JP2007538069A - Method for producing haloorganoalkoxysilane - 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

  The present invention relates to a method for producing certain haloorganosilicon compounds. More specifically, the present invention relates to a process for producing haloorganoalkoxysilanes such as chloropropyltrimethoxysilane.

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

  U.S. Pat. No. 6,191,297 describes a two-stage process involving ethanol esterification of the product obtained from a platinum-catalyzed hydrosilylation reaction of trichlorosilane and allyl chloride. This method is very material intensive and plant intensive due to the low yield and significant production of by-product (propyltrichlorosilane).

A potentially economical route is the direct hydrosilylation reaction of triethoxysilane and allyl chloride. Platinum is the most widely used hydrosilylation catalyst, and it has also been reported to use it in the hydrosilylation reaction of allyl chloride with triethoxysilane. According to US Pat. No. 3,795,656, a Pt-catalyzed hydrosilylation reaction of allyl chloride with triethoxysilane has yielded a yield of 70%. Belyakova et al. , Obshch. Khim 1974, 44, 2439-2442 describes a Pt-catalyzed hydrosilylation reaction between silane and allyl chloride, and 14% yield for chloropropyltriethoxysilane. As disclosed in JP-A-11-199588, in the Pt-catalyzed hydrosilylation reaction of trimethoxysilane and allyl chloride, chloropropyltrimethoxysilane is obtained in a yield of 70%.

  The main constraint on the hydrosilylation reaction between allyl chloride and silane is a competitive elimination reaction. With platinum, the competitive elimination reaction is more pronounced with alkoxysilanes than with chlorosilanes. Rhodium and palladium mainly give elimination products.

  Iridium has been reported to be a very efficient catalyst for the hydrosilylation reaction between allyl chloride and triethoxysilane. According to US Pat. No. 5,616,762, the iridium-catalyzed hydrosilylation reaction of triethoxysilane and allyl chloride is described as being very selective to chloropropyltriethoxysilane with very few by-products. . Japanese Patent Application No. 4-225170 (Japanese Patent Application Laid-Open No. 06-10052) reports similar results regarding the iridium-catalyzed hydrosilylation reaction of allyl chloride and trimethoxysilane. In U.S. Pat. No. 4,658,050, an olefin iridium complex is used in the iridium-catalyzed hydrosilylation reaction of alkoxysilane and allyl chloride.

Ruthenium has been reported to be a very efficient catalyst for the hydrosilylation reaction of allyl chloride with trimethoxysilane. Japanese Patent No. 2976011 discloses that a Ru-catalyzed hydrosilylation reaction of triethoxysilane and allyl chloride yields chloropropyltriethoxysilane in a yield of about 41%. US Pat. No. 5,559,264 describes the hydrosilylation reaction of methoxysilane and allyl chloride in the presence of a ruthenium catalyst and preferably in the substantial absence of a solvent to give a chloroalkylalkoxysilane. Tanaka et al. , J. et al. Mol. Catal. 1993, 81, 207-214 report a ruthenium carbonyl-catalyzed hydrosilylation reaction of trimethoxysilane and allyl chloride. Japanese Patent Application No. 8-261232 (Japanese Patent Laid-Open No. 10-085605) discloses the same reaction. The activation of ruthenium carbonyl for use as a hydrosilylation catalyst is described.
US Pat. No. 6,191,297 US Pat. No. 3,795,656 JP-A-11-199588 US Pat. No. 5,616,762 Japanese Patent Laid-Open No. 06-100572 US Pat. No. 4,658,050 Japanese Patent No. 2976011 US Pat. No. 5,559,264 Japanese Patent Laid-Open No. 10-085605 Belyakova et al. Obshch. Khim 1974, 44, 2439-2442 Tanaka et al. , J .; Mol. Catal. 1993, 81, 207-214

In the present invention, a method for producing a haloorganoalkoxysilane of the following formula,
(R ¹ ) _x (R ² O) _3-x SiCH ₂ CHR ³ CR ⁴ R ⁵ X
Wherein R ¹ is alkyl having 1 to 6 carbon atoms, R ² is alkyl having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms or hydrogen, ⁴ is alkyl having 1 to 6 carbon atoms, hydrogen or halogen, R ⁵ is hydrogen or alkyl having 1 to 6 carbon atoms, X is halogen, and x is 0, 1 or 2.
In a reaction medium to which a catalytically effective amount of a ruthenium-containing catalyst and a reaction-promoting effective amount of an electron-donating aromatic compound are added, an olefin halide having the following general formula is added:
H ₂ C = CR ³ CR ⁴ R ⁵ X
(Wherein R ³ , R ⁴ , R ⁵ and X have the above-mentioned meanings.)
A molar excess of alkoxysilane of the general formula
(R ¹ ) _x (R ² O) _3-x SiH
(Wherein R ¹ , R ² and x have the above-mentioned meanings)
A method comprising reacting is provided. The aromatic compound may contain an electron donating group to promote the reaction. In addition, the aromatic compound must be present in an amount sufficient to promote the reaction but not inhibit the reaction. Furthermore, the aromatic compound should be present simultaneously with the ruthenium catalyst in the alkoxysilane or catalyst solution described above.

  The haloorganoalkoxysilane formation reaction between the olefin halide and the alkoxysilane in the presence of the ruthenium catalyst and the aromatic compound promoter as described above is considered to proceed by the following reaction.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｘ及びｘは上述の意味を有する。

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and x have the above-mentioned meanings.

  The method of the present invention can be carried out in various commercially available equipment currently used for hydrosilylation reactions, including equipment for carrying out hydrosilylation reactions in a continuous manner.

  If the process is integrated with a source of trimethoxysilane produced directly from, for example, metallic silicon and methanol, not only does it eliminate the use of corrosive and harmful hydrochlorosilanes, but also the use of products derived from hydrochlorosilanes. Production of large amounts of chlorine-containing waste by-products can be eliminated.

  Several factors have been found to be important for obtaining high yields of haloorganoalkoxysilanes in a one-step hydrosilylation reaction between an olefin halide and an alkoxysilane. First, when all reactants are brought together from the beginning in a batch reaction, the selectivity for the desired haloorganoalkoxysilane is highest at low temperatures and low reaction rates. Secondly, increasing the temperature to increase the reaction rate can maintain selectivity by limiting the concentration of olefin halide in the reaction mixture. Thirdly, most inert solvents (especially aromatic solvents) can adversely affect rate, selectivity, or both, especially when used at relatively high levels for reaction solvents, especially in batch systems.

  Preferably, the process involves the slow addition of the olefin halide to the reaction medium containing the alkoxysilane, in a semi-batch or continuous operation, in the presence of a ruthenium metal containing catalyst and an electron donating aromatic compound as a cocatalyst. It is carried out by reacting. This order of addition effectively keeps the concentration of unreacted olefin halide in the reaction medium to a minimum relative to the alkoxysilane, and thus a very large molar excess of alkoxysilane relative to the olefin halide in the reaction medium. The amount is established effectively. In a typical embodiment, the maximum addition rate of olefin halide to alkoxysilane is determined by the reaction rate. The rate of reaction will be apparent to those skilled in the art, whether using small laboratory reactors or very large commercial reactors, reaction temperature, catalyst concentration, electron donating aromatics It depends to some extent on the cocatalyst concentration and the heat transfer limit of the reactor.

  A preferred mixing sequence can be achieved in semi-batch or continuous operation. In a semi-batch operation, the reactor is initially charged with the majority of the molar excess of alkoxysilane, preferably the total required amount. Next, an aromatic compound and a ruthenium catalyst can be added to the alkoxysilane and allowed to react with the olefin halide. Alternatively, the olefin halide is slowly added to a reactor containing a molar excess of alkoxysilane and the alkoxysilane and olefin halide are reacted in the presence of a ruthenium catalyst and an aromatic compound promoter. As used herein, “slow addition of olefin halide” generally means a rate of less than about 3 moles per hour per mole of alkoxysilane, preferably less than 1 mole per hour per mole of alkoxysilane. For example, in a half-batch operation, if 1 mole of olefin halide is added to a reactor containing 2 moles of alkoxysilane in 15 minutes, a rate of 2 moles of olefin halide added per mole of alkoxysilane is achieved. After the olefin halide is added to the reactor, the reaction is continued until complete conversion of the olefin halide is achieved. This is primarily a function of temperature, catalyst concentration and aromatic cocatalyst concentration, but complete conversion is generally achieved in 1-15 hours, more usually in 1-10 hours. The completion of the reaction in 1 to 5 hours is not uncommon. A portion of the alkoxysilane can be added in admixture with the olefin halide or can be added simultaneously with the addition of the olefin halide as a separate stream.

  In continuous operation, the reactor typically contains an olefin halide and an olefin halide such that the molar ratio of alkoxysilane to olefin halide is about 1.3 to about 3.0, preferably about 1.8 to about 2.3. A separate stream of alkoxysilane is charged. Such an operation ensures that the proper excess of alkoxysilane is present in the reactor under steady operating conditions. For the preferred alkoxysilane (methoxysilane) and the preferred olefin halide (allyl chloride), the preferred molar ratio is from about 1.6 to about 2.3. In continuous operation, the aromatic compound cocatalyst and ruthenium catalyst can be added separately to the olefin halide and alkoxysilane, or preferably in a reactor charged with an independent stream of olefin halide and alkoxysilane as described above. Can be added as

  The aromatic compound cocatalyst used in the process of the present invention is indicated by a reaction promoting amount, ie (high product purity and / or low production of by-products such as organoalkoxysilanes and haloalkoxysilanes. As such, it must be present in the reaction medium in an amount that is less than the amount that inhibits the reaction but that increases the yield of the reaction. In general, an effective amount of aromatic compound promoter is about 1 to about 100 molar equivalents per mole of ruthenium metal, preferably about 5 to about 50 molar equivalents per mole of ruthenium metal, and more preferably about 20 per mole of ruthenium metal. Within the range of about 30 molar equivalents.

  Other hydrosilylation reaction conditions (eg, temperature, mole ratio of reactants, pressure, time and catalyst concentration) are not strictly limited. There is wide latitude in adjusting these factors for economical and safe use of various manufacturing equipment. Such equipment typically has equipment for heating, cooling, stirring, maintaining an inert atmosphere, and purification (eg, by filtration or distillation). Thus, the equipment commonly used in the prior art for large-scale commercial hydrosilylation reactions is the reflux condensation of hydrosilicon compounds in a zone containing a heterogeneous supported hydrosilylation catalyst and an electron donating aromatic compound promoter. It can be used in the process of the present invention, including an apparatus for adding an olefin halide to a sex stream.

  Reaction conditions include a reaction temperature of about 50 to about 130 ° C, with about 60 to about 80 ° C being preferred. In general, the process is carried out at a pressure above atmospheric pressure, with atmospheric pressure being preferred. It has been observed that the process of the present invention can provide high yields of the desired chloroalkylalkoxysilane in a true batch system. However, batch reactions are usually carried out at low temperatures, resulting in long reaction times. Accordingly, it is preferred to carry out the hydrosilylation at high temperatures by adding an olefin halide to a molar excess of alkoxysilane in the presence of a ruthenium metal-containing catalyst and an aromatic compound promoter. One particularly preferred mode of operation (semi-batch mode) includes the total required amount of alkoxysilane (eg, about 1.6 to about 2.3 molar equivalents of trimethoxysilane relative to the total amount of olefin halide to be added). By slowly adding the total required amount of olefin halide to the reactor over a period of time, an olefin halide addition rate of less than 3 moles per hour per mole of alkoxysilane is achieved.

In one embodiment, the reactor includes a ruthenium 5~100ppm as RuCl ₃ hydrate based on the weight of the total reactants. In another embodiment, the reaction medium contains about 15-25 ppm ruthenium based on the weight of the total reactants in the reactor. In yet another embodiment, the reactor together with the containing ruthenium 5~50ppm based on the weight of the total reactants as RuCl ₃ hydrate, comprises a reaction promoting effective amount of an aromatic compound co-catalyst, the reaction is about It is carried out at 50 to about 130 ° C, preferably at about 60 to about 80 ° C. Excess alkoxysilane, ruthenium catalyst and aromatic cocatalyst can be effectively recycled to the next batch.

  The method of the present invention is nearly quantitative for the conversion of olefin halides to the desired haloorganoalkoxysilane product, particularly when chloropropyltrimethoxysilane is obtained by reaction of allyl chloride with trimethoxysilane, The production of undesirable by-products is greatly reduced. This reduces the amount of material to be discarded or discarded as waste, material to be isolated as a separate stream (eg, by distillation) or discharged from the reaction system. Since the method of the present invention is highly exothermic, external heating is usually unnecessary and the reaction time is correspondingly short. In general, the only significant amount of impurities that need to be removed from the reaction product is a slight excess of unreacted alkoxysilane, residual catalyst, and aromatic co-catalyst. These can be recycled to the next batch without purification. Low levels of residual halide that may be present in the product can be neutralized by methods known in the art. When the hydrosilylation product of the present invention is used as an intermediate for the production of other organofunctional silicon compounds, its purity after initial synthesis is sufficient to eliminate the need for additional purification (eg, by distillation). obtain.

  For example, when applied to the production of chloropropyltrimethoxysilane, the process of the present invention is higher (calculated on a molar basis relative to the limiting reactant) than any one-stage or two-stage process described in the prior art. This product is given in yield. This is accomplished by adding an effective amount of an aromatic co-catalyst and an effective amount of ruthenium catalyst to the reaction medium. This process also achieves such yields using significantly lower levels of ruthenium metal containing catalysts than any of the processes described in the prior art. In addition, the method of the present invention uses an effective amount of an electron donating aromatic compound that significantly increases product and minimizes waste. This method also provides a high yield per unit volume of equipment used because the use of inert solvents is eliminated and a large amount of waste by-products is not produced. The preferred mixing order of the reactants in the present invention is indeed the opposite of that used to maximize the yield of chloropropyltrichlorosilane in one reported example of a platinum catalyzed reaction of trichlorosilane and allyl chloride. . Moreover, the yields obtained are significantly higher than those reported for platinum catalyzed reactions of triethylsilane and allyl chloride. In this case, the yield is maximized by always adding allyl chloride containing trichlorosilane as a hydrosilylation cocatalyst to triethylsilane.

  The process of the present invention does not require operation at pressures above atmospheric pressure, but by using a closed reactor to prevent the possibility of accidental release of the allyl halide to the environment, high pressure (eg, It is also possible to use pressures up to 2 atmospheres). If a reaction temperature below the atmospheric boiling point of the alkoxysilane is desired, a pressure below atmospheric pressure can also be used.

Suitable olefin halides for use in the present invention include allyl chloride, methallyl 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.

  Alkoxysilanes suitable for use in the present invention include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and the like. . Of these alkoxysilanes, ethoxysilanes are preferred, and triethoxysilane is most preferred.

  The ruthenium metal containing catalyst and the aromatic compound cocatalyst must be present in the reaction medium. These can be added dissolved in alkoxysilanes or olefin halides, or both can be present in a heterogeneous form in the catalyst zone into which the reactants are introduced. A variety of homogeneous and heterogeneous forms of ruthenium metal-containing compounds can be used as catalysts, and the usage level (based on the metal contained) can be as low as in a commercially implemented platinum catalyzed hydrosilylation reaction. For example, a ruthenium concentration of about 2 to 300 ppm is generally suitable.

If oxygen is required for catalyst activation, the amount of oxygen normally present in the commercial feed, particularly in the reactant itself, should generally be sufficient. This is especially true for ruthenium carbonyl catalysts. If further catalyst activation is required, the catalyst is encountered by simply adding dilute oxygen (eg, a mixture containing 3% O ₂ in N ₂ ) to one or more reactants or reaction media. This can be achieved by increasing the oxygen level. If the catalyst is a ruthenium-phosphine complex, there will likely be a need for independent activation.

Suitable ruthenium metal containing catalysts can be selected from homogeneous and heterogeneous ruthenium metal containing compounds and complexes. Examples 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 supported Ru, Al ₂ O ₃ supported Ru, carbon supported Ru, Ru (AcAc) ₃ , RuBr ₃ and the like. In the formula, Ph is a phenyl group, and AcAc is an acetylacetonate group.

Ruthenium metal-containing compounds constituting ruthenium complexes 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 ) Is ineffective as a catalyst for the reaction of trimethoxysilane with an olefin halide in the presence or absence of oxygen. This lack of catalytic activity is consistent with the results of previous researchers who investigated the hydrosilylation of allyl chloride with triethoxysilane. If a phosphine ligand is present, a ligand other than hydrogen or chlorine or another ligand in addition to hydrogen or chlorine (eg carbonyl and olefin ligands) should also be present, with slightly higher levels Activation oxygen may be required. A ruthenium complex containing an aromatic compound (for example, a (π-arene) ruthenium complex containing 1 mol equivalent or more of an aromatic compound relative to a ruthenium metal) is also suitable. Examples of (π-arene) ruthenium complexes are (p-cymene) ruthenium (II) chloride dimer or (benzene) ruthenium (II) chloride dimer.

Preferred ruthenium catalysts are ruthenium chloride compound, RuCl ₃ hydrate is most preferred. The catalyst recovered from one batch can be recycled to the next batch without substantial loss of activity. The usage level of the catalyst is in the range of 1.0 to 300 ppm as the amount of contained Ru metal based on the total amount of charged reactants, but 5 to 50 ppm is preferable.

Suitable aromatic compounds include, for example, benzene, ethylbenzene, diethylbenzene, triethylbenzene, n-butylbenzene, di-t-butylbenzene, bibenzyl, toluene, t-butyltoluene, anisole, 1-phenylhexane, 1-phenyl. Dodecane, Nakyrene® (mixture of C _{8 to} C ₁₂ n-alkylbenzene), Terminol® (mixture of ethylbenzene and bibenzyl isomers), m-xylene, mesitylene, p-cymene, diphenylmethane, triphenyl There are phenylmethane, phenyl ether, phenothiazine and biphenyl. These are about 1 to about 100 molar equivalents relative to the number of moles of ruthenium metal, preferably about 5 to about 50 molar equivalents relative to the number of moles of ruthenium metal, and more preferably about 20 relative to the number of moles of ruthenium metal. It can be present in an amount of about 30 molar equivalents.

  The haloorganoalkoxysilane product of the process of the present invention can be purified by standard means (eg, distillation) or can be used directly without purification when used as an intermediate for subsequent production.

  As described above, the reaction can also be carried out in a continuous mode by adding the alkoxysilane and olefin halide reactant to the reactor such that the alkoxysilane is present in the desired molar excess. At steady state, the reactor contains an excess of alkoxysilane mixed with the haloorganoalkoxysilane product sufficient to allow substantially quantitative production of the desired product. Excess alkoxysilane is advantageous because it can be recovered from the product stream and recycled.

  While the precise scope of the invention is set forth in the following claims, the following specific examples illustrate specific embodiments of the invention and, more particularly, in the manner in which the invention is evaluated. Various aspects are described. However, these examples are described solely for purposes of illustration and should not be construed as limiting the invention. Abbreviations g, ppm, equiv. , GC and TMS represent grams, parts per million, molar equivalents, gas chromatography and triethoxysilane, respectively. The temperature is given in ° C. The% yield is measured by GC using an internal standard except when the yield is determined by actual weight after vacuum distillation of the product. Unless otherwise noted, all reactions were performed at atmospheric pressure under an inert atmosphere of nitrogen using standard laboratory glassware. In each example, the structure of the product was confirmed by GC, GC / mass spectrometry, infrared spectroscopy or nuclear magnetic resonance.

All reactions in the following examples were performed under a nitrogen atmosphere. Allyl chloride, methallyl chloride, trimethoxysilane and RuCl ₃ hydrate was used without further purification. TMS was distilled in a 5-stage Oldershaw tower at atmospheric pressure and stored in glass or stainless steel bottles. Typically, the purity of TMS was about 98% (wt / wt). All GC data was expressed as weight percent (wt / wt) and normalized for excess TMS.

  The following abbreviations and trade names (indicating their properties) are used in the examples.

実施例１
周囲温度で、トリメトキシシラン２９．０２ｇ（０．２３５１モル）をトルエン０．０１６ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０２５ｇ（２４ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 1
At ambient temperature, 29.02 g (0.2351 mol) of trimethoxysilane was added to 0.016 g of toluene and 0.025 g (24 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. The trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例２
周囲温度で、トリメトキシシラン２８．９１ｇ（０．２３４２モル）をトルエン０．０５６ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０２５ｇ（２４ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 2
At ambient temperature, 28.91 g (0.2342 mol) of trimethoxysilane was added to 0.056 g of toluene and 0.025 g (24 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. The trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例３
周囲温度で、トリメトキシシラン２８．９１ｇ（０．２３４２モル）をトルエン０．６４ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０５０ｇ（４７ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 3
At ambient temperature, 28.91 g (0.2342 mol) of trimethoxysilane was added to 0.64 g of toluene and 0.050 g (47 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. The trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例４
周囲温度で、トリメトキシシラン２８．９１ｇ（０．２３４２モル）をトルエン０．６４ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０５０ｇ（４７ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 4
At ambient temperature, 28.91 g (0.2342 mol) of trimethoxysilane was added to 0.64 g of toluene and 0.050 g (47 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. The trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例５
周囲温度で、トリメトキシシラン２８．６７ｇ（０．２３２３モル）をＴｈｅｒｍｉｎｏｌ（登録商標）５９ ０．０１６ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０２０ｇ（１９ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、７８℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 5
At ambient temperature, 28.67 g (0.2323 mol) of trimethoxysilane was added to 0.016 g of Thermolol® 59 and a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Treated with 020 g (19 ppm Ru). This trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例６
周囲温度で、トリメトキシシラン１５０．３４ｇ（１．２２０３モル）をエチルベンゼン０．２８０ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０８０ｇ（２３ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル５９．５６ｇ（０．７７０５モル）で処理した。トリメトキシシラン溶液を８０〜８１℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 6
At ambient temperature, 150.34 g (1.2203 mol) of trimethoxysilane was added to 0.280 g of ethylbenzene and 0.080 g (23 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. The trimethoxysilane solution was heated and treated with 59.56 g (0.7705 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 80-81 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例７
周囲温度で、トリメトキシシラン１６０．７８ｇ（１．３０５６モル）をｎ−ブチルベンゼン０．１４０ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０８０ｇ（２２ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル６３．７２ｇ（０．８２４３モル）で処理した。トリメトキシシラン溶液を８０〜８１℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 7
At ambient temperature, 160.78 g (1.3056 mol) of trimethoxysilane was added to 0.140 g of n-butylbenzene and 0.080 g of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate ( 22ppmRu). This trimethoxysilane solution was heated and treated at 80 ° C. with 63.72 g (0.8243 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 80-81 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例８
周囲温度で、トリメトキシシラン１６１．９６ｇ（１．３１４７モル）をアニソール０．１１０ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０８０ｇ（２２ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル６４．１７ｇ（０．８３０１モル）で処理した。トリメトキシシラン溶液を８０〜８１℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 8
At ambient temperature, 161.96 g (1.3147 mol) of trimethoxysilane was added to 0.110 g of anisole and 0.080 g (22 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. This trimethoxysilane solution was heated and treated at 80 ° C. with 64.17 g (0.8301 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 80-81 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例９
周囲温度で、トリメトキシシラン１６５．２２ｇ（１．３４１３モル）をジフェニルメタン０．１７０ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０８０ｇ（２２ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル６５．４７ｇ（０．８４６９モル）で処理した。トリメトキシシラン溶液を８０〜８１℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 9
At ambient temperature, 165.22 g (1.3413 mol) of trimethoxysilane was added to 0.170 g of diphenylmethane and 0.080 g (22 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. This trimethoxysilane solution was heated and treated at 65 ° C. with 65.47 g (0.8469 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 80-81 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１０
周囲温度で、トリメトキシシラン２８．３４ｇ（０．２２９６モル）をビベンジル０．０２４ｇ及び塩化ルテニウム（III）水和物のメタノール溶液としての３．８５％Ｒｕ（ｗｔ／ｗｔ）０．０２０ｇで処理した。このトリメトキシシラン溶液を加温し、７８℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 10
At ambient temperature, 28.34 g (0.2296 mol) of trimethoxysilane was treated with 0.024 g of bibenzyl and 0.020 g of 3.85% Ru (wt / wt) as a methanol solution of ruthenium (III) chloride hydrate. did. This trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１１
周囲温度で、トリメトキシシラン１６５．２２ｇ（１．３４１６モル）をトリフェニルメタン０．２５０ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０８０ｇ（２２ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、７８℃で塩化アリル６５．４８ｇ（０．８４７０モル）で処理した。トリメトキシシラン溶液を８０〜８１℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 11
At ambient temperature, 165.22 g (1.3416 mol) of trimethoxysilane was added to 0.250 g of triphenylmethane and 0.080 g (22 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. ). This trimethoxysilane solution was heated and treated with 65.48 g (0.8470 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 80-81 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１２
周囲温度で、トリメトキシシラン２８．６１ｇ（０．２３１８モル）をビベンジル０．０２４ｇ及び塩化ルテニウム（III）水和物のメタノール溶液としての３．８５％Ｒｕ（ｗｔ／ｗｔ）０．０２０ｇで処理した。このトリメトキシシラン溶液を加温し、６０℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を６０〜６３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を６０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 12
At ambient temperature, 28.61 g (0.2318 mol) of trimethoxysilane was treated with 0.024 g of bibenzyl and 0.020 g of 3.85% Ru (wt / wt) as a methanol solution of ruthenium (III) chloride hydrate. did. This trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 60 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 60-63 ° C. After the addition was complete, the reaction was continued at 60 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１３
周囲温度で、トリメトキシシラン１６１．１６ｇ（１．３０８２モル）をビベンジル０．１９０ｇ及び塩化ルテニウム（III）水和物のメタノール溶液としての３．８５％Ｒｕ（ｗｔ／ｗｔ）０．０８０ｇ（２２ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、７０℃で塩化アリル６３．８５ｇ（０．８２６０モル）で処理した。トリメトキシシラン溶液を７０〜７２℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を７０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 13
At ambient temperature, 161.16 g (1.3082 mol) of trimethoxysilane was added to 0.190 g of bibenzyl and 0.080 g (22 ppmRu) of 3.85% Ru (wt / wt) as a methanol solution of ruthenium (III) chloride hydrate. ). This trimethoxysilane solution was heated and treated at 70 ° C. with 63.85 g (0.8260 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 70-72 ° C. After the addition was complete, the reaction was continued at 70 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１４
周囲温度で、トリメトキシシラン２８．４１ｇ（０．２３０２モル）をビベンジル０．０３２ｇ及び塩化ルテニウム（III）水和物のメタノール溶液としての３．８５％Ｒｕ（ｗｔ／ｗｔ）０．０２０ｇで処理した。このトリメトキシシラン溶液を加温し、７８℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 14
At ambient temperature, 28.41 g (0.2302 mol) of trimethoxysilane was treated with 0.032 g of bibenzyl and 0.020 g of 3.85% Ru (wt / wt) as a methanol solution of ruthenium (III) chloride hydrate. did. This trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１５
周囲温度で、トリメトキシシラン１６３．０３ｇ（１．３２４８モル）をビベンジル０．２５ｇ及び塩化ルテニウム（III）水和物のメタノール溶液としての３．８５％Ｒｕ（ｗｔ／ｗｔ）０．１００ｇで処理した。このトリメトキシシラン溶液を加温し、９５℃で塩化アリル６４．６６ｇ（０．８３６４モル）で処理した。トリメトキシシラン溶液を９４〜９６℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を９５℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 15
At ambient temperature, 163.03 g (1.3248 mol) of trimethoxysilane was treated with 0.25 g of bibenzyl and 0.100 g of 3.85% Ru (wt / wt) as a methanol solution of ruthenium (III) chloride hydrate. did. This trimethoxysilane solution was heated and treated at 95 ° C. with 64.66 g (0.8364 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 94-96 ° C. After the addition was complete, the reaction was continued at 95 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１６
周囲温度で、トリメトキシシラン２８．３２ｇ（０．２２９４モル）を（ｐ−シメン）塩化ルテニウム（II）二量体の２．２３％Ｒｕ（ｗｔ／ｗｔ）ジクロロメタン溶液０．０３６ｇで処理した。このトリメトキシシラン溶液を加温し、７８℃で塩化アリル１１．２ｇ（０．１４４９モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 16
At ambient temperature, 28.32 g (0.2294 mol) of trimethoxysilane was treated with 0.036 g of a 2.23% Ru (wt / wt) dichloromethane solution of (p-cymene) ruthenium (II) chloride dimer. This trimethoxysilane solution was heated and treated with 11.2 g (0.1449 mol) of allyl chloride at 78 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１７
周囲温度で、トリメトキシシラン１６０．０７ｇ（１．３００８モル）を、トルエン０．０７４ｇ、塩化ルテニウム（III）水和物０．１２０ｇ及びメタノール６２ｇからなる触媒溶液（Ｒｕに対してトルエン１．７モル当量）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル６３．４０ｇ（０．８２１３モル）で処理した。トリメトキシシラン溶液を７９〜８２℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 17
At ambient temperature, 160.07 g (1.3008 mol) of trimethoxysilane was added to 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 toluene with respect to Ru). Molar equivalent). This trimethoxysilane solution was heated and treated at 80 ° C. with 63.40 g (0.8213 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 79-82 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

触媒溶液
塩化ルテニウム（III）水和物をメタノール中に溶解し、この溶液を室温で表記量のジフェニルメタンで処理して２種の溶液を調製した。

Catalyst solution Ruthenium (III) chloride hydrate was dissolved in methanol, and this solution was treated with the indicated amount of diphenylmethane at room temperature to prepare two solutions.

混合後、得られた溶液は直ちに使用することができた。

After mixing, the resulting solution could be used immediately.

Example 18
At ambient temperature, 163.93 g (1.3330 mol) of trimethoxysilane were treated with 0.200 g (21 ppmRu) of catalyst solution A prepared as described above. This trimethoxysilane solution was heated and treated at 80 ° C. with 64.89 g (0.8394 mol) of allyl chloride. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 79-81 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

実施例１９
８時間（４回のターンオーバー）にわたり、１リットルガラス反応器にシリンジポンプを用いてトリメトキシシランを１．４７ｇ／ｍｉｎの速度で添加し、塩化アリルを０．７８ｇ／ｍｉｎの速度で添加し、調製した触媒溶液Ｂを０．１６７ｍＬ／ｈｒの速度で添加した。滞留時間が２時間になるようにして、攪拌反応器内に一定のレベルを維持した。反応器は７５℃に保った。触媒添加量は約２０ｐｐｍＲｕであり、トリメトキシシランと塩化アリルとの比は約２．０：１．０に保った。反応器上には水コンデンサーを使用した。運転開始直後、反応器は約５３％のクロロプロピルトリメトキシシラン、約４１％のトリメトキシシラン及び約２０ｐｐｍのＲｕ（ｗｔ／ｗｔ）を含んでいた。反応器内の粗ＣＰＴＭＳは、反応器内での４回のターンオーバーに関する平均ＧＣデータとしてのｗｔ％及び標準偏差に基づけば、下記の成分からなっていた。

Example 19
Over 8 hours (4 turnovers), trimethoxysilane was added at a rate of 1.47 g / min and allyl chloride was added at a rate of 0.78 g / min using a syringe pump into a 1 liter glass reactor. The prepared catalyst solution B was added at a rate of 0.167 mL / hr. A constant level was maintained in the stirred reactor so that the residence time was 2 hours. The reactor was kept at 75 ° C. The amount of catalyst added was about 20 ppm Ru, and the ratio of trimethoxysilane to allyl chloride was kept at about 2.0: 1.0. A water condenser was used on the reactor. Immediately after start-up, the reactor contained about 53% chloropropyltrimethoxysilane, about 41% trimethoxysilane and about 20 ppm Ru (wt / wt). The crude CPTMS in the reactor consisted of the following components based on wt% and standard deviation as average GC data for 4 turnovers in the reactor.

連続運転中、反応器内の材料は１５段型Ｏｌｄｅｒｓｈａｗ塔の頂部から２番目の段に連続的に供給した。塔のリボイラー温度は１６７〜１６９℃に保った。軽質分は、新鮮なトリメトキシシランと共に、１．１７ｇ／ｍｉｎの速度で反応器に再循環させた。４回の反応器ターンオーバーに関する平均ＧＣデータとしてのｗｔ％及び標準偏差に基づく軽質分の組成は、以下の通りであった。

During continuous operation, the material in the reactor was continuously fed to the second stage from the top of the 15-stage Oldershaw column. The column reboiler temperature was maintained at 167-169 ° C. The light fraction was recycled to the reactor with fresh trimethoxysilane at a rate of 1.17 g / min. The composition of light weight based on wt% and standard deviation as average GC data for 4 reactor turnovers was as follows:

塔のリボイラーユニットからのストリップ材料をＣＰＴＭＳ貯留器に連続的に供給した。８時間（４回のターンオーバー）にわたり、得られた粗ＣＰＴＭＳを２．２１ｇ／ｍｉｎの速度で捕集したが、４回の反応器ターンオーバーに関する平均ＧＣデータとしてのｗｔ％及び標準偏差に基づくその組成は、以下の通りであった。

Strip material from the tower reboiler unit was continuously fed to the CPTMS reservoir. Over 8 hours (4 turnovers), the resulting crude CPTMS was collected at a rate of 2.21 g / min, but based on wt% and standard deviation as average GC data for 4 reactor turnovers. Its composition was as follows.

実施例２０
周囲温度で、トリメトキシシラン２８．４８ｇ（０．２３０７モル）をビベンジル０．０３４ｇ及び塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０３３ｇ（３０ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル１３．３０ｇ（０．１４５４モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を７０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Example 20
At ambient temperature, 28.48 g (0.2307 mol) of trimethoxysilane was added to 0.034 g of bibenzyl and 0.033 g (30 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. Processed. This trimethoxysilane solution was heated and treated with 13.30 g (0.1454 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 70 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

比較例１
周囲温度で、トリメトキシシラン１５４．９２ｇ（１．２５８１モル）を塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０７０ｇ（２３ｐｐｍＲｕ）で処理して加温した。８０℃で、このトリメトキシシラン溶液を塩化アリル６１．４０ｇ（０．７９４３モル）で処理した。発熱反応が認められ、塩化アリルの添加中はトリメトキシシラン溶液を７９〜８１℃に保った。シリンジポンプを用いて塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、反応混合物を周囲温度に放冷し、次いで分析した。この反応に関するＧＣデータは以下の通りであった。

Comparative Example 1
At ambient temperature, 154.92 g (1.2581 mol) of trimethoxysilane was treated with 0.070 g (23 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate and warmed. did. At 80 ° C., this trimethoxysilane solution was treated with 61.40 g (0.7943 mol) of allyl chloride. An exothermic reaction was observed, and the trimethoxysilane solution was kept at 79-81 ° C. during the addition of allyl chloride. Allyl chloride was added over 1 hour using a syringe pump. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the reaction mixture was allowed to cool to ambient temperature and then analyzed. The GC data for this reaction was as follows:

比較例２
周囲温度で、トリメトキシシラン１５６．５７ｇ（１．２７２３モル）を塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０８０ｇ（２３ｐｐｍＲｕ）で処理して加温した。８０℃で、このトリメトキシシラン溶液を塩化アリル６２．１０ｇ（０．８０３３モル）で処理した。発熱反応が認められ、塩化アリルの添加中はトリメトキシシラン溶液を７９〜８１℃に保った。シリンジポンプを用いて塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、反応混合物を周囲温度に放冷し、次いで分析した。この反応に関するＧＣデータは以下の通りであった。

Comparative Example 2
At ambient temperature, 156.57 g (1.2723 mol) of trimethoxysilane was treated with 0.080 g (23 ppmRu) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate and heated. did. At 80 ° C., this trimethoxysilane solution was treated with 62.10 g (0.8033 mol) of allyl chloride. An exothermic reaction was observed, and the trimethoxysilane solution was kept at 79-81 ° C. during the addition of allyl chloride. Allyl chloride was added over 1 hour using a syringe pump. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the reaction mixture was allowed to cool to ambient temperature and then analyzed. The GC data for this reaction was as follows:

比較例３
Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ社から購入した塩化アリルを使用した点を除き、比較例１と同様にして実施例３を実施した。この反応に関するＧＣデータは以下の通りであった。

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

比較例４
Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ社から購入した塩化アリルを使用した点を除き、比較例１と同様にして実施例４を実施した。この反応に関するＧＣデータは以下の通りであった。

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

すべての反応は、塩化アリルに対して６０％モル過剰量のＴＭＳ及び２０〜３０ｐｐｍのＲｕ（ＲｕＣｌ_３水和物のメタノール溶液）を用いて７８〜８３℃で実施した。その際、塩化アリルを１時間にわたり添加し、次いで７８〜８３℃に１時間保った。すべてのＧＣデータは、各成分のＧＣ値を次の値（１００．０−ＴＭＳのＧＣ値）で割ることにより、過剰のＴＭＳについて正規化した。すべてのＧＣデータは、ＳＶ Ｃｈｒｏｍ社の実験室員によって求められた。

All reactions were carried out at seventy-eight to eighty-three ° C. using a 60% molar excess of TMS and 20~30ppm of Ru (methanol RuCl ₃ hydrate) relative to allyl chloride. At that time, allyl chloride was added over 1 hour and then kept at 78-83 ° C for 1 hour. All GC data was normalized for excess TMS by dividing the GC value of each component by the next value (100.0-TMS GC value). All GC data was determined by SV Chrom laboratory personnel.

Comparative Example 5
This comparative example was carried out in the same manner as Example 1 reported in US Pat. No. 6,015,920 (Schilling Jr. and Bowman). Over a period of 8 hours (4 turnovers), a 1 liter glass reactor was charged with 1.45 g / min fresh trimethoxysilane, 0.78 g / min allyl chloride, and 3.85% Ru (wt) of ruthenium (III) chloride. / Wt) 0.114 mL / hr of methanol solution was added. A constant level was maintained in the stirred reactor so that the residence time was 2 hours. The reactor was kept at 75 ° C. The amount of catalyst added was about 20 ppm Ru, and the ratio of trimethoxysilane to allyl chloride was kept at about 2.0: 1.0. A water condenser was used on the reactor. Immediately after start-up, the reactor contained about 53% chloropropyltrimethoxysilane, about 41% trimethoxysilane, and about 20 ppm Ru (wt / wt). The crude CPTMS in the reactor consisted of the following components based on wt% and standard deviation as average GC data for 4 turnovers in the reactor.

連続運転中、反応器内の材料は１５段型Ｏｌｄｅｒｓｈａｗ塔の頂部から２番目の段に連続的に供給した。塔のリボイラー温度は１６７〜１６９℃に保った。軽質分は、新鮮なトリメトキシシランと共に、１．１６ｇ／ｍｉｎの速度で反応器に再循環させた。４回の反応器ターンオーバーに関する平均ＧＣデータとしてのｗｔ％及び標準偏差に基づく軽質分の組成は、以下の通りであった。

During continuous operation, the material in the reactor was continuously fed to the second stage from the top of the 15-stage Oldershaw column. The column reboiler temperature was maintained at 167-169 ° C. The light fraction was recycled to the reactor with fresh trimethoxysilane at a rate of 1.16 g / min. The composition of light weight based on wt% and standard deviation as average GC data for 4 reactor turnovers was as follows:

塔のリボイラーユニットからのストリップ材料をＣＰＴＭＳ貯留器に連続的に供給した。８時間（４回のターンオーバー）にわたり、粗ＣＰＴＭＳを２．２１ｇ／ｍｉｎの速度で捕集したが、４回の反応器ターンオーバーに関する平均ＧＣデータとしてのｗｔ％及び標準偏差に基づくその組成は、以下の通りであった。

Strip material from the tower reboiler unit was continuously fed to the CPTMS reservoir. Over 8 hours (4 turnovers), crude CPTMS was collected at a rate of 2.21 g / min, but its composition based on wt% and standard deviation as average GC data for 4 reactor turnovers. It was as follows.

比較例６
周囲温度で、トリメトキシシラン２８．７３ｇ（０．２３２８モル）を塩化ルテニウム（III）水和物の３．８５％Ｒｕ（ｗｔ／ｗｔ）メタノール溶液０．０３３ｇ（３０ｐｐｍＲｕ）で処理した。このトリメトキシシラン溶液を加温し、８０℃で塩化アリル１３．３０ｇ（０．１４５４モル）で処理した。トリメトキシシラン溶液を７８〜８３℃に保ちながら塩化アリルを１時間にわたり添加した。その添加完了後、反応を８０℃で１時間続けた。しかる後、溶液をＧＣで分析した。この反応に関するＧＣデータは以下の通りであった。

Comparative Example 6
At ambient temperature, 28.73 g (0.2328 mol) of trimethoxysilane was treated with 0.033 g (30 ppm Ru) of a 3.85% Ru (wt / wt) methanol solution of ruthenium (III) chloride hydrate. This trimethoxysilane solution was heated and treated with 13.30 g (0.1454 mol) of allyl chloride at 80 ° C. Allyl chloride was added over 1 hour while keeping the trimethoxysilane solution at 78-83 ° C. After the addition was complete, the reaction was continued at 80 ° C. for 1 hour. Thereafter, the solution was analyzed by GC. The GC data for this reaction was as follows:

Claims (10)

A process for producing a haloorganoalkoxysilane of the formula:
(R ¹ ) _x (R ² O) _3-x SiCH ₂ CHR ³ CR ⁴ R ⁵ X
Wherein R ¹ is alkyl having 1 to 6 carbon atoms, R ² is alkyl having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms or hydrogen, ⁴ is alkyl having 1 to 6 carbon atoms, hydrogen or halogen, R ⁵ is hydrogen or alkyl having 1 to 6 carbon atoms, X is halogen, and x is 0, 1 or 2.
In a reaction medium to which a catalytically effective amount of a ruthenium-containing catalyst and a reaction-promoting effective amount of an electron-donating aromatic compound are added, an olefin halide having the following general formula is added:
H ₂ C = CR ³ CR ⁴ R ⁵ X
(Wherein R ³ , R ⁴ , R ⁵ and X have the above-mentioned meanings.)
A molar excess of alkoxysilane of the general formula
(R ¹ ) _x (R ² O) _3-x SiH
(Wherein R ¹ , R ² and x have the above-mentioned meanings)
A process comprising reacting. An electron-donating aromatic compound is benzene, ethylbenzene, diethylbenzene, triethylbenzene, n-butylbenzene, di-t-butylbenzene, bibenzyl, toluene, t-butyltoluene, anisole, 1-phenylhexane, 1-phenyldodecane, 2. The method of claim 1 selected from the group consisting of m-xylene, mesitylene, p-cymene, diphenylmethane, triphenylmethane, phenyl ether, phenothiazine and biphenyl. The method of claim 1 or claim 2, wherein the electron donating aromatic compound is present in an amount of about 1 to about 100 molar equivalents relative to the number of moles of ruthenium metal. The method of any one of claims 1 to 3, wherein the electron donating aromatic compound is present in an amount of about 20 to about 30 molar equivalents relative to the number of moles of ruthenium metal. The olefin halide is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene and 2-chloropropene, and the alkoxysilane is trimethoxysilane, methyldimethoxysilane, The method according to any one of claims 1 to 4, wherein the method is selected from the group consisting of dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, and diethylethoxysilane. The process of any one of claims 1 to 5, wherein the cumulative molar ratio of alkoxysilane to olefin halide is in the range of about 1.3 to about 3.0. The process according to any one of claims 1 to 6, wherein the reaction is carried out at a temperature of about 50 to about 130 ° C. Ruthenium-containing catalysts are 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 8. Any one of claims 1 to 7 selected from the group consisting of P) ₃ Ru (CO) H ₂ , Fe-supported Ru, Al ₂ O ₃ -supported Ru, carbon-supported Ru, Ru (AcAc) _3, and RuBr _3. The method according to claim 1. 9. A process according to any one of claims 1 to 8, wherein the amount of ruthenium present in the reaction medium is from about 5 to about 100 ppm by weight with respect to the reactants. A method for producing a chloroalkylmethoxysilane having the following general formula:
_{(CH 3) x (CH 3} O) 3-x SiCH 2 CHR 3 CR 4 R 5 Cl
(Wherein R ³ is alkyl or hydrogen having 1 to 6 carbon atoms, R ⁴ is alkyl having 1 to 6 carbon atoms, hydrogen or chlorine, and R ⁵ is hydrogen or having 1 to 6 carbon atoms. And alkyl is 0, 1 or 2.)
In a reaction medium to which a ruthenium-containing catalyst containing about 5 to about 100 ppm ruthenium based on the total weight of the reactants and about 1 to about 100 molar equivalents of an electron-donating aromatic compound relative to the number of moles of ruthenium metal is added. And olefin chlorides of the general formula
H ₂ C = CR ³ CR ⁴ R ⁵ Cl
(Wherein R ³ , R ⁴ and R ⁵ have the above-mentioned meanings.)
A molar excess of methoxysilane of the general formula
(CH ₃ ) _x (CH ₃ O) _3-x SiH
(In the formula, x has the above-mentioned meaning.)
Reacting at a temperature of about 60 to about 130 ° C. such that the cumulative molar ratio of methoxysilane to olefin chloride is about 1.3 to about 3.0.