Gas-phase dehydrogenation silylation process using heterogeneous rhenium catalyst

Abstract

The process for preparing vinyl-functionalized chlorosilanes is carried out by the dehydrogenation and silylation of hydridochlorosilane and ethylene, both in the gas phase, in the presence of a heterogeneous rhenium catalyst. This process can be used to prepare vinyldimethylchlorosilane at ambient pressure.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application is a U.S. national phase application under Section 371 of the U.S. Patent Act for International Application PCT / US23 / 76638, filed on 12 October 2023 and currently pending, and this application claims the benefits of U.S. Provisional Patent Application 63 / 416,956, filed on 18 October 2022 under Section 119(e) of the U.S. Patent Act.

[0002] (Field of invention) The process for preparing vinyl-functionalized chlorosilanes involves the use of a rhenium catalyst. More specifically, this process is carried out by the dehydrogenation and silylation of hydridochlorosilane and ethylene, both in the gas phase, in the presence of a heterogeneous rhenium catalyst.

[0003] (Introduction) Hydrosilylation reactions are generally known in the art and involve the addition reaction between silicon-bonded hydrogen and aliphatic unsaturated elements. Hydrosilylation reactions are used in a variety of applications, such as crosslinking components in curable compositions. Hydrosilylation reactions can also be used to prepare individual components or compounds, for example, components to be included in such curable compositions. Typically, hydrosilylation reactions are carried out in the presence of platinum metal catalysts due to their excellent catalytic activity and stability. Platinum metals are generally much more expensive than other metals with lower catalytic activity, but non-platinum catalysts can be unstable when exposed to ambient conditions. In particular, non-platinum catalysts are prone to undesirable side reactions with ambient oxygen and water, which can limit their use and potential end applications.

[0004] Like hydrosilylation reactions, dehydrogenation silylation reactions are also known in the art and similarly involve a reaction between silicon-bonded hydrogen and an aliphatic unsaturated compound. However, in dehydrogenation silylation, the aliphatic unsaturated compound is bonded to silicon in a vinyl form. Dehydrogenation silylation reactions can be used to prepare unsaturated compounds (e.g., olefin-functionalized compounds) that can undergo further functionalization and / or coupling reactions (e.g., via hydrosilylation).

[0005] Unfortunately, catalysts for dehydrogenation silylation reactions suffer from many of the same drawbacks as hydrosilylation catalysts, such as sensitivity to oxygen, water, and even light. Furthermore, while recent advances in hydrosilylation catalysts have overcome these drawbacks, many catalyst systems suitable for hydrosilylation reactions are not practical for use in dehydrogenation silylation reactions. For example, many such catalysts exhibit preferred selectivity, particularly in addition reactions with minimally substituted olefins, thus resulting in non-selective reactions with undesirable product mixtures and low yields. In addition, many conventional dehydrogenation silylation conditions are not functional group tolerant and therefore have limited applications. [Overview of the project]

[0006] A process for preparing vinyl-functionalized chlorosilanes involves the dehydrogenation silylation reaction of silicon-bonded hydrogens of (A) hydridochlorosilane and (B) ethylene in the presence of (C) a heterogeneous metal catalyst. [Brief explanation of the drawing]

[0007] [Figure 1] A schematic diagram of a process apparatus for preparing vinyl-functionalized chlorosilane according to the present invention is shown.

[0008] [Table 1] [Modes for carrying out the invention]

[0009] The starting materials used in the process introduced above are further described as follows:

[0010] (A) Hydridosilane Starting material (A) used in the process described herein is a hydridosilane, i.e., an organosilicon compound having at least one silicon-bonded hydrogen atom (i.e., Si-H group) and at least one silicon-bonded chlorine atom (i.e., Si-Cl group). Hydridosilanes have the general formula R (3-x) HSiCl x where the subscript x can be 1 - 3, or 1 or 2, and each R is independently selected from alkyl groups having 1 - 18 carbon atoms. For example, when the subscript x is 1 or 2, the hydridosilane can be an organohydridosilane. For example, the subscript x can be 1, in which case (A) hydridosilane can be an organohydridosilane, which can include a diorganohydridosilane of the formula R2HSiCl. Alternatively, the subscript x can be 2, in which case the organohydridosilane includes an organohydridodichlorosilane of the formula RHSiCl2. Alternatively, the subscript x can be 3, in which case (A) hydridosilane can be trichlorosilane (HSiCl3). Alternatively, combinations of hydridosilanes can be utilized, in which case, for example, the subscript x has an average value such that 1 < x < 3. Alternatively, combinations of organohydridosilanes can be utilized, in which case, for example, the subscript x has an average value such that 1 < x < 2.

[0011] In the above formula for organohydridochlorosilane, each R is independently selected from alkyl groups having 1 to 18 carbon atoms. Suitable alkyl groups for R can independently be linear, branched, cyclic, or a combination thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl); and hexyl, octyl, decyl, and dodecyl, as well as branched saturated hydrocarbon groups having, for example, 6 to 18 carbon atoms. Alternatively, the alkyl group of R may have 1 to 16, or 1 to 14, or 1 to 12, or 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 2 carbon atoms.

[0012] If the subscript x is 1 and the organohydridochlorosilane is a diorganohydridochlorosilane, then each R may be the same as or different from the other R in the diorganohydridochlorosilane. Alternatively, each R may be the same as the other R in the diorganohydridochlorosilane. Alternatively, for example, if the subscript x = 2, one R may be different from another R in another molecule of the organohydridochlorosilane in the above formula. Alternatively, each R may be independently selected from methyl and ethyl groups. Alternatively, each R may be methyl. For example, the organohydridochlorosilane is of the formula HSiCl x (CH3) (3-x)Organohydridochlorosilane may have the following characteristics, where the subscript x is 1 or 2 as described above. Alternatively, organohydridochlorosilane may include chlorodimethylsilane (i.e., of formula HSiCl(CH3)2), dichloromethylsilane (i.e., of formula (CH3)HSiCl2), diisopropylchlorosilane (i.e., of formula HSiCl(CH(CH3)2)) or a combination thereof. Alternatively, organohydridochlorosilane may include chlorodimethylsilane, dichloromethylsilane, or a combination thereof. Alternatively, organohydridochlorosilane may include chlorodimethylsilane, or may be chlorodimethylsilane. Organohydridochlorosilanes such as chlorodimethylsilane are known in the art and are commercially available, for example, from Sigma Aldrich in St. Louis, Missouri, USA. Other organohydridochlorosilanes such as diisopropylchlorosilane are commercially available from Gelest, Inc. in Morrisville, Pennsylvania, USA.

[0013] (B) Ethylene The starting material (B) in the processes described herein is ethylene. Ethylene is used in gaseous form, in or as part of the starting material (B). Ethylene is not particularly limited and may be used in its neat form (i.e., without or substantially without other components or compounds). In other words, the starting material (B) may consist of ethylene, may consist essentially of ethylene, or may include ethylene in combination with other components. Alternatively, the dehydrogenation silylation reaction process described herein may include introducing a reactor fluid containing ethylene, or consisting essentially of ethylene, or consisting of ethylene, into a reactor containing at least the starting material (C) heterogeneous metal catalyst. The reactor fluid may contain (or may include) non-ethylene components, such as a carrier vehicle, which will be understood by those skilled in the art, typically contain (or are) substances that are inert under the reaction conditions used in the dehydrogenation silylation process (i.e., will not react with the starting materials (A), (B), and (C)). Examples of such carrier vehicles include inert gases such as nitrogen (N2), helium (He), argon (Ar), and combinations thereof. (B) Ethylene may be used in its pure form and may consist essentially of ethylene (i.e., substantially no carrier vehicle or no carrier vehicle at all). Ethylene is known in the art and is commercially available, for example, from Sigma Aldrich in St. Louis, Missouri, USA.

[0014] The dehydrogenation silylation reaction process can utilize any amount of starting materials (A) and (B), more specifically, (A) hydridochlorosilane and (B) ethylene, in amounts or ratios that vary depending on the desired properties of the reaction (e.g., conversion rate) and / or the characteristics of the starting materials used. Typically, the starting material (B), ethylene, is utilized in a stoichiometric ratio of at least 1:1, based on the number of silicon-bonded hydrogen groups per molecule of the starting material (A), hydridochlorosilane, to be vinylized (i.e., the number of Si-H groups that can undergo the dehydrogenation silylation reaction). Thus, the amount of (B) ethylene is typically selected based on the amount, type, and solubility of the starting material (A), as will be understood by those skilled in the art. To maximize the conversion rate of (A) hydridochlorosilane to vinyl-functionalized chlorosilane, an excess or great excess of (B) ethylene may be utilized. For example, the starting materials (A) and (B) may be utilized in a stoichiometric (molar) ratio (A):(B) of 1:>1. Alternatively, ethylene may be used in an amount sufficient to provide a molar ratio (B):(A) of (B) ethylene to (A) hydridochlorosilane of 1:1 to 100:1, e.g., 1:1 to 50:1, or 1:1 to 25:1, or 1:1 to 20:1, or 1:1 to 15:1, or 1:1 to 10:1, or 2:1 to 10:1, or 2:1 to 6:1. Higher or lower ratios may also be used. For example, a large excess of (B) ethylene (e.g., >100:1 (B):(A)) may be used.

[0015] (C) Heterogeneous metal catalyst The starting material (C) is a heterogeneous metal catalyst. The heterogeneous metal catalyst comprises rhenium (Re) and a support. The heterogeneous metal catalyst can be prepared by any convenient means, such as initial wetting of the support using the Re compound. For example, the Re compound is commercially available from, for example, Sigma-Aldrich, with the formula Re2(CO) 10, may contain rhenium decacarbonyl of ReCl5, Re3Cl9, NH4ReO4 and HReO4. The Re compound can be dissolved in a solvent, for example, THF, and then mixed with a support. Thereafter, the solvent can be removed, for example, by heating and / or under reduced pressure. After removing the solvent, organic substances and volatile inorganic substances can be removed from the Re compound by further heat treatment, thus leaving Re metal particles on the support as a heterogeneous catalyst. The support is not important, and the support can be selected from the group consisting of activated carbon, graphite, silicon carbide, alumina, ceria, silica, magnesium oxide, and calcium oxide, all of which are commercially available. Alternatively, the support can be activated carbon or alumina.

[0016] Alternatively, the heterogeneous metal catalyst may optionally further contain an additional metal (i.e., a metal other than rhenium). The additional metal can be selected from the group consisting of silver (Ag), cobalt (Co), nickel (Ni), palladium (Pd), and iridium (Ir). Alternatively, the additional metal can be any one of Ag, Co, Ni, Pd, or Ir. Alternatively, the additional metal can be selected from the group consisting of Ag and Co. The heterogeneous metal catalyst containing Re, the support, and the additional metal may be prepared, as described above, for example, by incipient wetness of the support using a Re compound and an additional metal compound. The solutions of the Re compound and the additional metal compound can be mixed with the support in any order. For example, the solvent solution of the Re compound described above can be mixed with the support, the solvent can be removed by heating, and then the additional metal compound (dissolved in the solvent) can be mixed with the support, and then the solvent can be removed. Alternatively, the solvent solution of the additional metal compound can be mixed with the support, the solvent can be removed, and then the solution of the Re compound can be mixed with the support.

[0017] (C) The amount of the heterogeneous metal catalyst is sufficient to catalyze the dehydrogenative silylation reaction of the silicon-bonded hydrogen of (A) hydridochlorosilane and (B) ethylene. The exact amount of the heterogeneous metal catalyst (C) depends on various factors, including the type of reactor used in the process and the flow rates of (A) hydridochlorosilane and (B) ethylene. For example, the reactor used in the process can be any reactor suitable for contacting a gas and a solid, such as a fixed-bed reactor, a fluidized-bed reactor, or an autoclave reactor. The heterogeneous metal catalyst can be disposed within a fixed-bed reactor or a fluidized-bed reactor, and ethylene and hydridochlorosilane can be supplied to the reactor individually or as a mixture. Alternatively, (C) the heterogeneous metal catalyst can be disposed within an autoclave reactor or supported within a catalyst basket therein.

[0018] Process step A process for producing a reaction product containing a vinyl-functional chlorosilane is described herein. This process comprises Optionally, pre-1) reducing a (C) heterogeneous metal catalyst comprising rhenium and a support as described above; 1) In a reactor, under conditions for carrying out a dehydrogenative silylation reaction, (A) A hydridochlorosilane of the formula R{x} (3-x) HSiCl{3-x} x (where each R is independently selected from alkyl groups having 1 to 18 carbon atoms and the subscript x is from 1 to 3) (as described above), (B) ethylene (as described above), and (A) the hydridochlorosilane and (B) the ethylene are each in the gas phase, Optionally, contacting starting materials, which are an inert gas, in a way that the dehydrogenative silylation reaction is carried out in the presence of a (C) heterogeneous metal catalyst (as described above), thereby preparing a reactor effluent containing a vinyl-functional chlorosilane.

[0019] The process can optionally further include one or more additional steps. The additional steps are 2) After step 1), the reactor effluent is cooled, thereby condensing the material containing vinyl-functionalized chlorosilane and optionally unreacted (A) hydridochlorosilane. 3) Gas / liquid separation after step 2), 4) Recirculating unreacted gaseous ethylene after step 2) or step 3), 5) After one or more of steps 1), 2), 3), 4), and 6), recirculate the unreacted hydridochlorosilane. 6) Purification of vinyl-functionalized chlorosilane, and 7) Repeat step 1) using gaseous ethylene from step 4) and / or unreacted hydridochlorosilane from step 5), and A group consisting of two or more of steps 2) to 7) may be selected.

[0020] Process Pre-1) Reduction of heterogeneous metal catalyst. Step pre-1) in the above process is to reduce (C) the heterogeneous metal catalyst. The reduction of the heterogeneous metal catalyst can be carried out by any convenient means. The reduction may involve heating a reactor containing (C) the heterogeneous metal catalyst at a temperature of >100°C to 500°C, or 100°C to 400°C, or 200°C to 300°C, while exposing it to hydrogen or a mixture of hydrogen and an inert gas, such as nitrogen or argon.

[0021] Process 1) In step 1) of the process described above, both (A) hydridochlorosilane and (B) ethylene are in the gas phase. The reactor used in step 1) can be any reactor suitable for contacting gas and solid, as described above. For example, (C) a heterogeneous metal catalyst may be placed in the reactor, and the starting materials containing (B) ethylene and (A) hydridochlorosilane may be supplied to the reactor individually or as a mixture in step 1). The gaseous hydridochlorosilane and ethylene (and any other starting materials, e.g., the inert gas described above) may be supplied at a flow rate and contact time effective to cause the dehydrogenation silylation reaction at a selected pressure and temperature. Alternatively, (C) a heterogeneous metal catalyst may be placed in an autoclave reactor or supported in a catalyst basket therein, and the starting materials containing (A) hydridochlorosilane and (B) ethylene may be added and maintained at a selected temperature and pressure to carry out the dehydrogenation silylation reaction in step 1).

[0022] The temperature in step 1) is sufficient for the dehydrogenation silylation reaction to occur and may be >125°C, or at least 200°C, while the temperature may be <400°C, or at most 300°C. Alternatively, the temperature in step 1) may be >125°C to <400°C; or the temperature may be 200°C to 300°C.

[0023] The reactor in step 1) may optionally be pressurized with ethylene (e.g., via a gas manifold). Alternatively, the starting materials (A) and (B) may be supplied to the reactor at ambient pressure, or 90 kPa to 500 psi (3447.4 kPa), or 90 kPa to 690 kPa, 100 kPa ± 10 kPa. Alternatively, higher pressures may be used. Those skilled in the art will balance productivity with other factors such as capital costs when designing the apparatus for carrying out step 1) of the process. An inert gas may optionally be added during step 1). For example, nitrogen or argon may be used to optimize process step 1).

[0024] Additional steps The above process may further include one or more additional steps, which can be performed in any convenient order as described above. For example, in step 2), the reactor effluent may be cooled to, for example, room temperature, or to a temperature <125°C, or to any temperature sufficient to condense the vinyl-functionalized chlorosilane and / or any unreacted hydridochlorosilane. The unreacted ethylene may be collected via gas / liquid separation in step 3), and the unreacted ethylene may optionally be recycled in the process of step 1).

[0025] The above process may further include step 6) purifying the vinyl-functionalized chlorosilane from the reactor effluent. Purifying the vinyl-functionalized chlorosilane means increasing the relative concentration of the vinyl-functionalized chlorosilane compared to other compounds combined with it (e.g., in the reactor effluent after step 1), or compared to its purified version (e.g., if the gas / liquid separation and / or recirculation steps described above are performed). As understood in the art, purification may include removing other compounds from such combinations (i.e., reducing the amount of impurities / other components combined with the vinyl-functionalized chlorosilane in the reactor effluent) and / or removing the vinyl-functionalized chlorosilane itself from the combination. Any suitable techniques and / or protocols for purification, e.g., distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, and chromatography, and combinations thereof, may be used, for example, sequentially or as part of a single procedure. Regardless of the specific technique selected, the purification of the vinyl-functionalized chlorosilane may be carried out sequentially (i.e., in a series) with the reaction itself and therefore may be automated. Alternatively, purification may be a standalone procedure in which the reactor effluent containing vinyl-functionalized chlorosilane is supplied.

[0026] The distillation for purifying vinyl-functional chlorosilane can be carried out at a pressure and temperature below atmospheric pressure (i.e., reduced temperature and reduced pressure). The reduced pressure and temperature are selected by one skilled in the art considering the reaction conditions and parameters selected, the starting materials utilized, and the vinyl-functional chlorosilane to be prepared. The reduced pressure typically operates as a vacuum, but any reduced pressure between vacuum and atmospheric pressure of 101.325 kPa can be utilized. For example, the reduced pressure can be >0 to 50, or >0 to 40, or >0 to 30, or >0 to 20, or >0 to 10, or >0 to 5, or >0 to 4, or >0 to 3, or >0 to 2 kPa.

[0027] Any unreacted hydridosilane can also be recovered during the gas / liquid separation during step 3) and / or during the purification in step 6), such as during the distillation step described above, and the process can further include a step 5) in which the unreacted hydridosilane can optionally be recycled in the process in step 1). Step 5) can be carried out before or after step 6) described above. The process can optionally further include a step 7) that repeats step (1). In step 7), the ethylene recovered via gas / liquid separation in step 3), the unreacted hydridosilane recovered as described above, or both the ethylene and the unreacted hydridosilane can be recycled.

[0028] The product produced by the above process has the formula (CH2=CH-)R (3-x) SiCl xThe vinyl-functionalized chlorosilane is a vinyl-functionalized chlorosilane in which each R is independently selected from an alkyl group of 1 to 18 carbon atoms, and the subscript x is 1 to 3, or 1 or 2, as described above. Alternatively, the vinyl-functionalized chlorosilane may be a vinyl-functionalized organochlorosilane having a formula selected from the group consisting of (CH2=CH-)R2SiCl, (CH2=CH-)RSiCl2, and combinations thereof. Alternatively, the vinyl-functionalized organochlorosilane may include vinyldimethylchlorosilane, vinylmethyldichlorosilane, or combinations thereof. The vinyl-functionalized chlorosilane prepared according to the above process can be used in various end uses, for example, as a separate component in compositions such as curable compositions, such as hydrosilylation reaction curable compositions.

[0029] A schematic diagram of a suitable apparatus for carrying out the above process is shown in Figure 1. The process apparatus 100 comprises a vaporizer 101 upstream of a fixed-bed reactor 102, upstream of a condenser 103, upstream of a distillation apparatus 104. Hydride chlorosilane can be supplied to the vaporizer 101 as a liquid via a hydride chlorosilane supply line 105. Hydride chlorosilane, such as dimethylchlorosilane, is heated and vaporized by the vaporizer 101. The hydride chlorosilane (in the gas phase here) exits the heater via a gaseous hydride chlorosilane outlet line 106. Ethylene is introduced via an ethylene supply line 107. Both ethylene and hydride chlorosilane, in the gas phase, are supplied to the reactor 102 via a gas supply line 108. The reactor 102 defines a cavity 102a that houses a heterogeneous metal catalyst 102b. The gaseous hydridochlorosilane and ethylene come into contact with the heterogeneous metal catalyst 102b in reactor 102, and if the hydridochlorosilane is dimethylchlorosilane, a dehydrogenation silylation reaction occurs as illustrated in Scheme 1 below. One or more of hydrogen, ethane, and ethyldimethylchlorosilane may be produced as byproducts of the dehydrogenation silylation reaction.

[0030] [ka]

[0031] The reactor effluent exits reactor 102 and enters condenser 103 via reactor effluent line 109. The reactor effluent contains unreacted ethylene, by-product ethane, and vinyl-functionalized chlorosilane products (e.g., vinyldimethylchlorosilane in scheme 1 above). When the reactor effluent is cooled in condenser 103, the unreacted ethylene and by-product ethane can be separated via condenser outlet line 110 and recycled back to reactor 102 via recirculation line 111 or discarded via purge line 112. The liquid crude product exits the condenser via liquid outlet line 113 and can be fed to distillation unit 104. Any by-products, such as vinyl-functionalized chlorosilane and ethyl-functionalized chlorosilane, can be separated into different distillation fractions. The vinyl-functionalized chlorosilane can exit distillation unit 104 via vinyl-functionalized chlorosilane line 114, and any remaining by-products can exit distillation unit 104 via by-product outlet line 115.

[0032] Those skilled in the art will recognize that Figure 1 illustrates an example and that other means for carrying out the processes described herein are within the scope of the present invention. For example, instead of supplying ethylene to reactor 102 together with gaseous hydridochlorosilane, ethylene may be introduced directly into reactor 102 by moving the ethylene supply line 107. Alternatively, the ethylene supply line 107 may introduce ethylene upstream or downstream of any recirculation line 111. Recirculating unreacted ethylene is optional, and therefore the recirculation line 111 may be omitted. The fixed-bed reactor 102 may be replaced with a fluidized-bed reactor, a multi-tube reactor distributing hydridochlorosilane from gas supply line 108 into a plurality of smaller tubes, or other types of reactors suitable for contacting gas and solid. Alternatively, two or more reactors suitable for contacting gas and solid may be used in series or in parallel to improve the conversion rate, and hydridochlorosilane and ethylene may be supplied to a second reactor with a fresher catalyst so that production can continue while the heterogeneous metal catalyst in the first reactor is being regenerated or replaced when the heterogeneous metal catalyst in the first reactor is consumed. [Examples]

[0033] These examples are intended to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as described in the claims. The starting materials used in these examples are listed in Table 1.

[0034] [Table 2]

[0035] Catalyst Preparation (CP) Examples CP Example 1: Preparation of 3% Re on activated carbon Inside the glove box, place activated carbon (1.00g, Cabot NORIT 3 EXTRA) in a jar and dissolve Re2(CO) in THF (1mL). 10A solution of (0.0542 g) was added dropwise with gentle shaking. The carbon was allowed to stand for 30 minutes, and then THF was removed under vacuum at room temperature for 15 hours. A total of 1.110 g was isolated, which suggests that some THF was not removed during the evacuating process.

[0036] CP Example 2: Preparation of 10% Cu / a-Al2O3 6.79 mL of saturated copper nitrate aqueous solution (density = 1.67 g / mL) and 7.02 mL of distilled water were placed in a 20 mL vial. Then, 1.41 mL of ethylene glycol was added to the vial. The cap was placed on top of the vial and the contents were mixed by shaking vigorously for 30 seconds.

[0037] Next, 4.931 g of ALAP C1-5α-alumina support (lot number BL073321, SS070636 TB) was added to the solution in the vial. After immersing the support in the solution for 3 hours, it was removed and placed in a small ceramic dish.

[0038] The dish was transferred to an air-purged (20 L / min) Lindberg Blue M furnace, heated to 88°C at a rate of 2°C / min, held at 88°C for 10 hours, heated to 260°C at a rate of 2°C / min, held at 260°C for 90 minutes, and then cooled to room temperature. After cooling, the sample was collected and weighed (5.497 g).

[0039] CP Example 3: Preparation of ~3% Ni on activated carbon In a glove box, a jar containing a solution of activated carbon (1.00 g, Cabot NORIT 3 EXTRA) and bis(cyclooctadiene)nickel(0) (0.145 g) was placed and mostly dissolved in toluene (2 mL). This solution was then added dropwise to the carbon while gently shaking at 60°C. A small amount of undissolved solid Ni(COD)2 was not added to the support. The carbon was allowed to stand for 10 minutes, and then volatile substances were removed under vacuum at room temperature for 1 hour. A total of 1.31 g was isolated, suggesting that some toluene had not been removed.

[0040] Comparative Example 1 - Gas-phase dehydrogenation and silylation of ethylene using chlorodimethylsilane with 3% Ru on activated carbon A heterogeneous metal catalyst, 3 wt% Ru / C (1.38 g, extruded, provided by Johnson Matthey), was loaded into the center of an Inconel reactor tube (3 / 8” OD). The length of the packed catalyst bed was 3 inches. The catalyst was packed between two beds of quartz beads (approximately 6–8 inches each). The reactor tube was connected to a flow setup, and the catalyst was reduced cumulatively for 5 hours under an H2 / N2 flow (90 sccm each) at a temperature in the range of 100–300°C. Chlorodimethylsilane (HSiMe2Cl) was supplied to the reactor via a bubbler with N2 as the carrier gas using a mass flow controller. Ethylene gas was supplied to the reactor via a mass flow controller from a cylinder equipped with a pressure regulator. The ethylene / SiH ratio was maintained constant at 2 mol / mol throughout the experiment. All supply lines to the reactor were preheated to 170°C. Throughout the experiment, the reactor temperature The temperature varied between 200 and 400°C. The gas flow rate was adjusted accordingly to obtain residence times ranging from approximately 3 to 5 seconds. The back pressure regulator was bypassed to maintain atmospheric pressure within the reactor. The reactor outlet was connected via a three-way valve assembly used for periodic sample injection to an online GC / TCD / MS for qualitative and quantitative analysis of reagents and products. The supply line to the GC was heat-trace and maintained at 150°C. A dry eye trap was used downstream of the reactor to condense the product. The results are shown in Table 2. This example demonstrates that, unlike the dehydrogenation silylation of Me2HSiCl with ethylene in both gas phases using a Ru / C catalyst, the Vi / Et ratio of the reaction product is much smaller than 1, as described in International Publication No. 2021-127179 for liquid-phase homogeneous Ru catalyst dehydrogenation silylation.

[0041] [Table 3] a NA indicates that ethylchlorodimethylsilane is below the GC detection limit.

[0042] Comparative example 2: Recirculated Ru / C In this Comparative Example 2, the same catalyst as in Comparative Example 1 was used. Please refer to Comparative Example 1 for catalyst loading and preparation. Prior to this experiment, the catalyst was reduced twice at a temperature of 500°C for 1.5 hours under an H2 / N2 flow (90 / 180 sccm each). Chlorodimethylsilane (HSiMe2Cl) was supplied to the reactor via a bubbler with N2 as the carrier gas using a mass flow controller. Ethylene gas was supplied to the reactor from a cylinder equipped with a pressure regulator via a mass flow controller. All supply lines to the reactor were preheated to 170°C. The reactor temperature was kept constant at 300°C throughout the experiment. A constant residence time of 3 seconds was obtained by keeping the total flow rate of ethylene and chlorodimethylsilane gases constant. The ethylene:SiH ratio was varied from 2 to 5 mol / mol throughout the experiment. The back pressure regulator was bypassed to maintain atmospheric pressure in the reactor. The reactor outlet was connected via a three-way valve assembly used for periodic sample injection into an online GC / TCD / MS for qualitative and quantitative analysis of reagents and products. The supply line to the GC was heat-trace and maintained at 150°C. A dry eye trap was used downstream of the reactor to condense the product. The results are shown in Table 3. This example demonstrates that the use of a Ru / C heterogeneous catalyst does not adequately catalyze the dehydrogenation silylation reaction, and each sample tested produced a product with a Vi / Et ratio much less than 1, even when the ethylene:SiH ratio was varied under the tested conditions.

[0043] [Table 4] a If ethylchlorodimethylsilane is below the GC detection limit, use NA.

[0044] Comparative Example 3 - Gas-phase dehydrogenation and silylation of ethylene using chlorodimethylsilane with 21% Ru on alumina A heterogeneous metal catalyst, 21 wt% Ru / Al2O3 (0.96 g, spherical), was loaded into the center of an Inconel reactor tube (3 / 8” OD). The length of the packed catalyst bed was 3 inches. The catalyst was packed between two beds of quartz beads (approximately 6–8 inches each). The reactor tube was connected to a flow setup, and the catalyst was reduced cumulatively for 5 hours under an H2 / N2 flow (60 / 180 sccm, respectively) at a temperature in the range of 100–300°C. Chlorodimethylsilane was supplied to the reactor via a bubbler with N2 as the carrier gas using a mass flow controller. Ethylene gas was supplied to the reactor from a cylinder equipped with a pressure regulator via a mass flow controller. Throughout the experiment, the reactor temperature was kept constant at 300°C. A constant residence time of 3 seconds was obtained by keeping the total gas flow rate constant. The ethylene:SiH ratio was maintained throughout the experiment. The concentration was varied from 2 to 10 mol / mol. The back pressure regulator was bypassed to maintain atmospheric pressure inside the reactor. The reactor outlet was connected via a three-way valve assembly used for periodic sample injection to online GC / TCD / MS for qualitative and quantitative analysis of reagents and products. The supply line to the GC was heat-trace and maintained at 150°C. A dry eye trap was used downstream of the reactor to condense the product. The results are shown in Table 4. This example demonstrates that attempts at gas-phase dehydrogenation silylation of chlorodimethylsilane with ethylene using a Ru / Al2O3 catalyst produce products with a Vi / Et ratio of less than 1 mol / mol for most of the operation, indicating low selectivity for the desired product under the tested conditions. Only one initial measurement showed the desired Vi / Et ratio, but this performance was not maintained during additional measurements.

[0045] [Table 5] a If ethylchlorodimethylsilane is below the GC detection limit, use NA.

[0046] Comparative Example 4 - Liquid-phase reaction of ethylene and chlorodimethylsilane with Ru / C A heterogeneous metal catalyst of 3 wt% Ru / C (506 mg, extruded, supplied by Johnson Matthey) was loaded into the center of an Inconel reactor tube (3 / 8” OD). The reactor tube was connected to a flow setup, and the catalyst was reduced cumulatively for 5 hours under an H2 / N2 flow (90 sccm each) at a temperature in the range of 100–300°C. The reactor was then purged with excess N2, sealed, and transferred to an inert glove box. In the glove box, 50 mL solutions of toluene (30.15 g) and chlorodimethylsilane (13.54 g) were prepared in glass screw-top containers. 1.13 g of nonane was also added. It was added as an internal reference standard for gas chromatography analysis. 1 g of the solution was weighed into another glass vial and combined with 4 g of toluene, and the starting concentration of chlorodimethylsilane was measured by gas chromatography. The remaining solution was then transferred to a 100 mL Parr reactor. The catalyst was then packed into the reactor vessel to prepare a slurry solution. The reactor was sealed and removed from the glove box. The Parr reactor was connected to the system, and the lines were purged with nitrogen for 10 minutes. The reactor was then stirred for 1 minute under pressurization. The reactor was purged three times with 100 psig of ethylene. After purging, the reactor was pressurized with 200 psig of ethylene while continuously stirring at 350 rpm. Ethylene was supplied to the reactor until the pressure stabilized at 200 psig. After saturation, the reactor was sealed and heated to 40°C while stirring at 350 rpm. After a 10-minute stabilization period, the reactor was further heated to 100°C under a controlled temperature gradient of 2°C / min to prevent temperature overshoot. The reactor temperature was maintained at 100°C for 120 minutes, after which heating was stopped and the reactor was exposed to the outside. The reactor was cooled with a fan. After cooling to room temperature, the reactor was depressurized and then purged three times with 100 psig of nitrogen. After one final depressurization, the reactor was connected to a 10 psig nitrogen flow, and this pressure was used to transfer the reactor solution to a stainless steel sample cylinder. The cylinder was sealed and transported to an inertified glove box, where the solution was collected in a glass vial. A 1 g aliquot was collected in another vial, diluted with 4 g of toluene, and analyzed by gas chromatography to determine the solution composition after the dehydrogenation coupling reaction.The resulting reaction solution showed a SiH conversion rate of 66% and a selectivity of 12% (mol Si) Me2ViSiCl. Next, the same additional reaction was carried out using this product mixture, except that the reactor temperature was maintained at 200°C for 120 minutes. The resulting reaction solution showed a SiH conversion rate of 100% and a selectivity of 48% (mol Si) Me2ViSiCl. This example demonstrates that Me2ViSiCl can be produced by the dehydrogenation silylation of ethylene with chlorodimethylsilane in a liquid phase (slurry) using a Ru / C catalyst. Using a heterogeneous Ru catalyst with the liquid-phase reactants yielded different results than when using the same metal (Ru) as the catalyst with the gaseous reactants (see Comparative Example 1). While we do not wish to be bound by theory, dehydrogenation silylation is thought to function differently in the liquid phase and the gas phase, and therefore, those skilled in the art do not have reasonable expectations of success in arriving at the present invention based on literature using liquid-phase hydridosilane reactants, as this does not predict the function of the present invention in which both ethylene and organohydridochlorosilane are in the gas phase during the dehydrogenation silylation reaction.

[0047] Example 1 - Gas-phase dehydrogenation silylation of ethylene with chlorodimethylsilane using 3% Re on activated carbon: A 0.5g sample of Re / C catalyst prepared according to CP Example 1 above was ground to a 30 / 50 mesh size and loaded into a 1 / 4-inch diameter reactor tube. The remaining reactor volume was filled with quartz chips and held in place between quartz wool plugs. The reactor was heated to 100°C with a nitrogen flow (200 sccm) and held for 1 hour. The catalyst was then reduced by heating to 350°C with a 5% hydrogen flow in argon and holding for 3 hours. The reactor was cooled to 125°C with a nitrogen flow. The nitrogen flow was stopped, and a mixture of ethylene and chlorodimethylsilane in an approximately 5:1 ratio was supplied to the reactor. This was achieved by bubbling 5% nitrogen in argon (8 sccm) through pure chlorodimethylsilane at ambient temperature and mixing the resulting vapor with ethylene (60 sccm). 3. After 3 hours, the reactor was heated to 200°C while continuing the reaction gas flow for 3 hours, then heated to 300°C for 4 hours, and finally to 400°C for 4 hours. Throughout the experiment, the product mixture was analyzed by inline Agilent 7890A GC with a Restek CC1263 column and TCD detector. The test methods and calculations were performed as described below. The chlorodimethylsilane conversion rate, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature determined by GC are shown in Table 5 below.

[0048] [Table 6]

[0049] The data in Table 5 shows that reaction products with a Vi / Et ratio of ≥1 were prepared at temperatures of 200°C to 300°C using a heterogeneous catalyst containing Re and a support under the tested conditions.

[0050] Comparative Example 5: No metal present. The procedure of Example 1 was followed, but instead of a catalyst, an activated carbon support was used directly without metal impregnation. The chlorodimethylsilane conversion rate, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature determined by GC are shown in Table 6 below.

[0051] [Table 7] a N / A = Ethylchlorodimethylsilane cannot be detected.

[0052] Comparative Example 6 - Gas-phase dehydrogenation silylation of ethylene using chlorodimethylsilane with 3% Ru on activated carbon: The procedure of Example 1 was followed, except that the catalyst was replaced with 3% Ru on carbon and the temperature conditions of 125°C and 400°C were omitted. The chlorodimethylsilane conversion rate, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature determined by GC are shown in Table 7 below.

[0053] [Table 8]

[0054] Comparative Example 7: The procedure was the same as in Example 1, except that the catalyst used was 10% Cu on α-Al2O3.

[0055] The conversion rate of chlorodimethylsilane, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature for the catalyst and comparative catalyst of the present invention, as determined by GC. The results of this Comparative Example 7 are shown in Table 8 below.

[0056] [Table 9] aN / A = Ethylchlorodimethylsilane cannot be detected.

[0057] Comparative Example 8: The procedure was the same as in Example 1, except that the catalyst used was 3% Ni on activated carbon and the catalyst was reduced at 350°C.

[0058] As shown in Table 9 below, the chlorodimethylsilane conversion rate, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature for the catalyst and comparative catalyst of the present invention, as determined by GC, are shown.

[0059] [Table 10] a N / A = Ethylchlorodimethylsilane cannot be detected.

[0060] Comparative Example 9 - Gas-phase dehydrogenation silylation of ethylene using chlorodimethylsilane with 1% Pt on activated carbon: The procedure was the same as in Example 1, except that the catalyst used was 1% Pt on carbon, and the 125°C temperature and temperature immersion steps were omitted.

[0061] The conversion rate of chlorodimethylsilane, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature determined by GC are shown in Table 10 below.

[0062] [Table 11]

[0063] Comparative Example 10 - Gas-phase dehydrogenation silylation of ethylene using chlorodimethylsilane with 5% Pd on activated carbon: The procedure was the same as in Example 1, except that the catalyst used was 1% Pd on carbon, and the 125°C temperature and temperature immersion steps were omitted.

[0064] The conversion rate of chlorodimethylsilane, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for generating silicon-containing species at a given temperature determined by GC are shown in Table 11 below.

[0065] [Table 12]

[0066] Comparative Examples 7-10 demonstrate that not all metals can catalyze the dehydrogenation and silylation of ethylene and chlorodimethylsilane under the tested conditions with a Vi / Et ratio of ≥1. Using copper, nickel, platinum, or palladium heterogeneous metal catalysts resulted in reaction products with low conversion rates and selectivity to the desired dimethylvinylchlorosilane.

[0067] CP Example 4: Re / C catalyst preparation by automated process 500 mg of carrier material was added to a round-bottom vial. Larger batches of single catalysts were prepared using multiple vials. These were placed on a vertical shaker table. Using an automated pump, the metal precursor (Re2(CO)) was dissolved in THF solvent. 10 The solution was added to each vial in a volume sufficient to fill the pores of the carrier to their initial positions. The concentration of the metal precursor in the solution was determined by the target amount of metal.

[0068] After adding the solution, a shaker table was activated to ensure that the liquid filled all the pores of the catalyst support material. Next, the catalyst was dried overnight at 120°C under an inert gas flow. After drying, the catalyst was placed in an oven and heated at 120°C for 3 hours, then increased to 500°C for 12 hours. Finally, the catalyst was cooled to 100°C. The entire heating and cooling sequence was carried out with a constant flow of 100 sccm of 5 volume% hydrogen in nitrogen, allowing for the reduction of the metal to its metallic state.

[0069] CP Example 5: Manual Catalyst Preparation with 3% Re / C 1 g of carrier material (e.g., Cabot NORIT 3 Extra activated carbon sizing using a 30-100 mesh sieve) was added to the vial. Zilenium decacarbonyl (Re2(CO)) dissolved in THF (1 mL) 10 A solution of (0.0542 g) was added dropwise with a spatula while mixing to ensure uniform distribution. The THF was removed overnight in a vacuum oven or in a normal oven at 120°C. The catalyst was then transferred to a pre-reduction furnace at 120°C for 3 hours, followed by 12 hours at 500°C. Finally, the catalyst was cooled to 100°C.

[0070] CP Example 6: Manual Catalyst Preparation with 3% Re / C Inside the glove box, place activated carbon (9.7g, Carbon Resources, pre-vacuum dried at 120°C) into a jar and add Re2(CO) 10 A solution (0.53 g dissolved in 10 mL of THF) was added dropwise with gentle shaking. The carbon was allowed to stand in a glove box for 2 hours, and then dried on a hot plate at 120°C in a fume hood. Based on the starting weights of the rhenium salt and carbon support, the composition was calculated to be 3% Re / C (w / w), which was stored in a sample vial for activity testing.

[0071] CP Example 7: Synthesis of Re polymetallic catalysts by automated process In a typical synthesis, 500 mg of the support material was added to a round-bottom vial. Multiple vials were used to prepare different catalyst compositions or larger batches of a single catalyst. These were placed on a vertical shaker table. Using an automated dispensing pump, an aqueous solution of the metal precursor was dispensed into each vial in a volume sufficient to fill the pores of the support material to their initial positions. The concentration of the metal precursor in the solution was determined by the target amount of metal relative to the specific catalyst.

[0072] After adding the first metal solution, the catalyst was dried overnight at 120°C under an inert gas flow. Next, the second metal solution was added to the dried catalyst while simultaneously shaking, in the same manner as the first addition.

[0073] After adding the second solution, the catalyst was placed in an oven and heated at 120°C for 3 hours, then at 500°C for 12 hours. Finally, the catalyst was cooled to 100°C. The entire heating and cooling sequence was carried out with a constant flow of 100 sccm of 5 volume% hydrogen in nitrogen, which enabled the reduction of the metal to its metallic state.

[0074] The total amount of metal added ranged from 3% to 10% by weight, and the molar ratios between metals (metal 1:metal 2 molar ratio) were 3:1, 1:1, or 1:3 mol / mol. Table 12 lists the metal combinations in the synthesized heterogeneous metal catalysts.

[0075] [Table 13]

[0076] Example 2: General procedure for gas-phase dehydrogenation silylation of ethylene with chlorodimethylsilane using a parallel quartz reactor: A heterogeneous metal catalyst (prepared according to the above examples, e.g., CP Examples 4, 5, or 7) was packed into a 152 mm x 3 mm inner diameter quartz reactor tube to create a volume-filled heating zone of approximately 40 mm. Quartz chips and quartz wool were packed into the top and bottom to hold the catalyst bed in place. Sixteen tubes were loaded into a common manifold for gas delivery and placed inside an electrically heated metal block via a clamshell element. The reactor was then heated to 350°C under 100 sccm of Ar, which was uniformly distributed to the sixteen tubes via a microfluidic flow tip. Next, the temperature was raised to 500°C for 3 hours while a 50 / 50 mixture of H2 and Ar was flowed at a total flow rate of 100 sccm. This was also uniformly distributed across the sixteen tubes. The temperature was then returned to the reaction temperature under the flow of Ar. Once the reaction temperature was reached, the flow of chlorodimethylsilane and ethylene was started. Chlorodimethylsilane was delivered via an ISCO syringe pump at a total flow rate of 0.055 mL / min, and ethylene was supplied at a flow rate of 60 sccm. These were mixed in a quartz-tipped vaporizer set to 180°C. The flow was then evenly distributed to each of the 16 tubes via a microfluidic flow tip. The residence time in each reactor tube was approximately 1.7 seconds.

[0077] Example 3: Gas-phase dehydrogenation silylation of ethylene with chlorodimethylsilane using 3% Re / C in a parallel quartz reactor: The catalyst sample prepared according to CP Example 5 was tested according to the conditions of Example 2. The performance obtained for this catalyst is shown in Table 13, which is the average of 6 GC measurements over 6 hours:

[0078] [Table 14]

[0079] Example 4: Gas-phase dehydrogenation silylation of ethylene with chlorodimethylsilane using 10% Re / C in a parallel quartz reactor: The catalyst sample prepared according to CP Example 5 was tested according to the conditions of Example 2. The performance obtained for this catalyst is shown in Table 14, which is the average of 6 GC measurements over 6 hours:

[0080] [Table 15]

[0081] Example 5 - Gas-phase dehydrogenation and silylation of ethylene using dimethylchlorosilane with a Re / C catalyst 3 wt% Re / C catalyst (2.5 g, synthesized according to CP Example 6) was loaded into the center of an Inconel (3 / 8” OD) reactor tube. The length of the packed catalyst bed was approximately 2 inches. The catalyst was packed between two beds of quartz beads (each approximately 6-8 inches). The reactor tube was connected to a flow setup, and the catalyst was reduced under an H2 / N2 flow (50 / 200 SCCM each) at 300°C for 4 hours. Dimethylchlorosilane (Me2HSiCl) with N2 as the carrier gas was supplied to the reactor via a bubbler (maintained at ambient temperature) using a mass flow controller. Ethylene gas was supplied to the reactor from a cylinder equipped with a pressure regulator via a mass flow controller. The inlet and outlet piping to and from the reactor was sealed using heat tape. The reactor was maintained at 170°C to prevent condensation of reactants and products. The reaction was carried out at reaction temperatures of 250°C and 300°C using a molar ratio of ethylene / Me2HSiCl = 4 for the supply. The reactor outlet was connected via a three-way valve assembly used for periodic sample injection to online GC (TCD)-MS for qualitative and quantitative analysis of reagents and products. The supply line to the GC was heat traced and maintained at 150°C. The results, obtained by averaging 7 GC injections and 4 GC injections at 250°C and 300°C, respectively, are shown in Table 15. This example demonstrates that Me2ViSiCl can be produced by the method of the present invention in the gas-phase dehydrogenation silylation of ethylene using Me2HSiCl and a Re / C catalyst in a reactor different from the one tested in Example 3.

[0082] [Table 16]

[0083] Example 6: Gas-phase dehydrogenation silylation of ethylene by chlorodimethylsilane using a polymetallic Re catalyst in a parallel quartz reactor: Catalyst samples prepared according to CP Example 7 were tested under the conditions of Example 2. In this experiment, multiple catalysts were tested in parallel, and all contained Re as the precipitated primary metal. The relative amounts of Re and the secondary metal were varied. The catalyst performance under the conditions of Example 2 is shown in Table 16 for 250°C and in Table 17 for 300°C:

[0084] [Table 17]

[0085] [Table 18]

[0086] Example 7: Gas-phase dehydrogenation silylation of ethylene with chlorodimethylsilane using a polymetallic catalyst containing Re as the second metal in a parallel quartz reactor: Catalyst samples prepared according to CP Example 7 were tested under the conditions of Example 2. In this experiment, multiple catalysts were tested in parallel, and all contained Re as the precipitated secondary metal. The relative amount of metal was varied. The catalyst performance under the conditions of Example 1 is shown in Table 18 for 250°C and in Table 19 for 300°C:

[0087] [Table 19]

[0088] In Table 18, 1This indicates that any deviation from 100% in this total is due to siloxanes that were not quantified. Table 18 shows that when Ru is used as the second metal under the conditions tested in this example, the Vi / Et ratio is < 1, and therefore ruthenium may be detrimental to the performance of heterogeneous metal catalysts under certain conditions.

[0089] [Table 20]

[0090] Table 19 also shows that when Ru is used as the second metal under the conditions tested in this example, the Vi / Et ratio is <1, indicating that ruthenium may be detrimental to the performance of heterogeneous metal catalysts under certain conditions. This example demonstrates that the presence of Re in the polymer composition results in a Vi / Et molar ratio >1, even when Re and the second metal are added in different orders during catalyst synthesis. Note: In Table 19, some of these samples had significant siloxane formation that did not result in a total selectivity of 100% in this table; any deviation from 100% in this total was due to siloxanes that were not quantified.

[0091] Comparative Example 11: Gas-phase dehydrogenation silylation of ethylene by chlorodimethylsilane using a Ru polymetallic catalyst in a parallel quartz reactor: Catalyst samples prepared according to CP Example 7 were tested under the conditions of Example 2. In this experiment, multiple catalysts were tested in parallel, and all contained Ru as the precipitated primary metal. The relative amounts of Ru and the secondary metal were varied. The catalyst performance under the conditions of Example 1 is shown in Table 20 for 250°C and in Table 21 for 300°C:

[0092] [Table 21]

[0093] [Table 22] [Industrial applicability]

[0094] The present invention provides a process for preparing vinyl-functionalized chlorosilanes having a Vi / Et ratio ≥ 1, as calculated as shown in Table 14 below. The heterogeneous rhenium catalyst used herein provides an unexpected benefit of selectivity for the dehydrogenated silylation reaction yielding the desired vinyl-functionalized chlorosilane product. The use of gaseous reactants in the process described herein offers the advantages of not requiring i) high pressure, ii) solvent, or iii) catalyst recirculation / recovery.

[0095] Definitions and Usage of Terms Unless otherwise specified in the context of this specification, the articles “a,” “an,” and “the” each refer to one or more, and the singular form includes the plural form. The “Summary of the Invention” and the “Abstract” are incorporated herein by reference. The terms “comprising” or “comprise” are used herein in their broadest sense, encompassing the ideas of “including,” “include,” “consisting essentially of,” and “consisting of.” The use of “for example,” “eg,” “such as,” and “including” to list examples is not limited to the examples listed. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to,” encompassing other similar or equivalent examples.

[0096] Abbreviations used herein have the definitions set forth in Table 22.

[0097] [Table 23]

[0098] Test method and calculation The above examples and comparative examples were analyzed as follows: Online analysis was completed using an Agilent (7890A) GC instrument equipped with a TCD detector connected to the product vapor line. The reactor effluent gas composition was quantified using response coefficients and retention times determined using calibration gas cylinders containing known amounts of EtMe2SiCl, ViMe2SiCl, Me3SiH, Me3SiCl, and Me2SiCl2. A remote sampling system was used to transfer the sample from the reactor product line to the GC inlet. Details of the GC instrument and program are summarized in Table 23.

[0099] [Table 24]

[0100] In the above examples and comparative examples, the conversion rate, Vi / Et ratio, and Vi selectivity were calculated as shown in Table 24 below. In Table 24, the calculation of experimental results is as follows: "in" = material supplied to the reactor, "out" = material leaving the reactor; and "SiH" represents dimethylchlorosilane.

[0101] [Table 25]

[0102] Embodiments of the present invention In the first embodiment, the process for producing a reaction product containing a vinyl-functional organochlorosilane is as follows: 1) Under conditions for carrying out a dehydrogenation silylation reaction in a reactor, including heating at a temperature of >100°C to <400°C, (A) Organohydridochlorosilane of formula R2HSiCl (wherein each R is independently selected from alkyl groups having 1 to 18 carbon atoms), and (B) Contains ethylene, (A) organohydridochlorosilane and (B) ethylene are brought into contact with the starting materials, each in the gas phase. The dehydrogenation silylation reaction is carried out in the presence of a heterogeneous metal catalyst (C) containing rhenium and a support, This includes preparing a reactor effluent containing a vinyl-functionalized organochlorosilane.

[0103] In a second embodiment, the process of the first embodiment further includes reducing (C) a heterogeneous metal catalyst before step 1).

[0104] In the third embodiment, in the process of the second embodiment, the reduction of (C) heterogeneous metal catalyst includes heating a reactor containing (C) heterogeneous metal catalyst at a temperature of >100°C to 400°C while exposing it to hydrogen or a mixture of hydrogen and an inert gas.

[0105] In the fourth embodiment, in any one of the processes of the first to third embodiments, step 1) includes heating (A) organohydridochlorosilane, (B) ethylene, and (C) heterogeneous metal catalyst at a temperature of 200°C to 300°C.

[0106] In the fifth embodiment, the process of any one of the first to fourth embodiments further includes an additional step, the additional step is 2) After step 1), the reactor effluent is cooled, thereby condensing the material containing vinyl-functionalized organochlorosilane and optionally unreacted (A) organohydridochlorosilane. 3) Gas / liquid separation after step 2), 4) Recirculating unreacted gaseous ethylene after step 2) or step 3), 5) Recirculate unreacted organohydridochlorosilane. 6) Purification of vinyl-functionalized organochlorosilanes, and 7) Repeat step 1) using gaseous ethylene from step 4) and / or unreacted organohydridochlorosilane from step 5), and A group consisting of two or more of steps 2) to 7) may be selected.

[0107] In the sixth embodiment, the process of any one of the first to fifth embodiments includes chlorodimethylsilane (Me2HSiCl).

[0108] In the seventh embodiment, in any one of the processes of the first to sixth embodiments, the carrier is selected from the group consisting of activated carbon, graphite, silicon carbide, alumina, ceria, silica, magnesium oxide, and calcium oxide.

[0109] In the eighth embodiment, the process described in any one of the first to seventh embodiments is performed, wherein, prior to step 1), Re2(CO) is applied to the substrate via initial wetting. 10 (C) A heterogeneous metal catalyst is further prepared by a process including the precipitation of (C).

[0110] In the ninth embodiment, in any one of the processes of the first to eighth embodiments, the vinyl-functionalized organochlorosilane has the formula (CH2=CH-)R2SiCl, where each R is independently selected from a monovalent hydrocarbon group of 1 to 18 carbon atoms.

[0111] In the tenth embodiment, in the process of the ninth embodiment, the vinyl-functionalized organochlorosilane includes vinyldimethylchlorosilane.

Claims

1. A process for producing a reaction product containing a vinyl-functionalized chlorosilane, 1) Under conditions for carrying out the dehydrogenation silylation reaction in the reactor, (A) Formula R （３－ｘ） HSiCl ｘ The hydridochlorosilane (wherein each R is independently selected from alkyl groups having 1 to 18 carbon atoms, and the subscript x is 1 to 3), and (B) Contains ethylene, (A) The hydridochlorosilane and (B) the ethylene are in the gas phase, and the starting materials are brought into contact with each other. The dehydrogenation silylation reaction is carried out in the presence of a heterogeneous metal catalyst (C) containing rhenium and a support, A process comprising preparing a reactor effluent containing the vinyl-functionalized chlorosilane.

2. The process according to claim 1, wherein step 1) includes heating at temperatures >125°C and <400°C.

3. The process according to claim 2, wherein the temperature is 200°C to 300°C.

4. The process according to any one of claims 1 to 3, further comprising (C) reducing the heterogeneous metal catalyst before step 1).

5. (C) The process according to claim 4, wherein reducing the heterogeneous metal catalyst comprises (C) heating the reactor containing the heterogeneous metal catalyst at a temperature of >100°C to 500°C while exposing it to hydrogen or a mixture of hydrogen and an inert gas.

6. The process further includes an additional step, and the additional step is 2) After step 1), the reactor effluent is cooled, thereby condensing the material containing vinyl-functionalized chlorosilane and optionally unreacted (A) hydridochlorosilane. 3) Gas / liquid separation after step 2), 4) Recirculating unreacted gaseous ethylene after step 2) or step 3), 5) Recirculate the unreacted hydridochlorosilane. 6) Purifying the vinyl-functionalized chlorosilane, and 7) Repeat step 1) using gaseous ethylene from step 4) and / or unreacted hydridochlorosilane from step 5), and The process according to any one of claims 1 to 3, selected from the group consisting of two or more steps 2) to 7).

7. The organohydridochlorosilane is, R ２ The process according to any one of claims 1 to 3, comprising HSiCl (wherein each R is independently selected from a monovalent hydrocarbon group having 1 to 18 carbon atoms).

8. The hydride chlorosilane is of formula (CH ３ ) ２ The process according to claim 7, comprising HCl chlorodimethylsilane.

9. The process according to any one of claims 1 to 3, further comprising (C) preparing the heterogeneous metal catalyst by a process that includes precipitating a rhenium compound on the substrate via initial wetting prior to step 1).

10. The rhenium compound is Re ２ (CO) １０ The process according to claim 9, including the process described in claim 9.

11. The process according to any one of claims 1 to 3, wherein the carrier is selected from the group consisting of activated carbon, graphite, silicon carbide, alumina, ceria, silica, magnesium oxide, and calcium oxide.

12. The process according to claim 11, wherein the carrier is selected from the group consisting of activated carbon and alumina.

13. wherein the vinyl-functional chlorosilane has the formula (CH ２ =CH--)R （３－ｘ） SiCl ｘ (where each R is independently selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms, and the subscript x is 1 to 3), the process according to any one of claims 1 to 3.

14. The process according to claim 13, wherein the vinyl-functionalized organochlorosilane includes vinyldimethylchlorosilane.

15. (C) The process according to any one of claims 1 to 14, wherein the heterogeneous metal catalyst further comprises an additional metal selected from the group consisting of silver (Ag), cobalt (Co), nickel (Ni), palladium (Pd), and iridium (Ir).

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