperature was raised to 310 ° C and the reaction continued under the above-mentioned conditions. After two hours, a mixture of 9 g of nickel powder and 30 g of Si-1 was again added to the reactor through the reservoir, and the reaction was followed for a further five seconds. Table 11 shows the composition and rate and selectivity parameters for the samples taken hourly during the experiment. The data show that the initial reaction rate (0.77% Si per hour) of the activated mass prepared from Si-1 and exogenously obtained nickel was higher than observed in Run 3A, despite the 35 ^° C. lower temperature in Run 4A The data also shows that this higher initial rate is greatly reduced in the absence of further nickel additions. The speed increase during the 6-7 hours was achieved by raising the temperature to 31O ⁰ C. A second nickel addition (equivalent to 1% by weight, based on the silicon in the reactor) made after the seventh hour caused the rate of reaction to increase to 1% Si per hour in the eighth hour. However, as the drop in speeds for hours 9-12 shows, the speed increase was only temporary. Thus, the effect of exogenously obtained nickel is short lived unless the addition is made frequently or continuously to maintain both a chemically active form of the nickel and an effective nickel concentration in the activated silicon.

Run 4B: The experiment of this example was performed by continuing Run 3C for eight hours. Additions of 9.1-9.6 g of nickel powder in 60 g of silicon, Si-4, were made at the beginning of the ninth, seventeenth, and twenty-first hour. The reaction was continued at 310-32O ⁰ C and 30 psig with 3.17 liters / min CH ₃ Cl and 2.17 liters / min H ₂ to 21 hours. At the end of this 21st hour, a sample of the cooled activated silicon was removed for nickel analysis.

Table 11: Composition of Samples and Performance Parameters for Run 4 A

Time TC DM MD M T D MD / DM MeSiH MeSiH / D Rate, (Mr) Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 5:34 Wt. % 2.27 % Si / hr 1 3.64 9:41 50.26 1.61 8.79 26.29 6.68 59.67 3:55 0.77 2 1:00 8.61 57.49 2:49 11.81 18.60 5:43 66.10 3:39 12:22 3 0.99 4.10 54.48 1.84 13.64 1.19 5.82 64.52 3.21 12:18 4 0.98 9.31 54.19 2.11. 13.61 19.80 4.74 63.50 3:04 12:17 5 0.91 10.87 51.54 1.60 14.63 20:55 4.27 62.41 4.61 12:16 6 "> 12:34 13.87 59.15 1.17 9.63 15.84 5.26 73.02 4:57 12:54 7 12:46 11:56 60.84 1:44 9.84 15.86 5:07 72.40 1.70 12:52 ₈ (b) 1.83 8.74 44.33 0.77 13.9 31.14 6:34 53.07 2.67 1:40 9 3.23 8:38 53.09 0355 11.71 4.23 6.69 61.47 3:58 0.61 10 4.23 8:50 56.82 0.69 11:52 18:24 7:36 65.32 3:50 12:42 11 3:55 7.76 57.12 0.93 12:10 18:54 6.99 64.88 3:58 12:40 I2 3.63 8:06 56.33 0.94 7.13 17.97 64.39 12:34 (a) - Temperature raised to 31O ⁰ C (b) - Nickel added

Table 12 estimates the composition of the hourly collected samples and the associated L- ¹ parameters (eg, speed, selectivity). It was observed that following the addition of 9.1 g of nickel to the ninth, seventeenth, and 9.6 g of nickel at the twenty-fourth hour to the reactor, the reaction rate increased to values (1.6-2.6% Si per hour). which are beyond those described in Example 3C. But as from the data for the periods 13. -16., 21. -23. and 28.-29. Hour is to be seen, any speed increase was only temporary. The experiment showed that the intermittent velocity enhancement caused by exogenous nickel in the silicon sample, Si-I, which has an inherent nickel deficiency, was also observed with silicon sample Si-4, which is an inherently effective nickel level Has. It is clear that a major effect of exogenous nickel is an increase in speed.

The nickel concentration of the activated silicon after the reaction was found to be 0.318 wt% by analysis. After the 28th hour, the reaction rate dropped to less than 1% Si per hour. Consequently, this result indicates that it is not enough to have nickel concentrations greater than 0.1 wt% in the activated silicon to observe increased rates of reaction. The nickel must also be present in a catalytically active form, preferably, as in Example 3, distributed through all activated silicon particles for best results.

Table 12: Composition of Samples and Performance Parameters for Run 4 B

Time TC DM MD M T D MD / DM MeSiH MeSiH / D Rate, (Mr) Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 1.61 Wt. % 0.68 % Si / hr G(.) 1.20 12:50 7.20 2:09 16:45 47.69 1.75 32.57 1.14 1.12 10 0.74 16:34 28.59 2.99 7.12 3P.27 1.74 44.93 1.30 1.77 11 12:28 17.62 30.68 3.31 10.94 37.17 2.70 48.30 1.61 1:57 12 0.83 13.72 37.09 3.63 9:42 35.31 2:44 50.81 1.75 1:53 13 1.31 16.5 39.13 3:32 8:57 31.62 2.91 55.18 1.64 0.99 14 1.12 13.69 39.82 3:36 9:39 31.62 2.27 53.51 1.96 1:06 15 1:56 17:54 39.83 2.97 8.83 29.27 2:44 57.37 1.92 0.96 16 1.78 16:33 39.76 3.62 9.25 29.96 1.91 56.09 0.71 0.60 17 " ' 12:58 11:23 21:42 2.29 18.70 45.78 2.14 32.65 1.24 2:42 18 1.31 14:50 31.01 2.77 13.64 36.77 2.16 45.51 1:33 2:04 19 2:05 14.78 31.99 2:34 13.77 35.07 2.24 46.77 1:44 1:44 20 2.24 14.87 33.34 2:46 13.67 33.42 2.26 48.21 1.62 1.30 21 2:33 15.63 35.26 2:04 13:34 31.40 2.27 50.89 1.74 0.93 22 2:46 16.9 36.45 1.97 12.86 30.17 2:38 52.54 1.98 0.81 23 2.29 16:48 39.22 2.28 11.62 28.11 2.15 55.70 0.65 0.63 ₂₄ .b) 0.88 9.22 19.80 1.73 23.72 44.63 2:43 29.02 1.18 2:32 25 1:46 12:47 30.28 2:05 17:41 36.33 2.61 42.75 1:38 2:33 26 2:00 12.71 33.16 1.84 6.17 33.23 2.74 45.87 1:44 1.65 27 2.18 12:40 33.96 1.70 17.65 32.11 2.85 46.36 1.66 1.15 28 2.11 12.86 36.65 1.66 16.92 29.80 2.93 49.51 1.90 0.82 29 2:03 13:39 39.29 1.65 15.93 27.71 52.68 0.65 (a) 9.1g. Ni added (b) 9.6 g. Ni added

Lauf4C: The experiment of this example was carried out at 310-332 ⁰ C, using 30psiguntor of 1.42 liters / min H ₂ and 1.44 liter / me. CH ₃ CI performed. The activated silicon was prepared from 900 g silicon, Si-4.45.0 g copper (I) chloric), C-6, and 0.9 g nickel powder (1 micron particle size, Alpha Inorganics, Lot # 100675) and gaseous HCl at 330-343 ° C as described in Run 2D. HCI activation was continued for 30 minutes. Thereafter, hydrogen was introduced at 2.4 liter for 30 minutes and Opsig to desorb the chlorosilanes from the activated silicon particles. The hydrogen-methyl chloride mixture was then injected. The Anfangsreaktionstempeiatur was 33O ⁰ C.

In addition to the hourly additions of nickel powder mixed with silicon Si-4 described in Table 13, to the reactor to maintain the catalytically active nickel at an effective level and to avoid a decrease in the rate observed in Runs 4 A and 4B , Added amounts of solids are listed in Table 13. Also shown in Table 13 are the average hourly temperatures, hourly weights, crude reaction product and hourly silicon weight calculated as it should be in the reactor at the beginning of each hour. The reaction was continued for a total of 29 hours at the end of which a cooled sample of the activated silicon was analyzed to find 0.203 wt% Ni.

Table 14 contains the composition of both the hourly samples and the rate and selectivity values for each sample. The data show that the frequent nickel powder additions give a steady and exceptionally high reaction rate compared to those observed in Runs 4A and 4B. When the nickel addition is maintained from 0.1 wt .-% of the activated silicon contained in the reactor, speeds in the amount of 3,34Gew be e.nalten .-% Si per hour at 330 ± 2 ⁰ C. The average continuous yield was 2.64 ± 0.34 wt% Sipro hour. At 320 ± 4 ⁰ C, the steady state velocity was 1.40 ± 0.18Gew. % Si per hour with nickel additions, equivalent to 0.05% by weight of the activated silicon. Nickel additions of 0.24 wt% of the activated silicon provide a constant rate of 1.25 ± 0.07 wt% Si per hour at 315 ± 4 "C.

The composition of the reaction product also depends on the addition of the Ni powder. Methyltrichlorosilane and dimethyldichlorosilane have increased in the hourly samples immediately after nickel addition. (See Table 11, Sample 8, Table 12, Samples 17:24). The higher levels of nickel used during hours 24-29 of Run 4C (see Table 13) also resulted in rather increased formation of methyltrichlorosilane during that period (see Table 14) compared to the first part of the experiment. Consequently, the nickel addition reduces the percentage of methylchlorohydrosilanes in the reaction product and also the MeSiH / D ratio. (See Table 11, Example 8; Table 12,

Samples 17,24). Consistent with this, it is necessary to control the nickel addition in order to maintain the rate advantages, minimize methyltrichlorosilane formation, and maintain selectivity for methylhydroquinones within desirable limits. It is preferred to feed nickel continuously or batchwise into the reactor in amounts ranging from 0.01-0.25 wt% of the activated silicon to meet these requirements.

Table 13: Reaction Conditions During Run 4C

Time Temp., ⁰ C Si Added Ni Added Crude Product Composition of Samples and Performance Parameters for Run 4C DM MD M T D MD / DM Si in reactor > MeSiH / D Rate, (Mr) 330 gm gm gm TC % % % % % 45.48 gm 1:42 '/ OSi / hr 1 333 _ 0.9 66.8 Wt. % 10:43 35.05 4:54 12:23 32.05 42.13 872.19 1.12 1.64 2 331 50.6 0.9 102.7 5.70 10.74 31.39 5:42 11.66 37.61 44.76 908.51 1.20 2:38 3 332 15.0 0.9 123.0 3.18 12:44 32.32 5:08 10:23 37.47 45.72 901.90 1.22 2.90 4 331 10.0 1.0 115.7 2:46 13.78 31.94 4.60 6.10 37.52 45.22 885.76 1.16 2.81 CJL 329 10.8 0.9 118.4 2.10 14:34 30.88 4.13 9.75 39.05 42.51 871.66 1:07 2.94 6 328 60.0 0.9 145.2 1.85 14.69 27.85 3.28 12:46 39.88 43.63 906.60 1:07 3:34 7 328 20.4 0.9 110.8 1.84 14.93 28.70 3:37 10.97 40.65 44.19 896.76 1.14 2.65 8th 330 25.4 0.9 110.3 1:38 14:23 29.96 3.78 10.74 38.85 4E.90 898.40 1.22 2:57 9 330 18.4 0.9 105.1 2:44 15:30 30.60 3.28 10.89 37.55 45.25 893.96 1.18 2:45 10 329 25.5 0.9 104.4 2:38 2.14 31.23 3:35 10.63 38.28 46.16 897.33 1.25 2:44 11 327 30.0 0.9 98.2 2:49 14.74 31.42 2.95 11:42 36.99 46.54 905.47 1.26 2.28 12 328 31.0 0.9 94.3 2:48 14:34 32.20 2.76 11:50 36.83 46.39 915.82 1.30 2.21 13 326 30.6 0.9 84.6 2:37 14:37 32.02 2.81 12:33 35.69 40.41 926.17 1:06 1.95 14 325 0 0 46.3 2.78 11.68 28.73 2:07 15.94 38.19 45.85 908.12 1.31 1:08 15 316 0 0 66.8 3:39 14.60 31.25 2.68 13.93 35.09 49.11 898.33 1:46 1:59 16 323 0 0 58.1 2:45 15.97 33.14 2:36 11.95 33.61 51.62 884.09 1.83 1:38 17 320 42.5 12:45 71.0 2.97 5.15 36.57 2.16 14.83 28.25 56.63 914.35 2:34 1.63 18 320 15.0 Ü.45 64.8 3.14 16:45 40.18 1.81 14:26 24.18 56.66 914.44 2.31 1:51 19 317 10.1 12:45 54.4 3.12 16:18 40.48 1.78 13.92 24.53 55.87 910.74 2.18 1 .29 20 318 20.5 12:45 50.7 3.11 16:00 39.87 1.77 13.85 25.65 B4.80 919.50 2.07 1 .19 21 311 20.1 12:45 51.2 2.86 15.67 39.13 1.77 14:35 26.42 48.96 928.66 1.65 ( .19 22 307 0 0 31.2 2.66 13:26 35.70 1.16 15.73 29.68 54.40 917.65 1.99 ( ) .72 23 314 0 0 39.1 4:47 15.86 38.54 1.64 13.89 27.35 50.97 911.08 1.98 24 314 26.2 2.25 52.9 2.72 14:47 36.50 1:33 18:10 25.79 50.34 928.99 1.85 .15 25 317 19.0 2.25 54.5 3.81 13.68 36.66 0.94 19:13 27.20 50.32 937.70 1.86 1 .21 26 318 15.0 2.25 55.5 2:39 13:55 36.77 0.87 19.8 27.01 50.55 940.97 1.88 .22 27 319 20.0 2.25 59.1 2.72 13:31 37.24 1.23 18.63 26.83 48.19 949.45 1.72 " .30 28 318 15.1 2.25 61.0 2.76 12:55 35.64 1:33 19.93 28.01 52.20 952.25 1.95 .33 29 10.0 2.25 57.4 2:54 13.69 38.51 1:35 17:22 26.79 949.56 .28 Table 14: 2:44 Time MeSiH (Mr) Wt. "/ 1 3:36 2 2.92 3 2.60 4 2:32 5 2.15 6 1.90 7 1.92 8th 2.11 9 2:00 10 2.23 11 2.13 12 2.25 13 2.23 14 2:46 15 2.14 16 2:08 17 2:43 18 2:44 19 2:50 20 2:49 21 2:50 22 2.69 23 2:43 24 2:52 25 2.68 26 2.71 27 2.80 28 2.84 29 2.81

Bolsplel 5

This example shows that selectivity for methylchlorohydrosilanes (MeSiH) is lower when nickel formate is used as the source of the nickel promoter instead of nickel powder. The use of nickel formate leads to higher methyltrichlorosilane formation. Two separate experiments are summarized in this example. Both experiments were carried out in reactor B.

Run 5 A: A mixture of 42.5 g of cuprous chloride catalyst, C-2, and 850 g of Si-3 was heated to 320 ° C under nitrogen fluidization (2.5 liter / min, 1 atm). Then, hydrogen chloride gas (2.5 liter / min, 1 atm) was introduced for 30 minutes. The total weight of the collected chlorosilanes was 108.6 g.

The reaction was carried out with a mixture of 1.4 liters / min of hydrogen and 1.4 liters / min of methyl chloride at 325 ± 2 ⁰ C and 3qpsig. During the reaction, the amounts of nickel powder and silicon were added at hourly intervals. The amounts thus added are shown in Table 15. The reaction product was collected every hour and analyzed by evaporation of the unreacted methyl chloride by gas chromatography. The reaction took a total of 21 hours. Table 16 shows the cooperation of the hourly samples and the associated speed and slectivity values. It is noteworthy that the activated silicone prepared from the sample Si-3 and the catalyst C-2; against the 50 vol .-% mixture of methyl chloride and hydrogen at 325-33O ⁰ C and 30psig in the absence of added nickel powder was unreactive. The data in Table 16 show that with the addition of 0.1-1 wt.% Nickel powder, the total concentration of methylchlorohydrosilane in the hourly reaction product was generally greater than 50 wt%, the MeSiH / D ratio was generally greater than 2 and the concentration of methyltrichlorosilane was generally less than 20% by weight. The addition of 0.1-0.2 wt% nickel powder in Run 5A (Samples 7-10, Table 16) provided the highest selectivity for methylchlorohydrosilanes.

Table 15: Hourly Additions of Nickel Promoter and Silicon in Runs 5A and 5B

Run5A

Run5B

Si Added Ni powder Sun Ni Added SiAdded Ni (OOCH) ₂ Si in Ni Added Time (Gm) Added Reactor (wt.%) Added Reactor (% Wt.) (Mr) _ (Gm) (Gm) _ - (Gm) (Gm) - 1 40 _ 824.48 0099 25 _ 766.73 12:10 2 17 0.85 859.19 0097 20 2.5 785.36 0099 3 14.3 0.85 873.17 12:10 20 2.5 801.50 0096 4 15 0.90 884.31 12:10 14.3 2.5 818.33 0095 5 0 0.9 895.56 12:10 10.5 2.5 829.03 0095 6 14.1 0.9 891.58 12:14 11.0 2.5 836.04 0094 7 10.4 1.3 900.98 12:19 20.4 2.5 844.25 12:19 8th 10.6 ' 1.7 906.87 0.19 12.5 5.1 862.09 12:19 9 10.6 1.7 913.89 0.18 12.1 5.3 867.83 12:18 10 11.2 1.7 919.82 12:45 10.1 5.0 869.61 12:18 11 10.4 4.2 925.56 12:45 10.1 5.0 868.73 12:18 12 10.8 4.2 929.44 12:45 13.3 5.0 867.8b 12:20 13 11.2 4.3 934.16 12:45 5.5 871.55 14 30.1 4.2 937.97 0.99 15 0 9.5 960.60 0 16 0 0 951.04 0 17 0 0 942.78 0 18 0 0 935.80 0 19 0 0 928.17 0 20 0 0 922.17 0 21 0 917.08

Table 16: Composition of Hourly Samples in Run 5A

Time TC DM MD M T D MeSiH MD / DM MeSiH / D Rate, (Mr) % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. 6.82 2.96 % Si / hr 1 34.03 5:51 37.55 1.75 6:59 14:57 43.06 4.63 3:32 0.63 2 18.92 9.13 42.30 1.61 12:54 15:50 51.43 4:54 3:41 12:35 3 18.85 9:40 42.70 1.29 12:50 15:26 52.10 4.62 3:00 12:36 4 17:35 9.18 42.37 1.71 12:18 17:21 51.55 4:46 2:57 12:39 (Jl 14.85 9:35 41.72 1.79 12:38 19.91 51.07 4.16 2:56 12:44 6 11.67 10:38 43.20 1.85 11.99 20.91 53.58 2.94 3:09 12:53 7 4:45 15.74 46.26 1.62 11.87 6.20 62.00 3.99 2.99 12:50 8th 5.11 8.14 45.31 1.72 13.90 19.88 59.39 3:34 2.75 12:39 9 3.85 13:58 45.29 1.60 14:27 21:41 58.87 3:36 2.82 12:51 10 5.17 13:57 45.59 1.90 12.82. 20.95 59.19 3:54 2.10 12:59 11 6:00 am 11:42 40.44 1.70 15.79 24.65 51.86 3.64 1.86 0.71 12 5.60 10.65 38.74 1.69 16.71 26.61 49.39 3.75 1.61 0.65 13 7.93 9.73 36.49 1:33 18.82 28.71 46.22 3.79 1:50 0.79 14 4:32 9:36 35.51 1:43 19:36 30.02 44.87 2.79 1.20 0.80 15 2.10 1.11 30.67 1.24 20:27 34.71 41.68 1:00

TC DM MD M T D MeSiH MD / OM -20- 288 152 Time Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 3:01 Rate, You) 2.76 12.87 9P.75 1:37 6.17 27.19 51.62 2.99 MeSiH / D % Si / hr 16 3.87 13.85 41.46 1:47 15:23 24.12 55.31 3.17 1.90 0.87 17 4:59 13:21 41.81 1:39 15.67 23:33 55.02 3.1Ü 2.29 0.74 18 4.69 13:12 41.65 1.74 15:11 23.69 54.77 3:09 2:36 0.82 19 5:53 13.61 41.98 1:56 15:51 21.81 55.59 3.19 2.31 0.65 20 5:53 13:11 41.82 1:59 16:10 5.22 54.93 2:55 12:55 21 2:49 12:47

Run 5B: Anhydrous nickel formate (Ni (KCOO) ₂ ) for use in the experiment of this example was prepared from nickel carbonate and formic acid by the method of Bircumshaw and Edwards (Jour Chem, Son., [1950], p. Dehydration was accomplished by washing the green precipitate with acetone and drying in vacuo (10 ^"6 torr) for 16 hours. The chemical analysis of the dried solid gave 31,60Gew .-% Ni, the formula for the Ni (HCOO) ₂ calculated. Nickel content is 31.77%.

The activated silicon of this run was vortexed by heating a mixture of 800 g of silicon Si-3 and 40.9 g of copper (I) chloride d C-2 under nitrogen (2.5 liter / min, 1 atm) fluidization to 325 ⁰ C, then nitrogen or nitrogen was replaced by HCl (2.5 liters / min, 1 atm). The HCI-Sttom was continued for 30 minutes. The weight of the collected chlorosilanes was 160.4g. The reaction was carried out for 13 hours with a mixture of 1.4 liters / min of hydrogen and 1.4 liters / min of methyl chloride at 325 ± 2 ° C and 30 psig. The amounts of the anhydrous nickel formate and 65 x 150 mesh silicon Si-3 added to the reactor at hourly intervals are shown in Table 15. The hourly samples were collected and analyzed as described above in Step Example ¹ 5 A.

Table 17 shows the composition, selectivities and rates of each hourly sample. The nickel additions during the hours 1-7 were 0.1% by weight of the silicium contained in the reactor, then in the hours 7-13 0.2% by weight. The data show that the MeSiH and MeSiH / D values of Table 17 are generally lower than those of Hours 1-10 of Table 16. The use of nickel formate also resulted in less (CHj) ₂ SiHCl (DM) and more CH ₃ SiCl ₃ (T) compared to the values observed with the same equivalent weight of nickel powder. In fact, the CH ₃ SiCl ₃ concentration in the hourly samples of Table 17 was generally above 20% by weight.

Example 6

This example illustrates the high selectivity for methylchlorohydrosilanes (MeSiH) that results from the use of silicon that yields about 60 ppm of chromium distributed throughout all the particles of activated silicon.

Run 6 A and SB: In this example two experiments are summarized. Both were listed in reactor B. Silicon sample Si-I with a total chromium concentration of 60 ppm was used in the run 6A experiment and Si-4 with 7.9 ppm chromium in run 6B. In both cases, the copper-chloride catalyst C-6 was used. The amounts of reagents used and other experimental conditions associated with the experiments of Runs 6A and 6B are given in Table 18. The activation procedure for the silicon and the experiments in Runs 6A and 6B were the same as those described above in Runs 4A and 3C, respectively.

Table 18 shows the average hourly composition and selectivity of the hourly samples collected during the two experiments. The data show that the silicon sample with 60ppm Cr (Run 6A) provides 72.65 weight percent methylchlorohydrosilane (MeSiH), while with 7.9ppm Cr (Run 6B), 54.80 weight percent MeSiH is obtained under the same reaction conditions were. The ratio MeSiH / D was 4.5-5.0 for the first sample and 1.7-2.0 for the second. However, the lower chromium content silicon sample was more selective for dimethylchlorosilane, (CH ₃ JjSiHCl) This was reflected by the lower MD / DM value for Run 6B (Table 18) Generally, selectivities for methylchlorohydrosilanes of at least 60 wt % realized with silicon samples containing 30-1500ppm Cr when the reaction was carried out with 50 / 50vol% hydrogenated methyl chloride.

Table 17: Composition of Hourly Samples in Run 5B

Time TC DM MD M T D MeSiH MD / DM MeSiH / D Rate, (Mr) Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % '/ OSi / hr 1 30.20 2.75 22:49 2.69 8.12 33.75 25.24 8.18 0.75 3.83 2 23.94 3:34 30.30 1.20 20:25 20.97 33.64 9:07 1.60 3:49 3 26.22 3:39 27.16 1:04 28.83 18:36 30.55 8:01 1.66 3:40 4 24.54 3.98 27.22 1:06 24.08 19:12 31.20 6.84 1.63 3:44 5 21:30 4:58 27.27 1.15 24.45 21:25 31.85 5.95 LFO D.42 6 15:51 5:54 27.74 1:48 2 (5.93 23.80 33.28 5:01 1st <> 3:33 7 15.64 4.83 26.55 1:32 26.28 25.38 31.38 5:50 1.2 \ 3.30 8th 7:56 1.11 46.10 12:43 19:10 15.80 57.10 4.19 3.6.! 3.78 9 5.81 10.72 39.57 12:52 22.86 20:52 50.29 3.69 2.4G 1.19 10 7.27 10:46 36.51 12:52 23.82 21:42 46.97 3:49 2.19 1.26 11 5.76 10:10 37.94 12:42 24.23 21:55 48.04 3.76 2.23 1.26 12 5:02 3.10 34.54 12:56 26.28 23:57 44.57 3:44 1.89 .11 13 4.14 9:33 30.30 0.68 28.43 27.12 39.63 3.25 1:46 .10

Example 7

This example shows that zinc and antimony also inhibit the selective synthesis of methylchlorohydrosilanes (MeSiH). The reactor A was charged with 290 g Si-5 and heated to 325 ⁰ C in a fluidizing nitrogen stream (1 liter / min). Then, the nitrogen stream was replaced by a stream of HCI at the same rate, for 30 minutes. The temperature rose

333 ^° C. A mixture of 12g copper catalyst C-1 and 10g silicon Si-5 was added through the reservoir. The HCI stream was continued for a further 15 minutes. Then, the HCI stream was replaced by a stream of nitrogen (600 ml / min), and the synthesis of methylchlorohydrosilanes (MeSiH) began. In total, 72.3 g of chlorosilanes were collected from the HCI activation step.

During the synthesis of the methylchlorohydrosilanes (MeSiH), 0.5g of Catalyst C-1 and 0.5g of Silicon Si-5 were added to the reaction mass every two hours through the reservoir. After the seventh hour, 0.1 g of SbCl ₃ and 0.5 g of silicon Si-5 were begun to be added, and the reaction was continued for another two hours. The reaction temperature was 330 ± 2 ⁰ C during the experiment.

Table 19 shows the composition and reaction parameters for the nine hourly samples. The addition of SbCl ₃ (equivalent to 370ppm SbCl ₃ and I97.5ppm Sb based on the silicon in the reactor) effectively destroys the selectivity for the methylchlorohydrosilanes (MeSiH) and decreases the reaction rate. The formation of dimethyldichlorosilane, methyltriochlorosilane and methyldichlorodisilanes was increased.

Table 18: Reaction Conditions and Reaction Performance in Runs 6A-6D

Si Catalyst Temp. Press. H ₂ CH ₃ CI DM MD D MeSiH 4.74 run 900 gm 45.1 gm ⁰ C psig lit / min Wt. % Wt. % Wt. % Wt. % MD / DM 12:52 6A Si-1 C-7 310 30 1.25 12.66 ± 59.99 ± 15.85 ± 72.65 ± 4.58 ± 2.26 ± 900 gm 45 gm 1.10 0.84 12:10 1.90 12:05 12:12 6B Si-4 C-7 312 ± 21 30 2.17 , 16.84 ± 37.96 ± 29.81 ± 54.80 ± 1.84 ± '0.82 0.80 1:40 1.25 12:13

The antimony level used was within the range taught in the art (for example, U.S. Patent 4,656,301) for promoting dimethyldichlorosilane formation. Together with previous experiments conducted in the absence of added antimony metal or compounds, this example shows that the antimony concentration in the activated silicon must be kept below 20 ppm in order to maintain that high selectivity for the methylchlorohydrosilanes (MeSiH ) can be realized simultaneously with a high reaction rate.

Example 8

This example shows that the content of dimethylchlorohydrosilane, (CH ₃ J ₂ SiHCl, in the direct synthesis product relative to methyldichlorohydrosilane, CH ₃ SiHCl ₂ , is increased by the addition of high purity CaSi ₂ to the activated silicon.

In this example, two experiments are summarized. Both were carried out in reactor A with 300 g of silicon Si-1 and 25 g of catalyst C-2, using the HCI activation method described in Example 1A. In any case, the reaction at 329 ± 2 ⁰ C with a mixture of methylene chloride (628ml / min) and Hj (548 ml / min) was carried out for a period of five hours before the addition of the Calciumsilicids.

Run 8A: CaSi ₂ (Corac, Inc.) with a certified purity of 99.5% was analyzed by X-ray diffraction by volumetric analysis to find that the purity was 99 ± 1% by weight. The sample further contained 0.1 wt% Al and 0.08 wt% Fe. 20g of this powder (-200mesh particle size) was mixed with 10g of catalyst C-2 and added to the reactor at the beginning of the sixth hour. The added CaSi ₂ reached up to 7.5% by weight of the silicon in the reactor. The reaction was continued for a further 3 hours with the 50.9% by volume H ₂ -CH ₃ Cl-GCmISCh. The analysis of the collected samples is shown in Table 19.

Table 19: Composition of Hourly Samples Collncted in Example 7

Time TC DM MD M T D MeSiH MD / DM MeSiH / D Rate, (Mr) Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 4.70 3.63 % Si / hr 1 27.39 9:44 44.33 1.87 2.19 14.78 53.77 2.15 1.85 0.68 2 0.98 18.77 40.33 4:03 3.93 31.94 59.10 2.15 1:43 12:39 ₃ (.l 12:29 16:37 35.15 4:04 8:03 36.06 51.52 1.79 1.18 0.92 4 - 16.84 30.16 5:58 7:46 39.93 47.00 1.76 0.96 0.68 5 '' - 15:34 27.04 4.90 8:50 44.23 42.38 1.61 0.72 1.12 6 - 13.69 3.22 5.85 8.97 49.36 35.72 1.61 0.85 0.90 7 - 15:14 24.32 4.89 9.27 46.28 39.46 1.85 12:27 1.14 ₈ (b) - 5.82 10.77 5:05 16:18 61.45 16:59 4.11 12:13 036 g (bl - 1.75 7.19 4:38 14.74 68.43 8.94 12:30

(a) 0.5gC-1 plus 0.5g Si-5 added at the beginning of the period.

(b) MethylchlorodisHanes were formed following SbCI ₃ addition viz: 0.75wt% In / # and 3.50wt% In # 9.

Run 8B: CaSi ₂ (commercial grade from Elkem Metals Co.) was determined to be 68 ± 4% by weight by X-ray diffraction and volumetric analysis. The sample also contained 1.9 wt% Al and 2.0 wt% Fe. 20g of the powder plus 13g of catalyst C-2 were added to the reactor at the beginning of the sixth hour of the experiment. The added CaSi ₂ reached up to 8.05 wt% of the silicon in the reactor at this time. The reaction was continued with the 50.9% by volume H ₂ -CH ₃ Cl mixture for five hours. Table 19 shows the analysis of the collected samples.

Table 19 also shows the average composition of the ten hour control samples collected in the experiments of runs 8A and 8B prior to the addition of the calcium silicide. The data show that 7-8 wt% high purity CaSi ₂ provides 20.1 gow% (CH ₃ I ₂ SiHCl, that is ~ 40% increase over the control In contrast, the less pure CaSi gave ₂ 9, 55 wt% (CH ₃ J ₂ SiHCl, about 48% decrease compared to the control In addition, the formation of (CH ₃ I ₂ SiHCl is increased compared to CH ₃ SiHCl ₂ and the ratio MD / DM decreased in comparison This example shows that the additions to the reaction should be substantially free of elements (for example Al, Fe) that reduce the selectivity for methylchlorohydrosilanes.

Example 9

This example illustrates the influence of the hydrogen content of the methyl chloride-hydrogen mixture on the selectivity and the rate parameters of the direct synthesis of methylchlorosilanes at atmospheric pressure.

Table 19: Analytical, Selectivity and Rate Data for Runs 8 A and 8 B

TC DM MD M T D MeSiH MD / DM MeSiH / D Rate, Wt. % Wt. % Wt. % Wt. % Wt. % Wf.% Wt. % 1.90 ± 0.84 ± % Si / hr NoCaSi ₂ _ 14:15 ± 26.64 ± 4.41 ± 6.22 ± 48.08 χ 40.79 ± 12:32 12:20 0.63 ± • 1.67 4:53 1:51 0.78 3:52 5.24 1.20 1:05 12:10 Run8A _ 20:10 24.15 3:47 10:11 42.18 44.25 0.61 Cerac CaSi ₂ 4:56 I.46 Run8B 12:51 9:55 43.54 2.69 7.30 36.41 53.09 0.73 Elkem CaSi ₂

Runs 9A-9K: Eleven experiments are summarized in this example. Each was carried out in reactor A using the amounts of silicon and copper catalyst shown in Table 20. The HCI activating method voi; Run 1A was applied. Table 23 also shows the flux rates of methyl chloride and hydrogen and reaction performance data. The average reaction temperature door during the experiments (7-8 hours) was 328 ± 3 ⁰ C. The Läufo9A-9H were carried out with activated silicon containing <23ppm tin, <2 ppm zinc, and 50 ppm nickel. The increase in hydrogen content leads to an increase in the selectivity for methylchlorohydrosilanes (MeSiH). In fact, the curve wt% MeSiH vs. Vol% was H ₂ S-shaped, with the beroich of fast MeSiH increase at 40-60 vol% H ₂ log. It follows that the reactions carried out under these conditions show an unstable reaction performance, since a small change in hydrogen content can lead to a large change in the product composition, hydrogen contents above 60% by volume give more stable selectivity values, but the relative molar conversion of the hydrogen decreases with increasing hydrogen atom. In addition, a sharp drop in reaction rate occurred at more than 50VoI. % H ₂ on. At about 50% by volume H ₂ (runs 9C and 3D) the Un conversion of the methyl chloride was about 11 mole%, that of hydrogen about 2 mole%.

The activated silicon in Runs 9I-9K contained 18ppm Ni, 15ppm Sn, and 15ppm Zn, respectively. Table 20 shows that the hydrogen content has essentially no effect on the rate of direct synthesis with this activated mass, and that the amount of M 'formed. 3thylchlorhydrosilane at 48-64Vol .-% H ₂ does not change. The Sciektivität for methylchlorohydrosilanes but was gerih & er n \ s in runs 9 A-9. The presence of undesirable amounts of tin shows a great negative influence on the formation of (CHa) ₂ SiHCl.

Table 20: Reaction Conditions and Results for Runs 9A to 9K

Example 9 9A 9B 9C 9D 9E 9F 9G 9H 9I C-4 7.44 ± 9J 9K Silicon Si-5 Si-5 Si-5 Si-5 Si-5 Si-5 Si-5 Si-5 Si-I 1013 1.22 Si-1 Si-1 300 g 300 g 300 g 300 g 300 g 300 g 300 g 300 g 246.9 g 472 21.45 ± 246.9 g 246.9 g Catalyst 25 g 24 g 25g 24 g 50 g 25 g 25g 24 g 3.1g 32 1.79 3.1g 3.1g C-1 C-1 C-2 C-I C-1 C-1 C-1 C-1 2.87 ± C-4 Γ-4 CH ₃ CI, ml / min 823 700 528 015.8 278 228 228 175 12:41 764 634 H ₂ ml / min 195 548 548 653.5 653.5 790 790 7SO 11.97 ± 708 944 Vol.% H ₂ 19 44 51 52 68 78 78 81 1.78 48 64 % DMwt. 2.34 ± 9.73 ± 16.02 ± 17.76 ± 10.22 ± 21.i.3 ± 21.33 ± 22.78 ± 55.17 ± 9.50 ± 10.71 ± 12:12 0.96 2.17 1.66 2.22 0.88 1:42 0.67 2:52 1.67 1.66 % Mdwt. 9.75 ± 18.96 ± 28.94 ± 32.48 ± 46.2? t 46.64 ± 48.28 + 46.71 ± 9f? QO + 27.54 + 27.14 ± 0.80 2:57 2.60 6:08 6.26 1:51 1.73 1:01 1:57 3.90 1.80 M wt%. 6.49 ± 6.40 ± 4.93 ± 4.31 ± 1.94 ± 2.85 ± 2.58 ± 3.36 ± 0.53 ± 2.72 ± 2.67 ± 12:29 12:23 12:48 12:59 12:30 12:08 12:12 12:20 12:05 12:09 12:22 lwt.% 13.81 ± 9.06 ± 5.64 ± 6.76 ± 4.25 ± 2.92 ± 3.04 ± 3.45 ± 2.97 ± 10.51 ± 9.29 ± 0.79 0.99 12:54 2:02 1.60 12:20 0 9 12:29 0.70 12:55 0.68 % Dwt. 67.62 ± 55.64 ± 44.16 + 38.66 ± 25.39 ± 26.00 + 24.62 ± 23.18 ± 13.1 ± 49.33 ± 50.05 ± 1:04 2:38 4:01 5:00 6:49 1.92 2.93 1.11 12:46 5.18 3.30 MeSiH wt.% 12.09 ± 28.69 ± 44.96 ± 50.24 + 68.32 ± 67.87 + 69.61 + 69.49 ± 37.04 ± 37.S4 0.85 3:53 4:49 7.11 8.23 2.3 £. 3.13 1:49 6:56 3:42 MeSiH / D 0.18 + 0.52 + , 1.02 + 1.35 ± 2.86 + 2.63 ± 2.86 + 3.01 ± 0.77 + 0.76 ± 12:02 12:09 12:10 12:42 0.77 12:34 12:46 12:20 12:21 12:12 MD / DM 17.4 ± 1.95 ± 1.62 ± 1.83 ± 2.09 ± 2.20 ± 2.27 ± 2.05 ± 2.92 ± 2.58 ± 0.3f 12:07 12:17 12:27 12:16 12:03 12:08 12:05 12:16 12:34 Rate,% Si / hr 1.08 ± 0.98 ± 0.96 ± 0.99 ± 0.47 ± 0.43 ± 0.48 + 0.34 + 1.26 ± 1.29 ± 12:01 12:09 12:06 12:59 12:08 12:06 12:01 12:03 12:13 12:26

Example 10

This example illustrates that the unstable reaction course in the production of methyl-hydrosilanesilanes (MeSiH), which can occur when 40-60 v / v H _{2 are used} at atmospheric pressure (0 psig), is avoided by carrying out the reaction at higher pressure can be.

Steps 10A-10F: Six experiments, all performed in reactor B, are summarized in this example. Di experiments yeasts with activated silicon containing <2ppm tin, <15ppm zinc and at least 80ppm Ni in a catalytic

containing active form. The HCI activation procedure was that described in Run 2D. The flow rates of methyl chloride and hydrogen are shown in Table 21, along with the numerical results of the experiments. The average reaction temperature of the barrels 1OA, 10B and 10C was 325 ± 3 ° C and that of the legs 10D, 10E and 10F 329 ± 2 ⁰ C. The pressure was maintained at 31 psig ± 1.

The data of Table 21 show that higher reaction rates were realized at 30 psig compared to Opsig (Runs A-9H) and that reproducible results could be obtained with 50-72 vol% H ₂ at overpressure. The decrease in speed with increasing hydrogen content in the feed gas is less dramatic at 30-60 psig than at atmospheric pressure. In Run 10B (62 vol% H ₂ ), the methyl chloride conversion was 28 mol% and the hydrogen conversion was 2.8 mol%. These values increased at lower hydrogen partial pressure so that at 50% by volume H ₂ (Run 10D) their values were -33 mol% and 4.5 mol%.

Consequently, more efficient utilization of silicon, methyl chloride and hydrogen occurs at pressures above 1 atmosphere absolute (Opsig).

Table 21: Reaction Conditions and Results for Runs 10A to 10F

run

10A

10B

10D

10E

Silicone g Si-4 Si-4 Si-4 Si-4 Si-4 Si-4 815 815 815 900 900 900 Catalyst g C-1 C-1 C-1 C-6 C-6 C-6 40.8 40.8 40.8 45.0 45.0 45.0 CHiCI, lit / min 1:40 1:08 0.81 1:40 1:08 0.81 H ₂ , lit./min 1:40 1.76 2:03 1:40 1.76 2:03 Duration, hr. 7 · 7 8th 13 6 8th Vol .-% H ₂ 50 62 71.5 50 62 71.5 % TCwt. 2.54 ± 2.63 ± 2.88 ± 2.31 ± 18.3 ± 2.64 ± 12:36 12:37 12:08 12:47 0.3b 12:13 % DMwt. 16.93 ± 19.34 ± 19.99 ± 13.99 ± 16.89 ± 17.54 ± 1:33 1:33 12:47 1.25 0.78 12:24 % Mdwt. 32.03 ± 40.20 ± 40.68 ± 30.88 ± 41.38 ± 44.15 ± 1.72 1.25 0.61 1:41 1:09 12:16 M wt%. 2.34 ± 3.22 ± 2.44 ± 3.73 ± 2.66 ± 1.95 ± 12:37 12:56 12:18 0.89 12:13 12:12 Twt%. 11:43 ± 10.51 ± 11.60 ± 11.5 ± 11.76 ± 10.4 ± 0.72 0.78 12:33 0.85 0.87 12:13 % Dwt. 34.73 ± 24.10 ± 22.41 ± 38.04 ± 24.13 ± 23.88 + 2.78 1.75 0.73 1:39 12:48 12:24 MeSiH wt.% 48.96 ± 59.54 ± 60.67 ± 44.87 ± 58.27 ± 61.69 + 2.82 1.80 0.66 1:47 1.85 12:32 MeSiH / D 1.42 + 2.48 ± 2.71 ± 18.1 ± 2.42 ± 2.60 ± 12:20 12:24 12:11 12:07 12:12 12:04 MD / DM 1.90 ± 2.09 ± 2.04 ± 2.23 ± 2.45 ± 2.54 ± 12:12 12:16 12:06 12:29 12:05 12:02 Rate,% Si / hr 2.72 ± 14.2 ± 1.66 ± 2.63 ± 18.2 ± 1.78 ± 12:10 12:06 12:08 12:34 12:06 12:06

Example 11

This example illustrates the direct synthesis of methylchlorohydrosilanes (MeSiH) containing CH ₃ SiH ₂ Cl (DH). Steps 11A-11G: All seven experiments of this example were performed in reactor B at gas flow rates that were insufficient to fluidize the denoted silica particles. For each experiment (11A-11G), the activated mass was prepared in an oven at 98O ⁰ C from the amounts of silicon and copper catalyst shown in Table 22. Immediately before the reaction with methyl chloride and hydrogen, however, the mass was etched with HCI at 300 ° C in Reactor B. The chlorosilanes formed were collected separately from the methyl chlorohydrosilane product (MeSiH) and weighed. Table 22 shows the flow rates of methyl chloride and hydrogen, reaction temperature and pressure, the duration and composition of the reaction products of each experiment.

For comparison, CH ₃ SiH ₂ Cl (DH) was prepared by disproportionation of CH ₃ SiHCl ₂ (MD) with hexamethylphosphoramide (HMPA) as described by Dunogues et al. (U.S. Patent 3,445,200, issued May 20, 1969 to Dunogues et al.), And the product was characterized by GC, GC / MS, and ²⁹ Si NMR. GC / MS shows a peak like m / e 80, a base poak at m / e 79 '(loss of H) and the following additional fragments: m / e 78 (loss of two Η-atoms), m / e 65 (loss of CH ₃ ) and m / e 45 (loss of Cl). The ^w Si NMR resonance was observed at -10.80 ppm (relative to tetramethylsilane).

Table 22: Reaction Conditions and Results for Runs 11A to 11G

11A

11C

11D

11E

11F

11G

Silicone, g Si-I Si-I Si-5 Si-I Si-5 Si-5 Si-5 921.5 783.6 1382 887.3 1425 1425 1425 Catalyst, g C-1 C-1 C-1 C-1 C-1 C-2 C-2 48.5 41.2 73 46.7 75 75 75 Temp ⁰ C 311 ± 4 307 ± 1 307 ± 1 206 ± 1 329 ± 4 335 ± 4 346 ± 3 Pressure, psig 0 20 30 40 40 50 50 CH ₃ Cl, 'lit / min 12:42 12:42 0.73 12:59 0.71 1:00 1:00 Hj, lit / min 12:47 12:39 1:08 0.92 1:33 1:08 1:08 Duration, hr. 8th 8th 8th 8th 8th 4 4 Vol.% H ₂ 51 49 60 61 65 51 51 % DHwt. * 5.94 • 5.17 0.79 ft # % TCwt. _ 1:35 3:34 2.67 1.19 12:24 12:35 % DMwt. 12:31 3.Q2 14.82 12:54 3:06 10.88 1.85 MDV / t.% 32.00 43.93 50.50 42.22 33.49 36.97 32.69 % MWt. 4:01 2.19 1:59 1.26 1:39 3.29 2.97 Twt%. 6:50 8.10 12.42. 11:56 15.68 9.30 10:19 % Dwt. 57.18 34.76 17.33 ' 36.58 44.40 39.32 51.95 MeSiH wt.% 32.31 53.69 65.32 47.93 37.34 47.85 34.54 MeSiH / D 12:57 1:55 3.77 1.31 0.84 1.22 0.67 MD / DM 103 11:50 3:41 78 10.74 3:40 17.67 Rate,% Si / hr 12:33 12:47 1.96 12:38 2:33 0.95 1:36

* DH incompletely resolved from methyl chlorides In GC. Pressed by capillary GC / MS and GC / FTIR.

The data show derTabelle 22 that CH ₃ SiHaCI (DH) was observed in the reaction products obtained psig and 300 to 350 ⁰ C in a fixed bed reactor at 0-50. In Runs 10A, 10C, 10F and 10G, the presence of CH ₃ SiH ₂ Cl (DH) was determined by capillary GC / MS and observation of an incompletely resolved shoulder on the falling edge of the methyl chloride peak in the packed column GC. There is insufficient separation of the CH ₃ SiH ₂ Cl (DH) from CH ₃ Cl in these examples, which allows no quantitative analysis by packed column GC. GC / FTIR was also used to demonstrate that the components, which were eluted with methylene chloride in the packed column GC, Si-H oscillation at about 2200 cm ^"1, 960cm" ^1, 910cm ^"1, 680 cm " ¹ and 510cm" ¹ have.

Example 12

This example illustrates the potentiating influence of methylchlorosilanes (M, T, D) on the rate of direct methylchlorohydrosilane (MeSiH) synthesis. The experiment of this example lasted a total of 51 hours, spread over a period of new days, during which the amounts of (CH ₃ I ₂ SiCl (D), CH ₃ SiCl ₃ (T) and (CH ₃ I ₃ SiCl (M) and their mixtures were injected directly into the fluidized bed of the activated silicon particles.

A mixture of 25Og of silicon Si-6 and 12.5 g of catalyst C-6 was sent to the reactor A. During the course of the experiment, no further amounts of silicon or catalyst were added. The mixture was heated to 350 ° C under argon (1 liter / min) fluidization. Meanwhile, a syringe with (CH ₃ I ₂ SiCI ₂ (D) mounted on an injection pump was attached to the reactor inlet tube using a non-corrosive, stainless steel Luerlok * fitting tube, which was located about 4 inches from the supporting frit on the reactor inlet tube This point is also downstream of the methyl chloride and hydrogen feeds to ensure maximum transport of the methylchlorosilane vapor into the fluidized bed The reactor inlet tube was electrically heated and completely enveloped with insulating material to ensure rapid and complete vaporization of the methylchlorosilane When the reactor temperature reached 35O ⁰ C and the initiation temperature was 110 ° C, argon was replaced by hydrogen (1 liter / min), and the injection of the (CH ₃ I ₂ SiCI ₂ (D)) thermocouple in the line records the steam temperature. The following hour, a total of 13.5 gm (CH ₃ I ₂ SiCl ₂ (D) was pumped through the pump iefert. The leaving the reactor (CH ₃ ) ₂ SiCl ₂ - (D) vapor was cooled with dry ice / isopropanol as a coolant. However, it was visually observed that some (CH ₃ I ₂ SiCl ₂ (D) escaped from the condenser, along with the hydrogen.) The direct synthesis of the methylchlorohydrosilanes (MeSiH) began after the reactor temperature had dropped to 33O ⁰ C and the gas flow was changed to 615 ml / min CH ₃ Cl and 500 ml / min H _2. (CH ₃ I ₂ SiCl ₂ (D) condensed during the activation step as described above was included in the first of the hourly samples samples were collected hourly (except the hours 23 and 24) and analyzed after evaporation of the excess methyl chloride. the temperature of the bed was maintained at 330-332 ⁰ C throughout the experiment.

The amounts injected during the experiment (CH ₃ I ₂ SiCl ₂ (D), CH ₃ SiCl ₃ (T) and (CH ₃ I ₂ SiCl (M) and the duration of the addition are listed in Table 23. When mixtures were used ( 15th-18th, 23rd-24th, 29th-32nd, 35th, 40th, 43rd), the table also adds the composition of the mixture 18-hour injected mixture 86.4 wt% (CH ₃ I ₂ SiCl ₂ (D) and 13.6 wt% CH ₃ SiCl ₃ (T) Table 23 also shows the absolute gravimetric amounts of the hourly components Samples calculated from quantitative GC analysis In the table, the sample weight refers to the total amount of methylchlorosilanes (M, T, D), methylchlorohydrosilanes (MeSiH), trichloroisilanes (TC) and unvaporized methyl chloride recovered during each sample period has been.

Table 24 shows the percent composition and the performance parameters of the hourly samples. The product weight is the weight of the methylchlorosilanes (M, T, D), methylchlorohydrosilanes (MeSiH) and trichlorosilanes (TC) actually formed during the direct synthesis. It was calculated by subtracting the weight of methyl chloride and

Weight of each injected compound from the sample weight. When calculating the values in Table 24, it was considered that the following relationship exists between the compounds in the sample:

amount recovered = amount injected + amount formed in the reactor - (amount absorbed in bed + in bed)

converted amount + loss amount by evaporation)

Losses due to adsorption, reaction and evaporation also occurred when no injections were made. GC and GC / MS analyzes of the methylchlorosilanes recovered from the injections in separate control experiments showed no conclusive evidence of chemical conversion of the injected methylchlorosilane. Accordingly, it was assumed in the calculations that the losses were approximately constant and negligible. The difference between the recovered material and the added material is what was formed in the direct synthesis. When the weight of a particular compound recovered in a sample was less than the amount injected, the deficit was transferred and subtracted from the subsequent sample until the net yield was realized. The empty entries in Table 24 for D, M, and T stand for those cases where deficiencies existed.

The data presented in Tables 23 and 24 show that during the addition of methylc'ilosilane (hours 5-8, 15-18, 23-24, 30-33, 36, 41, 44) the formation of the compound ( en) was suppressed and the overall rate of silicon conversion decreased. There was also an increase in the percentage of Mothylchlorhydrosilane (DM, MD, MeSiH) in the product, but the absolute amount of these compounds formed decreased. During hours 30-33, D + T injection was limited to the first 30 minutes of each hour. In that case, the decrease in hourly speed during the addition was not noticeable, and there was net formation of all products. The maximum rate of addition was 0.1-0 15g / min during the whole experiment.

Mixtures of D and T (hours 15-18, 23-24, 30-33) or M and T (hours 36, 41, 44) gave an increase in velocity after injection which was 2-5 times the pre-injection value. The high rates (up to 3.07% Si conversion per hour at 35 hours) obtained in this experiment at 0 psig by the direct synthesis of this invention for the production of methylchlorohydrosilanes (MeSiH) were unprecedented to those skilled in the art. Table 23 shows that the increased product formation is due not only to the compound (s) just injected, but to all. Methylchlorosilanes and methylchlorohydrosilanes (MeSiH). Note, however, that the percentage of (CH ₃ J ₂ SiHCl (DM) and CH ₃ SiHCl ₂ (MD) decreases after the addition (Table 24) Accordingly, the MD / DM ratio can be less than 1. The data also shows that that the ratio MD / DM can be controlled by the choice of methylchlorosilanes injected into the reactor The ratio was generally following the addition of D or M + T> 2 but <2 after the addition of D + T.

Example 13

This example illustrates the advantages of injecting (CH ₃ I ₃ SiCl (M) and / or CH ₃ SiCl ₃ (T) at rates> 0.1 g / min into the fluidized bed in the direct synthesis of methylchlorohydrosilanes (MeSiH) of this invention Silicon conversion rates of> 1% per hour and MeSiH / D ratios> 1 were obtained simultaneously.

Except as described below, the two separate runs of this example were carried out in Reactor A as described in Example 12. The range of injection rates for methylchlorosilane was 13A0.2-O, 3g / min.

The reaction temperature was 331 ± 2 ⁰ C. In the course of 13 B was the addition rate of about 2 gm / min, and the reaction temperature was maintained at 355 ± 2 ° C.

Table 23: Gravimetry Contents of Additives and Samples in Example 12

Time additives Additive Wt. Duration Sample Wt. CH ₃ CI TE DM MD M T D (Mr) D G minute G G G G G G G G 1 13.5 60 9.15 1796 0122 0973 2520 0238 0448 8994 2 6.24 0858 0070 0939 1576 0273 0365 2159 3 6.67 0870 - 0929 1930 0311 0412 2218 4 D 6.66 0511 0039 0905 1626 0390 0525 2665 5 7:50 60 8.26 1324 - 0518 1322 0090 0208 4798 6 7:58 60 9.11 1857 - 0670 1553 0145 0260 6607 7 7.61 60 10:10 0297 - 0591 1370 0203 0376 7265 8th 7.62 60 12:58 1478 - 0823 1751 0281 0499 7747 9 8.75 1021 - 0823 1712 0309 0562 4324 10 7:04 0608 - 0815 1689 0327 0601 3000 11 7.81 0865 - 0924 1874 0354 0645 3149 12 4.90 - _ 9346 0723 0267 0542 3022 13 3:47 0739 _ 0519 0900 0108 0308 0896 14 86.4% D 4:54 0596 - 0592 1400 0117 0359 1530 15 13.6% T 8.17 60 11.68 1405 - 0757 1576 0223 1071 6648 16 8:02 60 13:41 1855 _ 0945 1781 0304 1193 7331 17 7.16 60 12:51 1749 0940 1725 0318 1136 6643 18 7.77 60 15:33 2396 0120 1099 1222 0414 1473 8606 19 14:10 2139 - 1287 2188 0422 1260 6805 20 18.71 1218 - 1639 2735 0748 1976 10393 21 6:50 0977 _ 0814 1398 0231 0621 2458 22 75.0% D 9.86 1030 _ 1130 1961 0338 0928 3474 23-24 25.0% T 16.78 120 32.12 3777 - 2586 4195 0758 4143 16661

Time additives Additive Wt. 4.63 Duration Sample Wt. CH ₃ CI TC DM MD M T D 6805 (Mr) 9 minute G g g G G G G G 7480 25 1.94 14:47 1810 1538 2146 0433 1738 13014 26 0.84 2.16 1350 1892 2884 0540 1874 2030 27 4.62 25.23 1491 2632 3999 0923 3171 3925 28 6:01 0608 8871 1721 0180 0600 5566 29 83.2% D 9.64 1320 1149 2146 0246 0854 30 16.8% T 3.72 30 5.12 1634 1262 2056 0287 1245 6:44 - 7442 31 · 30 14:24 1972 1584 2500 0356 1424 9077 32 30 16:54 2316 1862 2860 0422 1637 7220 33 30 20:18 2763 2177 3370 0462 2331 13254 34 16:17 1413 2069 3147 0411 1910 1371 35 83.5% M 4.84 27.25 1760 3087 5180 0755 3214 36 16.5% T 60 8.72 1315 0987 2339 1766 0942 4098 4260 37 11.61 1.498 - 1325 3116 0526 1047 4712 38 6:37 10:50 0772 1392 2762 0207 1107 3509 39 13.10. 1652 1715 3402 0238 1381 3165 40 83.5% M 10.83 ' 1048 1784 3148 0193 1148 41 16.5% T 60 5.13 1650 1917 3646 1341 1331 4036 8375 42 15:56 2163 2155 4254 1276 1676 0718 43 76.2% 21:53 1182 2513 5604 0883 2973 44 23.8% M 60 8.12 1000 1047 2990 0592 1773 1638 2010 45 10:44 1265 1350 3745 0510 1932 1984 46 10.25 1168 1533 3797 0261 1481 2932 47 10:13 1287 1616 3829 0179 1235 2523 48 12:19 1716 1885 4290 0145 1252 2109 49 11:43 1275 1772 4435 0136 1290 5444 50 11.89 2197 1877 5378 0105 1124 51 18.87 0909 2125 7501 0181 2170

Table 24: Hourly Product Composition of Example 12

Time additives Product Wt. TC DM MD M T D MeSiH MeSiH / D MD / DM Rate, (Mr) D gms Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 2:59 % Si / hr 1 4.30 2.84 22.62 58.59 5:53 10:42 81.21 1.17 1.68 12:43 2 5:38 1.30 17:44 29.29 5:08 6.77 40.12 46.73 1.24 2:08 12:52 3 5.80 - 1.16 33.28 5:04 6.73 39.80 49.29 0.95 1.80 12:57 4 D 6.15 0.63 14.71 26.45 6:35 8:54 43.32 41.16 2:55 12:55 CJL D 2.14 - 24.23 61.83 4.21 9.73 86.06 2:32 12:22 6 D 2.63 _ 25.50 59.09 5:52 9.89 84.59 2:32 12:27 7 D 2:54 - 23:27 53.94 7.99 14.80 77.21 20:26 2.13 12:26 8th 3:48 - 23.64 50.30 8:07 1Ί.34 3.65 73.94 8:34 2:08 12:36 9 3.71 _ 22:18 46.15 8:33 16:15 8.19 68.33 0.83 2:07 12:38 10 6:43 - 12.66 26.26 5:08 9:35 46.66 38.92 0.89 2:03 0.62 11 6.95 _ 13:30 26.98 5:09 9.29 45.34 40.28 12:35 2:09 0.68 12 4.90 - 7:06 14.75 5:44 7.11 61.68 21.81 1:58 1.73 12:47 13 2.73 _ 19:00 32.95 3.95 11:29 32.81 51.95 1.30 2:37 12:28 14 86.4% D 3.94 - 1.15 35.50 2.96 7.75 38.78 50.51 2:08 12:40 15 13.6% T 2:56 - 29.62 61.66 8.72 91.28 12:28 86.4% D 1.89 16 13.6% T 3.10 _ 30.51 57.51 9.82 2.16 88.02 12:34 86.4% D 5.87 1.83 17 13.6% T 3.60 - 26.10 47.89 8.83 4:58 12.60 73.99 12:39 86.4% D 1.24 1.11 18 13.6% T 5.15 2:33 21:34 23.73 8:04 8.14 36.43 45.07 12:53 12:51 1.70 19 11.96 - 10.76 18:30 3:52 10:54 56.89 29.06 12:42 1.67 1.18 20 17:49 _ 9:37 15.64 4.28 11:30 59.42 25.01 0.90 1.72 1.74 21 5:52 - 14.75 25.32 4.18 11:24 44.50 40.07 0.89 1.74 12:58 22 75.0% D 7.83 - 14:43 25.04 4:32 11.85 44.36 39.47 1.66 1.62 0.82 23-24 25.0% T 11.62 _ 22:15 36.11 6:52 35.12 58.36 0.65 12:54 1:40 25 12.66 - 12:15 16.95 3:42 13.73 53.75 29.10 0.64 1:52 1:32 26 14.67 _ 12.90 19.66 3.68 12.77 50.99 32.56 12:51 • 1:52 1:57 27 23.74 9.11 16.85 3.89 13:36 54.82 27.94 2:55

additives Product Wt. TC DM MD M T D MeSiH MeSiH / D 27- 280 152 0.62 Time gms Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 1.28 Rate, 0.64 (Mr) 5:40 _ 16:12 31.86 3:33 11:11 37.58 47.98 0.84 MD / DM% Si / hr 0.69 28 83.2% D 8:32 - 13.81 25.79 2.96 10:26 47.18 39.60 1.94 1.98 29 16.8% T 5.79 _ 21.81 35.53 4.96 8:07 29.62 47.34 1.87 1.20 30 83.2% D 0.85 1.63 16.8% T 10:33 _ 15:33 24.21 3:45 10.63 46.38 39.54 1:55 31 , 83.2% D 0.70 1:58 16.8% T 13:38 - 13.91 21:37 3.15 11:18 50.39 35.28 1:53 32 83.2% D 1:06 1:54 16.8% T 12.80 - 1.17 26.33 3.62 12:14 40.90 43.34 1.70 33 0.72 1:55 3:07 14.76 - 2.14 21:32 2.79 12.94 48.93 35.34 0.62 0.66 34 83.5% M 25.49 _ 12:11 20:32 2.96 12.61 52.00 32.43 2:43 1:52 35 16.5% T 5:03 - 19.64 46.55 6:53 27.28 66.19 1.68 1.22 36 1:03 2:37 1.23 9:59 - 13.82 32.51 10.92 42.75 46.33 0.98 1:46 37 9:52 • _ 14.62 29.01 11.63 44.74 43.63 1:09 2:35 1.29 38 11:21 _ 15:30 30.35 12:32 42.03 45.65 1:41 1.98 1.29 39 83.5% M 9:59 _ 18.60 32.83 11.97 36.59 51.43 1.76 1.98 40 16.5% T 9.26 - 20.70 39.37 5.75 34.18 60.07 1.77 1.67 41 1:59 1.90 2.66 12:12 - 17.78 35.10 13.82 33.30 52.88 0.97 0.73 42 76.2% T 19:47 _ 12.91 28.79 15:27 43.03 41.70 5.62 1.97 43 23.8% M 4.76 _ 2.22 62.88 15:10 84.90 2.23 1:02 44 3.11 2.86 1.16 6.73 - 5.20 55.62 24.23 75.67 2.65 1.30 45 7.67 - 19.97 49.49 4:34 26.20 69.46 2.75 2.77 1:59 46 8.69 _ 18.60 44.07 12:29 14:21 22.83 62.67 2.10 2:48 1:57 47 10:47 - 17.71 40.96 1:38 11.95 27.99 58.67 2:46 2:37 1.68 48 10:16 _ 17:45 43.67 1:33 12.70 24.85 61.12 3:44 2.31 2.80 49 10:59 - 17.72 50.77 0.99 10.61 19.91 68.49 1.77 2:50 50 17.96 11.83 41.76 1:01 9.15 30.31 53.59 2.87 51 3:53

Run 13A: 250g of silicon Si-6 and 12.83g of catalyst C-6 were added to the reactor and heated to 350 ° C under argon (1 liter / min) fluidization, CH ₃ Cl (615 mL / min) and H ₂ 508 mL / min) then took the place of argon. Simultaneously by the injection pump CH ₃ SiCIa (T) and supplied in the reactor inlet tube, kept at 100 ⁰ C, evaporated. In total, 15.3 g of CH ₃ SiCl ₃ (T) were injected at an average rate of 0.26 g per minute over the next hour. Within about 30 minutes, the temperature during the injection rose to 370 ° C. After the first hourly sample was removed from the condenser, the reactor temperature was lowered to 330 ⁰ C. This temperature was maintained (within 2 ⁰ C) during the remaining 32 hours of the experiment.

Table 25 shows the amounts of CH ₃ SiCl ₃ (T) and (CH ₃ I ₃ SiCl (M) injected at the other times during the experiment and the duration of the additions.

The absolute weights of each compound present in the samples are also described in Table 25. The percent composition and performance parameters for the hourly product mixtures are summarized in Table 26. Run 13B: 250g of silicon Si-6 and 12.8g of catalyst C-6 were heated to 350 ° C in reactor A with argon as described in Example 12. The bed was fluidized for 48 hours at 35O ⁰ C before the reaction starts. CH ₃ Cl (615 ml / min), H ₂ (508 ml / min) and CH ₃ SiCl ₃ (T) were all injected simultaneously. 19,90g CH ₃ SiCl ₃ (T) was pumped into the heated reactor inlet (128 ⁰ C) during the 10 minute long injection period. The absence of visible liquid in the inlet tube during and immediately after injection confirms the rapid evaporation and rapid transport of the CH ₃ SiCl ₃ (T). The reactor temperature was initially 353 ^° C. No exothermic reaction was observed in this experiment. A second injection of CH ₃ SiCl ₃ (T), 20.21 g in 10 minutes took place during the second hour. Tables 27 and 28 show the data for the ten hours of this experiment.

The data of Tables 25-28 show that direct synthesis rates of> 1% Si conversion per hour and favorable selectivities (MeSiH> 50% by weight, MeSiH / D> 1) were achieved when the injections of the methylchlorosilanes were within 30 Minutes were completed, preferably within 20 minutes. Taken together with the results of Example 12, these data also show that it is advantageous for the overall reaction to use (CH ₃ I ₃ SiCl (M) and / or CH ₃ SiCl ₃ (T) as additives.) In mixtures, the (CH ₃ I ₃ SiCl (M) content should be lower than 0.001% by weight, but preferably 10-30% by weight In addition, when CH ₃ SiCl ₃ (T) is used, it is advantageous for the formation of higher-grade products, repeat the addition at more frequent intervals (1-10 h in laboratory work) to suppress the formation of CH ₃ SiCl ₃ (T), an economically less valuable product, to less than 10% by weight, in this example High rates are desirable for work on a commercial scale In fact, rates of addition corresponding to gas flows up to a level where the silicon is completely consumed in the reactor, are both high and low rates of addition of methylchlorosilane. vort However, it is preferred to use rates of addition that are considerably lower. Based on the flow rate of the methylstyrene and the weight of the silicon used in the experiments of this example, it can be calculated that during the injection period the amount of methylchlorosilanes (M, T, D) added is 0.2-2.0 times that Methyl chloride weight or should be 0.001-0.1 times the silicon weight in the reactor.

Table 25: Gravimetric Contents of Additives and Samples in Run 13A

Time (hr) additives Additive Wt. G Duration min. Sample Wt. G CH ₃ CI g TC g DM g MD g M g T g D g Time (hr) additives Additive Wt. G Duration min. Sample Wt. G CH ₃ CI g TC g DM g MD g M g T g D g

1 T 15.3 60 25.71 3186 - 2039 5137 0591 10551 4206 2 9.13 1173 - 0801 2320 0255 2126 2450 3 3.29 0457 0014 0288 1256 0084 0271 0920 4 3:39 0589 _ 0296 1165 0082 0247 1011 5 4.61 0612 - 0420 1376 0136 0282 1784 6 T 7:46 JO 11:56 0191 _ 0611 1670 0270 5759 2059 7 8.91 0687 - 0710 2045 0368 1019 4081 8th 1.63 0100 _ 0173 0472 0050 0165 0671 9 T 7.60 30 8.92 0940 - 0599 1323 0094 4409 1555 10 7.72 0931 - 1132 2057 0186 0831 2583 11 11:12 1343 - 1735 2876 0260 0851 4055 12 52.61% T 5.17 21 15.90 , 1918 - 1868 3196 1773 2323 4822 47.39% T 13 4.83 18 16:23 1833 - 2011 3387 1712 2355 4932 14 5:04 16 9.19 2212 - 2463 4435 1842 2591 5547 15 5.15 14 24.31 2232 _ 3170 5781 2074 3544 7509 16 M 4:34 14 5.81 0561 0034 0494 1097 2129 0451 1044 17 8.78 0750 - 1449 2549 0355 0930 2748 18 13:11 1437 - 2239 4394 0306 1150 3884 19 14.72 1615 - 2703 4949 0274 1526 3653 20 18:43 1749 - 2828 5658 0256 1732 6207 21 20:30 1886 - 3043 8388 0229 1870 4884 22 19:36 1829 - 2883 6393 0211 1990 6054 23 34.23 0969 0257 3666 9608 0599 6819 12312 24 M 11.85 14 21.74 3200 - 1120 3035 8070 4259 2056 25 13:10 1561 - 2231 3828 0529 1499 3452 26 18.5 2520 - 3005 5115 0316 1942 5152 27 5.21 2747 _ 3324 5772 0358 2551 6298 28 20.77 2316 - 2951 5346 0289 2414 7454 29 20:17 2199 _ 3041 5577 0309 2707 6,337 30 20.99 2506 - 2800 5472 0254 2517 7441 31 20.83 2568 - 2954 5993 0265 2891 6159 32 19.95 2541 - 2576 5766 0206 2569 6292 33 22.74 2496 2952 7093 0246 3490 6463

Table 26: Hourly Product Composition in Run 13A

Time additives Product Wt. TC DM MD M T D MeSiH MeSiH / D MD / DM Rate, (Mr) T gms Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 1.71 2:52 % Si / hr 1 11.97 3.17 42.90 4.94 35.13 59.93 1.27 2.90 1.17 2 5.83 13.74 39.79 4:37 42.10 53.53 1.68 4:36 12:57 3 2.56 0.55 11:24 49.02 3.28 35.91 60.26 1:44 3.94 12:25 4 2:55 11:59 45.61 3.21 39.59 57.20 1:01 3.28 12:25 5 T 3.72 11:30 37.03 3.66 48.01 48.33 1.11 2.73 12:36 6 4.61 13:25 36.23 5.86 44.66 49.48 0.68 2.88 12:45 7 7.20 9.86 28.39 5.10 56.65 38.25 0.96 2.73 0.70 8th 1:53 11:31 30.84 3.26 10.76 43.83 42.15 1.24 2.21 12:15 9 3:57 16.77 37.05 2.63 43.55 53.82 1.23 1.82 12:36 10 5.96 19:00 34.53 3.12 43.35 53.53 1.14 1.66 0.60 11 52.61% T 8.93 19:44 32.22 2.91 45.43 51.66 1:05 1.71 0.91 12 47.39% M 9.89 18.90 32.33 48.77 51.23 1:01 52.61% T 1.10 1.68 13 47.39% M 10:33 19:47 32.79 47.74 52.26 1:07 52.61% T 1.24 1.80 14 47.39% M 12:45 19.79 35.64 44.57 55.43 1.31 52.61% T 1.19 1.82 15 47.39% M 16.65 4.19 34.72 1.14 45.10 53.76 1.76 M 1.5 ' 2.22 16 12.3. 1:09 15.83 35.16 14:46 33.46 50.99 1.4.3 1.76 0.68 17 7.68 18.88 33.21 12:11 35.80 52.09 1.85 1.96 0.82 18 11:37 19.70 38.65 10:12 31.53 58.35 1.23

Product Wt. TC DM MD M T D MeSiH -29- .83 288 152 Time gms Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 2:00 Rate, (hr) additives 12.83 7.21 38.57 11.89 28.47 59.64 MeSiH / D MD / DM 2.76 % Si / hr 19 16:43 17:22 34.45 10:54 37.79 51.67 2.10 2.22 1:41 20 18:19 16.73 46.13 10:28 26.86 62.86 1.34: 2.62 1.81 21 17:32 16.65 36.91 11:49 34.95 53.56 2.34: 2.71 2:06 22 32.68 0.79 11:22 29.40 0.06 20.86 37.67 40.62 1.53 I 1.72 1.98 23 10:47 10.70 28.99 40.68 19.63 39.69 1.08: .70 3.67 24 m 1.11 20:26 34.77 13.62 31.35 55.03 2.02: .74 1.19 25 15:21 19.75 33.62 12.77 33.86 53.37 1.76 .81 1:36 26 17.95 18:52 32.17 14:21 35.10 50.69 1:58 1.83 1.90 27 18:17 16:25 29.43 13:29 41.03 45.68 1:44 1.95 2.27 28 17.66 17:22 31.58 15:32 35.88 48.80 1.11 2:03 2:33 29 18:23 15:36 30.02 13.80 40.82 45.38 1:36 2.24 2:32 30 18:00 16:42 33.30 6.16 34.22 49.72 1.11 2:40 2:44 31 17:21 14.97 33.52 14.93 36.58 48.49 1:45 2:48 32 8:00 pm 14.76 35.47 17:45 32.32 50.23 1:33 2:42 33 1:55 2.88

Table 27: Gravimetric Contents of Additives and Samplos in Run 138

Time additives Additive Wt. Duration additives Product Wt. DM 138 Sample Wt. CH ₃ CI DM MD M T D (Mr) T G minute T gms Wt. % MD G G G G G G G 1 T 19.90 10 T 0.70 21:35 Wt. % 28.99 3888 1858 3543 0151 16400 3151 2 20:21 10 15.80 23:14 40.71 42.46 5726 3656 6980 0361 20937 4800 3 6.21 19:46 44.19 27.45 3947 4098 9635 0.38 / 2446 6937 4 23.91 17.76 45.76 28.92 4685 4246 8855 0480 2655 7999 5 5.25 17:16 37.04 29.66 4614 4298 9628 0436 2652 8032 6 27.51 5.15 38.44 30.60 3088 4140 10468 0413 2919 9572 7 26.15 9.95 38.05 29.43 3281 2602 7072 0506 3552 12417 8th 26.31 14.64 29.45 29.79 3477 3852 10212 0363 2675 9211 9 27.15 13.80 38.81 30.61 3465 3747 11669 0245 2482 9002 10 30.37 13:25 42.99 33.62 3258 4024 11797 0323 3103 11115 Table 28: Hourly Product Composition in Run 38.85 Time M T D MeSiH Rate, (Mr) Wt. % Wt. % Wt. % Wt. % MeSiH / D MD / DM % Si / hr 1 1.74 36.20 62.06 1.71 1.91 0.93 2 2.29 30.38 67.33 2.22 1.91 1.72 3 1.84 32.94 65.22 1.98 2:35 2.31 4 2:01 9.74 33.45 54.80 1.64 2:09 2.61 5 1.74 10:59 32.07 55.67 1:53 2.24 2.80 6 1:50 10.61 34.79 53.10 0.83 2:53 3.15 7 1.94 13:58 47.48 39.40 1:53 2.96 3:03 8th 1:38 10:17 35.00 53.45 1.71 2.65 3.20 9 0.90 9.14 33.16 56.79 1:42 3.12 3:42 10 1:06 10:22 36.62 52.10 2.85 2.93 3.93

Example 14

This example illustrates that the vigorous action of the methylchlorosilanes as auxiliaries is realized with methyl chloride-hydrogen mixtures and not with methyl chloride alone.

The experiment of this example was carried out with 250 g of silicon Si-6 and 13.5 g of catalyst C-6, in a manner similar to that described in Example 12. During the first 19 hours, the direct synthesis proceeded with methylene chloride (1 liter / min) and intermittierten injections of (CHj) ₃ SiCl (M) (1, 8, 10.Stunde) and (CH ₃ I ₂ SiCl ₂ (D) During the next 26 hours, hydrogen (508 ml / min) and methyl chloride (615 ml / min) were used along with injections of (CH ₃ J ₂ SiCl ₂ (D) (21st, 26th hour) and CH ₃ SiCl ₃ (T) (36th, 43rd hour) The last four hours were again carried out with methyl chloride (1 liter / min) alone The amounts of injected methylchlorosilanes and the duration of injections are shown in Table 29.

Tables 29-30 show that with methyl chloride alone (1 to 19 hours), the direct synthesis of methylchlorosilanes and methylchlorohydrosilanes (MeSiH) proceeded very slowly (rates <0.5% per hour) despite the addition of (CH ₃ J ₃ SiCl (M) and (CH ₃ I ₂ SiCl ₂ (D) to the reactor at pulse rates of 1-1,5g / min. the introduction of 45 vol .-% H _2/55 vol .-% CH ₃ CI and the injection (CH ₃ J ₂ SiCl ₂ (D) (1.44g / min) in the 20th hour resulted in increased formation of all products, and this improved performance was confirmed by further additions of (CH ₃ I ₂ SiCl ₂ (D) ( 25. hour) and CH ₃ SiCl ₃ (33rd, 41st hour) as long as the mixture of methyl chloride and hydrogen was used (up to the 45th hour) .The re-introduction of methyl chloride alone (46.-49 ) at 1.0 liter / min caused a return to low speeds as observed during the first 19 hours.

In this example, direct synthesis was carried out with methyl chloride alone without zinc and tin promoters which favor high selectivities for and high formation rates of (CH ₃ I ₂ SiCl ₂ (D)

2, that these promoters do not favor methylchlorohydrosilanes (MeSiH). Experience has shown that in the direct synthesis with methyl chloride, the reaction rate is directly proportional to the partial pressure of methyl chloride (DeCooker, Ph.D Diss., Loc cit, p64-73, Sadowski et al., Z. Anorg. Chem., Vol. 443, p. 189 [1978]; Gorbunow et al., Russ. Chem. Rev., Vol. 45, p.291 [1974]). The observation of a higher reaction rate at lower methyl chloride partial pressure, as illustrated in this example of the direct synthesis of methyl chlorohydrosian (MeSiH), was unprecedented in the past.

Table 29: Gravimetric Contents of Additives and Samples of Example 14

CH ₃ CI additives Additive Wt. Duration Sample Wt. CH ₃ CI TC DM Table 29: Gravimetric Contents of Additives and Samples of Example 14 (Continued) additives Additive Wt. Duration Sample Wt. 1.25 CH ₃ CI TC DM MD M T T 0170 D 1823 Time (hr) + H ₂ 20 G minute G G G G G minute G 2.77 G G G G G G G 0275 G 2594 21 additives Additive Wt. Duration Sample Wt. CH ₃ CI TC DM Time (hr) 2:38 0118 _ 0219 MD M T 0195 D 3103 Time (hr) 22 M G minute G G G G 26 6.15 0067 - 0401 G G G 0475 G 2040 CH ₃ CI 1 23 15:50 15.0 21:17 3116 0239 0140 27 6.97 0120 - 0379 1996 13123 0734 0528 1274 2 24 6:01 0902 - 0101 28 7.86 0734 - 1080 0193 1749 0471 0652 0898 3 25 5:01 0719 - 0109 29 8.73 0671 - 1220 0206 0268 0605 0877 0148 4 3.61 0525 - 0093 30 15:17 1011 _ 1382 0180 0198 0574 9469 0778 5 2:48 0339 - 0092 31 T 10.98 0544 _ 1495 0238 0112 0425 1207 0512 6 1.68 - 0077 - 0053 32 2.22 11.5 14.86 1846 _ 0772 0222 0050 0380 1675 0509 7 M 12:30 0024 - 0008 33 16.88 1519 - 1780 0038 0008 0074 1826 0430 8th 8.79 7.5 12.71 2216 - 0160 34 17:32 1791 - 2447 0445 8746 0365 2002 2063 9 M 1.16 0173 - 0039 35 16.99 2184 - 2723 0169 0043 0224 1877 0519 10 8.69 6.0 9:55 0684 - 0091 36 16.63 2094 _ 2782 0286 7670 0310 1829 0983 11 1.15 0154 - 0034 37 15:44 2046 - 2718 0254 0066 0212 1814 15334 12 3.73 0169 - 0176 38 19:31 2017 - 2646 0419 0254 0649 10736 2830 13 0.87 0063 - 0028 39 T 12:49 0954 - 2511 0064 0029 0166 1622 1825 14 D 1.62 0092 - 0039 40 19:50 10 18:20 2352 _ 1041 0110 0050 0346 2339 1104 15 19:14 14 19.68 3214 - 0077 41 19:28 1478 _ 1835 0303 0256 0496 2437 1059 16 4:49 0226 - 0151 42 19.66 2226 - 2641 0184 0214 0885 2676 17 3.16 0118 - 0130 43 6:37 2574 - 2855 0142 0150 0795 0987 14018 18 2.24 0212 - 0098 44 1.27 2178 - 2847 0128 0080 0618 0241 1441 19 2:07 0339 _ 0081 45 12:29 0946 - 0490 0110 0063 0418 2030 D CH ₃ CI 46 12:28 0139 - 0046 2030 17:31 12 9.23 2879 - 1510 47 3960 0118 0605 4170 7.13 0478 - 1386 48 3183 0109 0533 7416 8.63 0922 - 1639 49 3345 0180 0617 8.30 0996 - 1550 2933 0180 0611 D D 13.85 0079 0073 1593 3272 0368 4295 G 7:42 5 24.03 - 0125 2787 5746 0651 7305 0419 0760 MD M 0544 G G 1577 0299 0026 1531 1213 0054 2:03!) 1101 0041 2769 2181 0123 1270 2897 0123 3318 2613 0163 4691 2842 0203 5361 1748 0065 5442 2947 0209 5:27!) 3965 0291 5097 4453 0333 5038 4652 0348 1840 4730 0340 3586 4713 0328 5623 4799 0324 5618 3283 0058 6014 3827 0142 2821 5143 0228 0719 5558 0237 5709 0236 0997 0129 0095 0030 ties Not Analyzed - Samples Not Analyzed

Table 30: Hourly Product Composition in Example 14

CH ₃ CI additives Product Wt. TC DM MD M T D MeSiH MeSiH / D rate 12:45 Time (hr) + H ₂ 20 M gms Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % 1.17 MD / DM% Si / hr 12:29 CH ₃ CI 1 21 4.93 4.85 2.84 40.47 14.88 36.96 43.31 12:11 14:25 12:35 2 22 3:36 - 3:01 5.75 2.14 77.22 8.76 12:10 1.91 12:25 3 23 4:02 - 2.71 5.12 4.15 77.13 7.83 12:13 1.89 12:18 4 24 2.89 - 3.22 6.24 19.88 70.66 9:46 12:26 1.94 12:14 5 25 2:03 - 4:53 11.73 20.95 62.79 16:26 12:31 2:59 12:02 • 6 26 1.55 - 3:42 14:32 24.52 57.74 17.74 12:31 4.19 12:16 7 27 M 12:27 - 2.99 14:18 27.61 55.22 17:17 0.78 4.74 12:08 8th 28 1.75 - 9.15 25.46 20.88 44.51 34.61 12:41 2.78 12:11 9 29 M 0.94 - 4.13 17.90 23.73 54.24 3.22 0.74 4:33 12:08 10 30 1.20 - 7.61 23.91 20.92 42.56 31.52 0.67 3.14 12:30 11 31 0.93 - 3.66 27.31 22.80 46.23 30.97 12:29 7:46 12:07 12 32 3.31 - 5:32 12.67 19.63 62.38 17.99 12:18 2:38 12:13 13 33 0.78 - 3:58 8.25 21:40 66.77 11.83 12:15 30.2 12:11 14 34 D 1:48 _ 2.64 7:44 23:41 66.51 8.10 2.82 12:13 15 35 1.13 - 6.80 26.77 22.62 43.81 33.57 3.94 12:18 16 36 1:43 - 10:53 12.83 14.92 61.72 23:36 12:32 1.22 12:18 17 37 2:07 _ 6.29 6.87 7.26 38.48 41.10 13:16 12:21 1:09 12:16 18 38 2:03 - 4.83 6.31 3.94 30.47 54.45 11:14 12:18 1.31 19 39 1.73 - 4.68 6:36 3.64 24.15 61.17 4.11 1:36 0.Γ5 40 D 12:55 41 6.19 - 24.38 63.94 1.91 9.77 88.32 2.62 0.62 42 5.21 - 26.60 61.08 2:09 10:23 87.68 64.95 30.2 0./5 43 5.86 - 27.98 57.11 3:07 10:53 1.31 85.09 2.21 2:04 1.31 44 7.30 _ 21.2 40.16 2:46 8:37 27.79 61.38 1.17 1.89 1.63 45 D 13.77 12:53 11:57 23.76 2.67 31.19 30.28 35.33 2:05 12:12 46 16.61 0.75 16.78 34.58 3.92 43.97 51.36 1.23 2:06 12:28 47 r 1.13 _ 19:34 26.36 2.26 15:00 37.04 45.70 2.13 1:36 G.24 48 2.70 - 14.84 44.88 2:00 10:17 28.11 59.72 2.72 3:02 12:58 49 2.26 _ 16.77 48.72 1.81 8.63 24.07 65.49 2:09 2.91 0.68 5:42 _ 19.94 40.27 2.27 8.77 28.75 60.21 ? ^r-'I 2:02 0.74 30.6 19:37 45.99 1.95 8:38 24.31 65.36 1.d6 2:37 0.88 6.85 _ 20:18 38.15 2:38 9:52 29.77 58.33 1:57 1.89 12:43 T 8.19 - 18:26 34.72 2:48 10.71 33.83 52.98 1.99 1.90 0.Ö2 3.86 - 20.3 45.34 1.69 32.94 65.37 1:43 2.26 1.28 8.25 - 21:57 3E.70 2:53 40.20 57.27 1:37 1.66 1:46 11:39 - 21:48 34.80 2:55 41.17 56.28 1:34 1.62 1:53 12.87 - 21:16 34.60 2:59 41.65 55.76 1:37 1.64 1:53 13:22 - 4.21 35.18 2.63 41.15 56.22 1:41 1.67 1:52 7.13 - 20.80 36.20 2.60 40.40 57.00 1.74 1:53 12.78 - 20.70 36.87 2:54 39.87 57.57 1.78 0.77 T 12.67 - 19.82 37.87 2:56 39.75 57.69 1.91 1.16 6.22 - 16.73 52.77 0.93 29.57 69.50 3.15 1.70 9:39 - 19:54 40.76 1:51 38.19 60.30 2:09 1.82 13.64 - 19:37 37.72 1.67 41.24 57.09 1.95 1.94 14:27 - 20.1 38.95 1.66 39.38 58.96 1.95 0.66 15:12 - 18.83 37.77 1:56 2:06 39.78 56.60 1:44 2:01 12:13 5:42 - 9:03 18:38 2:38 18:20 52.01 27.41 1:45 2:04 12:03 1.13 - 4:04 8:40 2.67 21:32 63.57 12:44 2:35 2:08 12:03 Samples Not Anal 1:58 1:38 Samples Not Analyzed 1:50 1:42 12:53 12:02

Claims (30)

1. Direct synthesis method for the selective production of Organohalogenhydrosilanen, characterized by the general formula RaHbSiX ₀ (I) by reacting activated silicon with a mixture of an organohalide of the general formula RX and hydrogen in contact with a catalytic amount of catalyst at elevated temperature, wherein R is a hydrocarbyl group having up to about 20 carbon atoms; X is a halogen atom;: d, b and c are integers having a value of 1 or 2, with the proviso that the sum of a + b '+ C = 4, wherein the concentration of the following metal atoms is activated Silicon bed is as follows: (i) Zn, Sb and Cd, together or individually, less than 0.05% by weight of the silicon; (ii) Sn less than 0.01% by weight of the silicon; (iii) Ni of about 0.001 - about 0.02 wt% of the silicon; (iv) Cr of about 0.001 - about 0.06 wt% of the silicon; and (v) Cu up to about 10% by weight of the silicon. 2. Direct synthesis process according to claim 1, characterized by the concentrations of said metals (i) Zn, Sb and Cd, individually or together, less than 0.01% by weight; (ii) Sn less than 0.005 wt%; (iii) Ni from about 0.002 to about 0.01 weight percent; (iv) Cr less than about 0.04 wt.% and (v) Cu of about 0.05 to about 3 wt%. 3. direct synthesis method according to claim 1, characterized by the concentration of said metals (i) Zn, Sb and Cd, individually or together, less than 0.005 wt%; (ii) Sn less than 0.0005 wt%; (iii) Ni from about 0.004 to about 0.008 wt%; (iv) Cr from about 0.005 to about 0.01% by weight; and (v) Cu of about 0.5 to about 1.5 wt%. 4. direct synthesis process according to claim 1, characterized in that R is methyl and X is chlorine. 5. direct synthesis process according to claim 1, characterized in that the catalyst (v) is a copper, silver or copper-silver mixed catalyst. 6. direct synthesis method according to claim 1, characterized in that the selectively produced Organohalogenhydro ^ iiane are a mixture of R ₂ SiHX and RSiHX ₂ , wherein R and X are defined as in claim 1 _t , and that said organohalide is methyl chloride, the said Catalyst is a copper catalyst and the total concentration of Zn + Sb + Cd less than 0.0008Gew .-% is that the Sn concentration about 0.0003Gew .-%, of Ni about 0.0018 wt .-% and that of Cr about 0.006% by weight. The direct synthesis method of claim 1, characterized in that about 1 to about 10 weight percent of a silicide of calcium, magnesium or copper is present in said activated silicon bed. 8. direct synthesis method according to claim 1, characterized in that said selectively produced Organohalogenhydrosilane form a mixture of R ₂ SiHX and RSiHX ₂ , that said organohaloganide is methyl chloride, and that said catalyst is a copper catalyst and wherein in said activated silicon bed about 2 to about 8Gew .-% calcium silicide are present. ö. Direct synthesis method according to claim 1, characterized in that the pressure is atmospheric pressure. 10. direct synthesis method according to claim 1, characterized in that the pressure is a superatmospheric pressure. 11. direct synthesis process according to claim 6, characterized in that R is methyl and X is chlorine. A direct synthesis method according to claim 1, characterized in that the selectively produced organohalohydrosilanes are a mixture of R ₂ SiHX, RSiHX ₂ and RSiHiX wherein R and X are as defined in claim 1, said organohalide being methyl chloride and said catalyst being copper Catalyst is. The direct synthesis method of claim 12, characterized in that from about 2 to about 8 weight percent calcium silicide is present in said activated silicon bed. 14. direct synthesis process according to claim 12, characterized in that R is methyl and X is chlorine. 15. direct synthesis method according to claim 1, characterized in that an auxiliary agent is introduced into the activated silicon bed of (i) a halosilane of the general formula where d has a value of 0 to 3 and e has a value of 1 to 4 and the sum of d + e = 4; or (ii) an organohalosilane of the general formula R'fSiX ₄ .. f is. wherein R 'is an alkyl group having 1 to about 6 carbon atoms and f has a value of 1 to 3; or (iii) an organohalosilane of the general formula R _a H _{b is} SiX _c , as defined in claim 1. 16. Direct synthesis process according to claim 15, characterized in that the auxiliary is introduced during the silicon activation. 17. Direct synthesis method according to claim 15, characterized in that the auxiliary agent is injected into the activated silicon during the course of the direct synthesis reaction. 18. direct synthesis method according to claim 1, characterized in that a promoter is introduced into the activated silicon, wherein the promoter from the group of nickel, chromium, rhodium and palladium. A direct synthesis method according to claim 18, characterized in that the promoter is the nickel atom in a concentration of about 0.002 to about 0.08% by weight of the activated silicon. 20. direct synthesis method according to claim 18, characterized in that the promoter is the chromium atom in a concentration of about 0.005 wt .-% of the activated silicon. 21. Direct synthesis method according to claim 18, characterized in that the promoter is the rhodium atom in a concentration up to about 1 wt .-% of the activated silicon. 22. Direct synthesis method according to claim 18, characterized in that the promoter of the palladium atom in a concentration up to about 0.5 wt .-% of the activated silicon. 23. Diraktsyntheseverfahren according to claim 12, characterized in that the method is carried out in a fixed bed reactor. 24. direct synthesis process according to claim 15, characterized in that the aid is dimethyldichlorosilane. 25. Direct synthesis process according to claim 15, characterized in that the auxiliary is methyltrichlorosilane. 26. Direct synthesis process according to claim 15, characterized in that the auxiliary is trimethylchlorosilane. 27. Activated silicon composition, characterized for use in the direct synthesis of organohalohydrosilanes of the general formula RaHbSiXc (I) by the reaction of the activated silicon with a mixture of an organohalide of the general formula RX and hydrogen, consisting of silicon and (i) Zn, Sb and Cd, individually or together, in a proportion of less than 0.05% by weight of silicon; (ii) Sn in less than 0.01% by weight of the silicon; (iii) Ni in about 0.001% to about 0.02% by weight of the silicon; (iv) Cr in about 0.001% to about 0.006% by weight of the silicon; and (v) Cu up to about 10% by weight of the silicon. 28. An activated silicon composition according to claim 27, characterized in that this composition contains: Silicon and (i) Zn, Sb and Cd, individually or together, in an amount of less than 0.01% by weight; (H) Sn, less than 0.005 wt%; (iii) Ni at about 0.002 to about 0.01 wt% (iv) Cr, less than about 0.04 wt%; and (v) Cu at about 0.05 to about 3 weight percent. 29. An activated silicon composition according to claim 27, characterized in that this composition contains: Silicon and (i) Zn, Sb and Cd, individually or together, in an amount of less than 0.005% by weight; (ii) Sn at less than 0.0005 wt%; (iii) Ni at about 0.004 to about 0.008 wt%; (iv) Cr at about 0.0005 to about 0.01 weight percent; and (v) Cu at about 0.5 to about 1.5 weight percent. The activated silicon composition according to claim 27, characterized in that said composition contains: Silicon in which the total concentration Zn + Sb + Cd is less than 0.0008 GeW ₁ - ⁰ Zo, the concentration of Sn being about 0.0003 wt%, the Ni concentration being about 0.0018 wt%, and the Cr Concentration is about C, 006Gow .-%.