KR20070010199A - Process for making haloorganoalkoxysilanes - Google Patents

Abstract

A haloorganoalkoxysilane is prepared by reacting an olefinic halide with an alkoxysilane in which the alkoxy group(s) contain at least two carbon atoms in a reaction medium to which has been added a catalytically effective amount of ruthenium-containing catalyst and a reaction- promoting effective amount of an electron-donating aromatic compound promoter. The process can be used to prepare, inter alia, chloropropyltriethoxysilane, which is a key intermediate in the manufacture of silane coupling agents. ® KIPO & WIPO 2007

Description

Production method of halo organic alkoxysilane {PROCESS FOR MAKING HALOORGANOALKOXYSILANES}

The present invention relates to a process for the preparation of some haloorganosilicon compounds. More particularly, the present invention relates to a process for the preparation of haloorganoxyalkoxysilanes, for example chloropropyltrimethoxysilane.

Chloropropyltrimethoxysilane is an important intermediate for the preparation of various amino-, mercapto- and methacryloyloxyorganosilanes used as silane coupling agents. Chloropropyltrimethoxysilane can also be converted to chloropropyltriethoxysilane, an important intermediate for the production of polysulfane-containing organoalkoxysilanes used in the production of silica-filled tires.

US Pat. No. 6,191,297 discloses a two step process involving ethanol esterification of the product obtained from platinum-catalyzed silicon hydride hydrosilation of trichlorosilane with allyl chloride. The process is very material- and plant-intensive due to low yield and significant byproduct formation, ie propyltrichlorosilane.

A potentially more economical route is the direct silicon hydride reaction of triethoxysilane with allyl chloride. Platinum is the most widely used silicon hydride catalyst and its use for the silicon hydride reaction of allyl chloride with triethoxysilane has been reported. According to US Pat. No. 3,795,656, a 70% yield was obtained in a Pt-catalyzed silicon hydride addition reaction of allyl chloride with triethoxysilane. Belyakova et al., Obshch. Khim 1974, 44, 2439-2442 discloses a Pt-catalyzed silicon hydride addition reaction of silyl and allyl chloride and 14% yield is reported for chloropropyltriethoxysilane. As disclosed in Japanese Patent No. 11,199,588, the Pt-catalyzed silicon hydride addition reaction of trimethoxysilane with allyl chloride produced 70% yield of chloropropyltrimethoxy-silane.

The primary limitation on the silicon hydride addition reaction of allyl chloride with silane is the competitive removal reaction. In the case of platinum, the competition elimination reaction is more prevalent with alkoxysilanes than chlorosilanes. Rhodium and palladium mainly provide removal products.

Iridium has been reported to be a very efficient catalyst for the silicon hydride reaction of allyl chloride with triethoxysilane. According to US Pat. No. 5,616,762, the iridium-catalyzed silicon hydride addition reaction of triethoxysilane with allyl chloride is highly selective for chloropropyltriethoxysilane with minimal byproducts. Japanese Patent Application No. 4 [1992] -225170 reports similar results for the iridium-catalyzed silicon hydride addition reaction of allyl chloride with trimethoxysilane. In US Pat. No. 4,658,050, the iridium-catalyzed silicon hydride addition reaction of alkoxysilanes with allyl chloride uses an olefin iridium complex.

Ruthenium has been reported to be a very efficient catalyst for the silicon hydride addition reaction of allyl chloride with trimethoxysilane. Japanese Patent No. 2,976,011 discloses a Ru-catalyzed silicon hydride addition reaction of triethoxysilane with allyl chloride to provide chloropropyltriethoxysilane in about 41% yield. U. S. Patent No. 5,559, 264 discloses the provision of chloroalkylalkoxysilanes by silicon hydride addition of methoxysilane and allyl chloride in the presence of a ruthenium catalyst, preferably in the substantial absence of a solvent. Tanaka et al., J. Mol. Catal. 1993, 81, 207-214 report ruthenium carbonyl-catalyzed silicon hydride addition reactions of trimethoxysilane with allyl chloride, and Japanese Patent Application No. 8 [1996] -261232 discloses hydrogenation for the same reaction. Activation of ruthenium carbonyl for use as a silicon addition reaction catalyst is disclosed.

Summary of the Invention

According to the invention, an olefin halide of the formula H ₂ C═CR ³ CR ⁴ R ⁵ X, wherein R ³ , R ⁴ , R ⁵ and X has the following meaning, is molar excess of the formula (R ¹ ) _x ( R ² O) Reaction medium with addition of an alkoxysilane of _{3- x} SiH, where R ¹ , R ² and x have the following meanings, a catalytically effective amount of a ruthenium-containing catalyst and a reaction promoting effective amount of an electron donating aromatic compound It provides a process for the preparation of haloorganoalkoxysilanes of the formula:

(R ¹ ) _x (R ² O) _{3- x} SiCH ₂ CHR ³ CR ⁴ R ⁵ X

Where

R ¹ is alkyl having 1 to 6 carbon atoms,

R ² is alkyl having 1 to 6 carbon atoms,

R ³ is alkyl or hydrogen of 1 to 6 carbon atoms,

R ⁴ is alkyl having 1 to 6 carbon atoms, hydrogen or halogen,

R ⁵ is hydrogen or alkyl of 1 to 6 carbon atoms,

X is halogen,

x is 0, 1 or 2.

The aromatic compound may contain an electron donating group to promote the reaction. In addition, the aromatic compound should be present in an amount sufficient to catalyze the reaction but not inhibit the reaction. Furthermore, the aromatic compound must be present simultaneously with the ruthenium catalyst in the above-mentioned alkoxysilane or catalyst solution.

The reaction wherein the olefin halide and alkoxysilane react in the presence of a ruthenium catalyst and an aromatic compound promoter to give a haloorganoalkoxysilane can be considered to proceed according to the following scheme:

Where

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and x have the meanings described above.

The process of the present invention can be carried out in a variety of commercially available devices which are currently used in silicon hydride addition reactions, for example in a device which carries out such reactions in a continuous manner.

By integrating the process of the present invention with, for example, a source of trimethoxysilane prepared directly from silicon metal and methanol, it avoids the use of corrosive and dangerous hydrochlorosilanes and avoids the use of large amounts of chlorine containing waste byproducts (products derived from hydrochlorosilanes). Can be eliminated).

Several factors have been found to be important for obtaining high yields of haloorganoalkoxysilanes from a one-step silicon hydride reaction between an olefin halide and an alkoxy silane. First, when all reactants are combined at the start in a batch reaction, the selectivity for the desired haloorganoalkoxysilane is highest at lower temperatures and at lower reaction rates. Secondly, when increasing the temperature to improve the reaction rate, selectivity can be maintained by limiting the concentration of olefin halides in the reaction mixture. Third, most inert solvents and especially aromatic solvents can have a detrimental effect on speed, selectivity or both, especially when used at relatively high levels typical of reaction solvents.

Preferably, the process is carried out by slowly adding the olefin halides to the reaction medium containing the alkoxysilane and reacting them in a semi-batch or continuous process in the presence of an electron-donating aromatic compound as ruthenium metal-containing catalyst and promoter. This order of addition effectively maintains the minimum concentration of unreacted olefin halide in the reaction medium relative to the alkoxysilane, thus effectively establishing a very large molar excess of alkoxysilane relative to the olefin halide in the reaction medium. In general practice, the maximum rate of addition of olefin halides to the alkoxysilane, as understood by those skilled in the art, depends on the reaction rate (partially dependent on reaction temperature, catalyst concentration, concentration of electron donor aromatic compound promoter). And the heat transfer limit of the reaction apparatus (whether a very large commercial reactor with a small laboratory reactor is used).

Preferred blending sequences can be achieved in a semi-batch or continuous process. In a semi-batch process, the reactor is first charged with a large amount, preferably with an entire molar excess of alkoxysilane. An aromatic compound and a ruthenium catalyst can then be added to the alkoxysilane and subsequently reacted with the olefin halide. On the other hand, the olefin halide is slowly added to the reactor containing molar excess alkoxysilane and the alkoxysilane and olefin halide are reacted in the presence of a solution of a ruthenium catalyst and an aromatic promoter. As used herein, slow addition of olefin halides generally means a rate of up to about 3 moles of olefin halide per hour per mole of alkoxysilane, preferably up to 1 mole per hour per mole of alkoxysilane. For example, in a semi-batch process, when 1 mole of olefin halide is added to a reactor containing 2 moles of alkoxysilane for 15 minutes, the addition rate of 2 moles of olefin halide / hour / alkoxysilane mole is carried out. Once the olefin halide has been added to the reactor, the reaction continues until the olefin halide is completely converted. While this is mostly a function of temperature, catalyst and aromatic promoter concentration, complete conversion can generally be achieved in 1 to 15 hours, more usually 1 to 10 hours. It is common for the reaction to be completed in 1 to 5 hours. A portion of the alkoxysilane can also be added simultaneously with the addition of the olefin halide in a mixture with the olefin halide or as a separate stream.

In a continuous process, the reactor is typically charged with a separate stream of olefin halides and alkoxysilanes in a molar ratio of about 1.3 to about 3.0, preferably about 1.8 to about 2.3 alkoxysilanes to olefin halides. Such a process ensures a suitable excess of alkoxysilane in the reaction vessel under steady state process conditions. For methoxysilane, which is a preferred alkoxysilane, and allyl chloride, which is a preferred olefin halide, the preferred molar ratio is about 1.6 to about 2.3. In a continuous process, the aromatic promoter and ruthenium catalyst can be added to the olefin halide and alkoxysilane separately or preferably as a catalyst solution in a reactor charged with separate streams of the above-mentioned olefin halides and alkoxysilanes.

The aromatic promoter used in the process of the present invention is exhibited by the reaction promotion amount in the reaction medium, i.e. less than the amount that inhibits the reaction (higher product purity and / or lowered production of by-products such as organoalkoxysilanes and haloalkoxysilanes). ) Should be present in an amount that increases the reaction yield. Generally, the effective amount of the aromatic promoter will range from about 1 to about 100 molar equivalents per mole of ruthenium metal, preferably from about 5 to about 50 molar equivalents per mole of ruthenium metal, more preferably from about 20 to about 30 molar equivalents per mole of ruthenium metal. Can be.

Other silicon hydride reaction conditions such as temperature, molar ratio of reactants, pressure, time and catalyst concentration are not very important. There is a wide range of tolerances for adjusting these factors in order to economically and safely use the various compartments of the production apparatus. Such devices will typically have facilities for purification in heating, cooling, stirring, maintenance of an inert atmosphere, and filtration or distillation. Thus, reflux of the silicon hydride compound in a band containing a heterogeneous supported silicon hydride reaction catalyst and an electron donating aromatic promoter in an apparatus typically used in the prior art for large scale commercial silicon hydride reactions, for example, olefin halides. Apparatus for adding to the coolable stream can be used in the process of the invention.

The reaction conditions may comprise a reaction temperature of about 50 to about 130 ° C, preferably about 60 to about 80 ° C. In general, the process is carried out at or above atmospheric pressure, with atmospheric pressure being preferred. The process of the present invention can provide a high yield of the desired chloroalkylalkoxysilane in a true batch system; Batch reactions will typically be carried out at lower temperatures and consequently longer reaction times. Accordingly, the silicon hydride addition reaction is preferably carried out at an elevated temperature by adding an olefin halide to the molar excess of alkoxysilane in the presence of a ruthenium metal containing catalyst and an aromatic promoter. One particular preferred mode of practice (semi-batch) is the slow addition of the entire amount of olefin halide over a period of time, so that from about 1.6 to about 2.3 molar equivalents of tri, relative to the total amount of alkoxysilane, such as allyl halide added Obtaining a rate of addition of less than 3 moles of olefin halide per hour per mole of alkoxysilane to the reactor containing methoxysilane.

In one embodiment, the reactor contains 5 to 100 ppm ruthenium as RuCl ₃ based on the weight of the total reactants. In a second embodiment, the reaction medium contains about 15-25 ppm ruthenium of the total reactant weight. In yet another embodiment, the reactor contains 5 to 50 ppm ruthenium and a reaction promoting effective amount of an aromatic promoter as RuCl ₃ hydrates, based on the weight of the total reactants, the reaction being about 50 to about 130 ° C., preferably Is carried out at about 60 to about 80 ° C. Excess alkoxysilane, ruthenium catalyst and aromatic promoter can be effectively recycled to the next batch.

The process of the invention is not preferred because it is almost quantitative for the conversion of olefin halides to the desired haloorganalkoxysilane product, especially in the reaction of allyl chloride with trimethoxysilane to give chloropropyl-trimethoxysilane. The generation of poor byproducts is significantly lowered. This reduces the amount of material that is destroyed or discarded as waste, isolated as a separate stream by distillation or withdrawn from the reaction system. Since the process of the present invention is highly exothermic, external heating is usually not necessary and the reaction time is correspondingly shorter. In general, the only significant amount of impurities that need to be removed from the reaction product are a slight excess of unreacted alkoxysilane, residual catalyst and aromatic promoter. These can be recycled to the next batch without purification. Low levels of residual halides that may be present in the product may be neutralized by methods well known in the art. When the silicon hydride reaction product of the present invention is used as an intermediate in the production of other organofunctional silicon compounds, its purity in the initial synthesis may be sufficient to eliminate the need for further purification, for example by distillation.

When applied, for example, to the preparation of chloropropyltrimethoxysilane, the process of the present invention provides higher product yields than any one or two stage process disclosed in the prior art, calculated on a molar basis from limiting reactants. . This is done by adding an effective amount of aromatic promoter and an effective amount of ruthenium catalyst to the reaction medium. The process also achieves such yields using significantly lower levels of ruthenium metal containing catalysts than any of the methods disclosed in the art. In addition, the process of the present invention utilizes an effective amount of electron donating aromatic compound that promotes a significant increase in product and minimizes waste. The method also provides higher yields per unit volume of the apparatus used, since the use of inert solvents is omitted and no significant amount of waste by-products are generated. The preferred blending order of the reactants in the present invention is in fact contrary to that used to maximize the yield of chloropropyltrichlorosilane from the reported platinum catalyzed reaction of trichlorosilane with allyl chloride. Furthermore, the yields obtained are reported for the platinum catalyzed reaction of triethylsilane with allyl chloride, which is maximized by adding to the triethylsilane allyl chloride necessarily containing trichlorosilane as a silicon hydride addition reaction promoter. Significantly higher than that.

The process of the present invention does not require performing at pressures above atmospheric pressure, but it is possible to use elevated pressures, for example below 2 atmospheres, by using a closed reactor to suppress accidental potential release of allyl halides to the environment. Pressures below atmospheric pressure may be used when aiming at reaction temperatures below the atmospheric boiling point of the alkoxysilanes.

Olefin halides suitable for use in the present invention include allyl chloride, metallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, 2-chloropropene and the like. Of these, allyl chloride, CH ₂ = CH ₂ CH ₂ Cl is preferred.

Suitable alkoxysilanes for use in the present invention include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, Diethylethoxysilane and the like. Among these alkoxysilanes, ethoxysilane is preferred, and triethoxysilane is more preferred.

The ruthenium metal-containing catalyst and aromatic promoter must be present in the reaction medium and can be added with the alkoxysilane or olefin halide in solution, or both can be present in heterogeneous form in the catalyst zone into which the reactants are introduced. Various homogeneous and dissimilar forms of ruthenium metal containing compounds can be used as catalysts and the level of use (based on the metals contained) can be as low as the levels of commercially practiced platinum catalyzed silicon hydride addition reactions. For example, ruthenium concentrations of about 2 to 300 ppm are generally suitable.

If oxygen is required for catalyst activation, the amount of oxygen typically present in commercial raw materials, in particular in the reactants themselves, will generally be sufficient. This is especially true for ruthenium carbonyl catalysts. If necessary, the addition of catalyst activation, this dilute oxygen, for example, can be easily carried out by the addition of a mixture of N ₂ 3% O ₂ in one or more of the reactants, or the reaction medium increases the level of oxygen in contact with the catalyst have. If the catalyst is a ruthenium-phosphine complex, further activation may be required.

Suitable ruthenium-metal containing catalysts can be selected from homogeneous and dissimilar ruthenium metal containing compounds and complexes comprising: Ru ₃ (CO) ₁₂ , [Ru (CO) ₃ Cl ₂ ] ₂ ; Cyclooctadiene-RuCl ₂ ; RuCl ₃ , (Ph ₃ P) ₂ Ru (CO) ₂ Cl ₂ ; (Ph ₃ P) ₃ Ru (CO) H ₂ ; Fe phase Ru; Ru in Al ₂ O ₃ phase; Ru on carbon; Ru (AcAc) ₃ ; RuBr ₃ and the like, where Ph is a phenyl group and AcAc is an acetylacetonate group.

Ruthenium metal containing compounds constituting a ruthenium complex containing only triphenylphosphine, hydrogen and chlorine ligands, for example (Ph ₃ P) ₃ RuCl ₂ , (Ph ₃ P) ₃ RuHCl and (Ph ₃ P) ₃ RuH ₂ has no effect as a reaction catalyst of trimethoxysilane with olefin halide in the presence or absence of oxygen. This lack of catalytic activity is consistent with the findings of previous researchers who investigated the addition of silicon hydride between allyl chloride and triethoxysilane. If phosphine ligands are present, other ligands other than hydrogen or chlorine, such as carbonyl and olefin ligands, must also be present, and slightly higher levels of activated oxygen may be required. Also suitable are ruthenium complexes containing aromatic compounds, for example (π-arene) ruthenium complexes with at least 1 molar equivalent of aromatic compounds relative to ruthenium metal. Examples of (π-arene) ruthenium complexes are (p-cymene) ruthenium (II) chloride dimers or (benzene) ruthenium (II) chloride dimers.

Preferred ruthenium catalysts are ruthenium chloride compounds, with RuCl ₃ hydrate being most preferred. The catalyst from one batch can be recycled to the next batch without significant loss of activity. The catalyst use level may range from 0.1 to 300 ppm of the Ru metal contained, based on the total reactant charge, with 5-50 ppm being preferred.

Examples of suitable aromatic compounds include benzene, ethylbenzene, diethylbenzene, triethylbenzene, n-butylbenzene, di-t-butylbenzene, bibenzyl, toluene, t-butyltoluene, anisole, 1-phenylhexane, 1 -Phenyldodecane, Nalkylene® (mixture of n-alkylbenzenes of C ₈ to C ₁₂ ), Therminol® (mixture of ethylbenzene and bibenzyl isomers), m-xyl Ethylene, mesitylene, p-cymene, diphenylmethane, triphenylmethane, phenyl ether, phenothiazine, and biphenyl, which are about 1 to about 100 molar equivalents, preferably ruthenium, relative to moles of ruthenium metal It may be present in an amount of about 5 to about 50 molar equivalents relative to moles of metal, more preferably about 20 to about 30 molar equivalents relative to moles of ruthenium metal.

The haloorganoalkoxysilane product of the process of the invention can be used directly, without intermediate purification, when purified by standard means, for example by distillation, or as an intermediate for subsequent preparation.

As indicated above, the reaction can also be carried out in a continuous manner by adding the alkoxysilane and olefin halide reactants to the reactor in the desired molar excess of silane. At steady state, the reactor will contain sufficient excess alkoxysilane in a mixture with the product haloorganoalkoxysilane to allow substantial quantitative yield of the desired product. The excess alkoxysilane can be recovered from the product stream and recycled for convenience.

While the exact scope of the invention is shown in the appended claims, the following specific examples illustrate some aspects of the invention and, more particularly, point out several aspects of the method for evaluating the invention. However, these examples are shown for illustrative purposes only and should not be construed as limitations on the present invention. The abbreviations g, ppm, equivalents, GC and TMS refer to grams, parts per million, molar equivalents, gas chromatography and trimethoxysilane, respectively. The temperature is expressed in degrees Celsius. The yield percentage is measured by GC using an internal standard, but vacuum distillation of the product is carried out when the yield is measured by actual weight. Unless otherwise indicated, all reactions were run on standard laboratory glassware at atmospheric pressure under an inert atmosphere of nitrogen. In each example, the product structure was confirmed by GC, GC / mass spectrometry, infrared spectroscopy, or nuclear magnetic resonance.

All reactions of the following examples were carried out under a nitrogen atmosphere. Allyl chloride, metallyl chloride, trimethoxysilane and RuCl ₃ hydrate were used without further purification. TMS was distilled using a 5 tray Oldershaw column under atmospheric pressure and stored in glass bottles or stainless steel bottles. Typical TMS purity was ˜98% (weight / weight). All GC data are expressed in weight percent by weight (weight / weight) and normalized to excess TMS.

The following abbreviations and trade names (with descriptions) are shown in the Examples:

Abbreviation Explanation

TMS trimethoxysilane

Cl-TMOS Chlorotrimethoxysilane

TMOS tetramethoxysilane

Propyl-TMS n-propyltrimethoxysilane

Cl-CPTMS 3-chloropropylchlorodimethoxysilane

CPTMS 3-chloropropyltrimethoxysilane

Bis TMS propane bis (trimethoxysilyl) propane

Isobutyl-TMS Isobutyltrimethoxysilane

Cl-CIBTMS 3-chloroisobutylchlorodimethoxysilane

CIBTMS 3-Chloroisobutyltrimethoxysilane

Bis TMS isobutane bis (trimethoxysilyl) isobutane

Mixture of n-alkylbenzenes consisting of Nalkylene® C ₈ to C ₁₂

Therminol® Mixtures of ethylbenzene, bibenzyl and related isomers.

Example  One

At ambient temperature, 29.02 g (0.2351 mol) of trimethoxysilane were treated with 0.016 g of toluene and 0.025 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (24 ppm Ru). The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  2

At ambient temperature, 28.91 g (0.2342 mol) of trimethoxysilane were treated with 0.056 g of toluene and 0.025 g of 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (24 ppm Ru). The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  3

At ambient temperature, 28.91 g (0.2342 mol) of trimethoxysilane were treated with 0.64 g of toluene and 0.050 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (47 ppm Ru). The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  4

At ambient temperature, 28.91 g (0.2342 mol) of trimethoxysilane were treated with 0.64 g of toluene and 0.050 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (47 ppm Ru). The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  5

At ambient temperature, 28.67 g (0.2323 moles) of trimethoxysilane were added to 0.016 g of Suminol® 59 and 0.020 g of 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (19 ppm Ru). Treated. The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  6

At ambient temperature, 150.34 g (1.2203 mol) of trimethoxysilane were treated with 0.280 g of ethylbenzene and 0.080 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (23 ppm Ru). The trimethoxysilane solution was warmed and treated with 59.56 g (0.7705 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 80-81 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  7

At ambient temperature, 160.78 g (1.3056 mole) of trimethoxysilane were treated with 0.140 g of n-butylbenzene and 0.080 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (22 ppm Ru). The trimethoxysilane solution was warmed and treated with 63.72 g (0.8243 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 80-81 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  8

At ambient temperature, 161.96 g (1.3147 mol) of trimethoxysilane were treated with 0.110 g of anisole and 0.080 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (22 ppm Ru). The trimethoxysilane solution was warmed and treated with 64.17 g (0.8301 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 80-81 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  9

At ambient temperature, 165.22 g (1.3413 moles) of trimethoxysilane were treated with 0.170 g of diphenylmethane and 0.080 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (22 ppm Ru). The trimethoxysilane solution was warmed and treated with 65.47 g (0.8469 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 80-81 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  10

At ambient temperature, 28.34 g (0.2296 mol) of trimethoxysilane were treated with 0.024 g of benzyl and 0.020 g of 3.85% Ru (weight / weight) as methanol solution of ruthenium (III) chloride hydrate solution. The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  11

At ambient temperature, 165.22 g (1.3416 moles) of trimethoxysilane were treated with 0.250 g of triphenylmethane and 0.080 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (22 ppm Ru). The trimethoxysilane solution was warmed and treated with 65.48 g (0.8470 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 80-81 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  12

At ambient temperature, 28.61 g (0.2318 mol) of trimethoxysilane were treated with 0.024 g of benzyl and 0.020 g of 3.85% Ru (weight / weight) as methanol solution of ruthenium (III) chloride hydrate solution. The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 60 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 60-63 ° C. After the addition was completed, the reaction was maintained at 60 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  13

At ambient temperature, 161.16 g (1.3082 moles) of trimethoxysilane were treated with 0.80 g of 3.85% Ru (weight / weight) as a methanol solution of bibenzyl 0.190 g and ruthenium (III) chloride hydrate solution (22 ppm Ru). The trimethoxysilane solution was warmed and treated with 63.85 g (0.8260 mol) of allyl chloride at 70 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 70-72 ° C. After the addition was completed, the reaction was maintained at 70 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  14

At ambient temperature, 28.41 g (0.2302 mol) of trimethoxysilane were treated with 0.032 g of benzyl and 0.020 g of 3.85% Ru (weight / weight) as methanol solution of ruthenium (III) chloride hydrate solution. The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  15

At ambient temperature, 163.03 g (1.3248 moles) of trimethoxysilane were treated with 0.25 g of benzyl and 0.100 g of 3.85% Ru (weight / weight) as methanol solution of ruthenium (III) chloride hydrate solution. The trimethoxysilane solution was warmed and treated with 64.66 g (0.8364 moles) of allyl chloride at 95 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 94-96 ° C. After the addition was completed, the reaction was maintained at 95 ° C for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  16

At ambient temperature, 28.32 g (0.2294 moles) of trimethoxysilane were treated with 0.036 g of a 2.23% Ru (weight / weight) dichloromethane solution of (p-cymene) ruthenium (II) chloride dimer. The trimethoxysilane solution was warmed and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  17

At ambient temperature, 160.07 g (1.3008 mol) of trimethoxysilane were treated with a catalyst solution consisting of 0.074 g of toluene, 0.120 g of ruthenium (III) chloride hydrate and 62 g of methanol (1.7 molar equivalents of toluene to Ru). The trimethoxysilane solution was warmed and treated with 63.40 g (0.8213 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 79-82 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Catalyst solution

Two solutions were prepared by dissolving ruthenium (III) chloride hydrate in methanol and treating the solution with the specified amount of diphenylmethane at ambient temperature:

After mixing, the resulting solutions are ready for use.

Example  18

At ambient temperature, 163.93 g (1.3330 moles) of trimethoxysilane were treated with 0.200 g of Catalyst Solution A (21 ppm Ru) as prepared above. The trimethoxysilane solution was warmed and treated with 64.89 g (0.8394 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 79-81 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Example  19

Over the course of 8 hours (4 turnovers), trimethoxysilane was added at a rate of 1.47 g / min, allyl chloride was added at a rate of 0.78 g / min, and the prepared catalyst solution B was used with a syringe pump. To a 1 liter glass reactor at a rate of 0.167 mL / hour. Constant levels were maintained in the stirrer reactor so that the residence time was 2 hours. The reactor was maintained at 75 ° C. The catalyst load was -20 ppm Ru and the ratio of trimethoxysilane to allyl chloride was maintained at -2.0: 1.0. A water cooler was used on the reactor. At start up, the reactor contained ˜53% chloro-propyltrimethoxysilane, ˜41% trimethoxysilane and ˜20 ppm Ru (weight / weight). The crude CPTMS in the reactor was based on the average GC weight percent and standard deviation for four turnovers in the reactor.

During the continuous process, the material in the reactor was continuously fed to the second tray from the top of the 15 tray old show column. The reboiler temperature of the column was maintained at 167-169 ° C. It was recycled back to the reactor with fresh trimethoxysilane at a rate of 1.17 g / min. The above composition, based on the average GC data weight percent and standard deviation for four reactor turnovers, is as follows:

Strip material from the column reboiler unit was continuously fed into the CPTMS receiving bath. Over the course of 8 hours (4 turnovers), the resulting crude CPTMS was collected at a rate of 2.21 g / min and its composition based on the average GC wt% and standard deviation for 4 turnovers was as follows: :

Example  20

At ambient temperature, 28.48 g (0.2307 mol) of trimethoxysilane were treated with 0.034 g of benzyl and 0.033 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (30 ppm Ru). The trimethoxysilane solution was warmed and treated with 13.30 g (0.1454 mol) of metallyl chloride at 80 ° C. Metallyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

compare Example  One

At ambient temperature, 154.92 g (1.2581 mol) of trimethoxysilane were treated with 0.070 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (23 ppm Ru). At 80 ° C., the trimethoxysilane solution was treated with 61.40 g (0.7943 mol) of allyl chloride. An exothermic reaction was observed and the trimethoxysilane solution was maintained at 79-81 ° C. throughout the allyl chloride addition. The allyl chloride was added over 1 hour using a syringe pump. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the reaction was cooled to ambient temperature and then analyzed. GC data for this reaction are as follows:

compare Example  2

At ambient temperature, 156.57 g (1.2723 moles) of trimethoxysilane were treated with 0.080 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (23 ppm Ru). At 80 ° C., the trimethoxysilane solution was treated with 62.10 g (0.8033 mol) of allyl chloride. An exothermic reaction was observed and the trimethoxysilane solution was maintained at 79-81 ° C. throughout the allyl chloride addition. The allyl chloride was added over 1 hour using a syringe pump. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the reaction was cooled to ambient temperature and then analyzed. GC data for this reaction are as follows:

compare Example  3

Example 3 was carried out in the same manner as in Comparative Example 1 except that allyl chloride used was purchased from Aldrich Chemical. GC data for this reaction are as follows:

compare Example  4

Example 4 was carried out in the same manner as in Comparative Example 1 except that allyl chloride used was purchased from Aldrich Chemical. GC data for this reaction are as follows:

All reactions were added with allyl chloride for 1 hour using 60% molar excess of TMS, 20-30 ppm Ru (RuCl ₃ hydrate methanol solution), at 78-83 ° C. for 1 hour at 78-83 ° C. Addition was carried out. All GC data was normalized to excess TMS by dividing the GC value of each component by the following value: (100.0-GC value of TMS). All GC data were obtained by the SV Chrom Researcher.

compare Example  5

This comparative example was performed similar to Example 1 as reported in US Pat. No. 6,015,920 to Schilling Jr. and Bowman. Over an 8 hour course (4 turnovers), 1.85 g / min of novel trimethoxysilane, 0.78 g / min of allyl chloride, and 3.85% Ru of a solution of ruthenium (III) chloride at 0.114 mL / hour Weight / weight) Methanol solution was added to a 1 liter glass reactor. Constant levels were maintained in the stirrer reactor so that the residence time was 2 hours. The reactor was maintained at 75 ° C. The catalyst load was -20 ppm Ru and the ratio of trimethoxysilane to allyl chloride was maintained at -2.0: 1.0. A water cooler was used on the reactor. At start up, the reactor contained ˜53% chloropropyltrimethoxysilane, ˜41% trimethoxysilane and ˜20 ppm Ru (weight / weight). The crude CPTMS in the reactor was based on the average GC weight percent and standard deviation for four turnovers in the reactor.

During the continuous process, the material in the reactor was continuously fed to the second tray from the top of the 15 tray old show column. The reboiler temperature of the column was maintained at 167-169 ° C. It was recycled back to the reactor with fresh trimethoxysilane at a rate of 1.16 g / min. The above composition, based on the average GC data weight percent and standard deviation for four reactor turnovers, is as follows:

Strip material from the column reboiler unit was continuously fed into the CPTMS receiving bath. Over the course of 8 hours (4 turnovers), crude CPTMS was collected at a rate of 2.21 g / min and its composition based on the average GC wt% and standard deviation for 4 turnovers was as follows:

compare Example  6

At ambient temperature, 28.73 g (0.2328 mol) of trimethoxysilane were treated with 0.033 g of a 3.85% Ru (weight / weight) methanol solution of ruthenium (III) chloride hydrate (30 ppm Ru). The trimethoxysilane solution was warmed and treated with 13.30 g (0.1454 mol) of metallyl chloride at 80 ° C. Metallyl chloride was added over 1 hour while maintaining the trimethoxysilane solution at 78-83 ° C. After the addition was completed, the reaction was maintained at 80 ° C. for 1 hour. After this time, the solution was analyzed by GC. GC data for this reaction are as follows:

Claims (10)

Molar excess of the olefin halides of formula H ₂ C═CR ³ CR ⁴ R ⁵ X, wherein R ³ , R ⁴ , R ⁵ and X have the following meanings: (R ¹ ) _x (R ² O) _{3 - x} SiH (where R ^1, R ² and x are to mean having) including alkoxysilane and, Sikkim electron-donating aromatic compound is reacted in a reaction medium of a ruthenium-containing catalyst and the reaction promotion effective amount of a catalytically effective amount Method for producing a halo organic alkoxysilane of the formula: (R ¹ ) _x (R ² O) _{3- x} SiCH ₂ CHR ³ CR ⁴ R ⁵ X Where R ¹ is alkyl having 1 to 6 carbon atoms, R ² is alkyl having 1 to 6 carbon atoms, R ³ is alkyl or hydrogen of 1 to 6 carbon atoms, R ⁴ is alkyl having 1 to 6 carbon atoms, hydrogen or halogen, R ⁵ is hydrogen or alkyl of 1 to 6 carbon atoms, X is halogen, x is 0, 1 or 2. The method of claim 1, Electron-donating aromatic compounds include benzene, ethylbenzene, diethylbenzene, triethylbenzene, n-butylbenzene, di-t-butylbenzene, bibenzyl, toluene, t-butyltoluene, anisole, 1-phenylhexane, 1- And phenyldodecane, m-xylene, mesitylene, p-cymene, diphenylmethane, triphenylmethane, phenyl ether, phenothiazine, and biphenyl. The method according to claim 1 or 2, Wherein the electron donating aromatic compound is present in an amount of from about 1 to about 100 molar equivalents relative to moles of ruthenium metal. The method according to any one of claims 1 to 3, Wherein the electron donating aromatic compound is present in an amount of from about 20 to about 30 molar equivalents relative to the moles of ruthenium metal. The method according to any one of claims 1 to 4, The olefin halide is selected from the group consisting of allyl chloride, metallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene and 2-chloropropene, and the alkoxysilane is trimethoxysilane, methyl A method selected from the group consisting of dimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane and diethyl ethoxysilane. The method according to any one of claims 1 to 5, The cumulative molar ratio of alkoxysilane to olefin halide ranges from about 1.3 to about 3.0. The method according to any one of claims 1 to 6, The reaction is carried out at a temperature of about 50 to about 130 ° C. The method according to any one of claims 1 to 7, Ruthenium-containing catalysts include Ru ₃ (CO) ₁₂ , [Ru (CO) ₃ Cl ₂ ] ₂ , cyclooctadiene-RuCl ₂ , RuCl ₃ , (Ph ₃ P) ₂ Ru (CO) ₂ Cl ₂ , (Ph ₃ P) ₃ Ru (CO) H ₂ , Fe phase Ru, Al ₂ O ₃ phase Ru, carbon phase Ru, Ru (AcAc) ₃ , and RuBr ₃ . The method according to any one of claims 1 to 8, The amount of ruthenium present in the reaction medium is from about 5 to about 100 ppm by weight of the reactants. Molar excess of the olefin chloride of the formula H ₂ C═CR ³ CR ⁴ R ⁵ Cl, wherein R ³ , R ⁴ and R ⁵ has the following meaning (CH ₃ ) _x (CH ₃ O) _{3- x} About 1 to about 100 for moles of ruthenium containing catalyst and ruthenium containing catalyst containing methoxysilane of SiH (where x has the following meaning) and about 5 to about 100 ppm ruthenium based on the total weight of the reactants A chloroalkylme of formula: comprising reacting a molar equivalent of methoxysilane to olefin chloride from about 1.3 to about 3.0 at a temperature of about 60 to about 130 ° C. in a reaction medium to which a molar equivalent of electron donating aromatic compound is added. Process for preparing oxysilane: (CH ₃ ) _x (CH ₃ O) _{3- x} SiCH ₂ CHR ³ CR ⁴ R ⁵ Cl Where R ³ is alkyl or hydrogen of 1 to 6 carbon atoms, R ⁴ is alkyl, hydrogen or chloride having 1 to 6 carbon atoms, R ⁵ is hydrogen or alkyl of 1 to 6 carbon atoms, x is 0, 1 or 2.