Gas phase dehydrosilylation process using heterogeneous rhenium catalyst

Abstract

A process for preparing vinyl-functional chlorosilanes is carried out by dehydrosilylation of hydrogenated chlorosilanes and ethylene, both in the gas phase, in the presence of a heterogeneous rhenium catalyst. The method can be used for preparing vinyldimethylchlorosilane under ambient pressure.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit under 35 USC §119(e) of U.S. Provisional Patent Application No. 63 / 416,956, filed on October 18, 2022. U.S. Provisional Patent Application No. 63 / 416,956 is hereby incorporated by reference. Technical Field

[0003] A process for preparing vinyl functional chlorosilanes comprises the use of a rhenium catalyst. More particularly, the process is carried out by dehydrogenative silylation of hydrochlorosilanes and ethylene, both in the gas phase, in the presence of a heterogeneous rhenium catalyst. Background Art

[0004] Hydrosilylation is generally known in the art and involves an addition reaction between silicon-bonded hydrogen and an aliphatic unsaturated group. Hydrosilylation is utilized in various applications, such as for crosslinking components of curable compositions. Hydrosilylation can also be used to prepare individual components or compounds, such as for components included in such curable compositions. Typically, hydrosilylation is performed in the presence of a platinum-based catalyst due to the excellent catalytic activity and stability of platinum-based catalysts. Although platinum metals are generally much more expensive than other metals with less catalytic activity, non-platinum catalysts may suffer from instability when exposed to environmental conditions. Specifically, non-platinum catalysts may be prone to undesirable side reactions with ambient oxygen and water, thereby limiting their use and potential end applications.

[0005] Similar to hydrosilylation reactions, dehydrogenative silylation reactions are also known in the art and similarly involve the reaction between silicon-bonded hydrogen and aliphatic unsaturated groups. However, in dehydrogenative silylation, the aliphatic unsaturated groups are bonded to silicon vinyl groups. Dehydrogenative silylation reactions can be used to prepare unsaturated compounds (e.g., olefin functional compounds), which can further undergo additional functionalization and / or coupling reactions (e.g., via hydrosilylation).

[0006] Unfortunately, the catalysts used for dehydrogenative silylation suffer from many disadvantages associated with hydrosilylation catalysts, such as sensitivity to oxygen, water and even light. In addition, although such disadvantages have been overcome by recent advances in hydrosilylation catalysts, many catalytic systems suitable for hydrosilylation reactions are not practical for use in dehydrogenative silylation reactions. For example, many such catalysts show selectivity that is conducive to addition reactions, especially for minimally substituted olefins, resulting in non-selective reactions with undesirable product mixtures and low yields. In addition, many conventional dehydrogenative silylation conditions are not functional group tolerant, and are therefore limited in use. Summary of the invention

[0007] A method for preparing vinyl-functional chlorosilanes comprises the dehydrogenative silylation reaction of (A) a hydrochlorosilane and (B) ethylene in the presence of (C) a heterogeneous metal catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 A schematic diagram of the process setup according to the invention for preparing vinyl-functional chlorosilanes is shown.

[0009] Reference numerals

[0010] Schematic diagram of the 100 method equipment

[0011] 101 Vaporizer

[0012] 102 Reactor

[0013] 102a Cavity

[0014] 102b Heterogeneous Metal Catalysts

[0015] 103 Condenser

[0016] 104 Distillation Unit

[0017] 105 Hydrochlorosilane feed line

[0018] 106 Gaseous hydrochlorosilane export pipeline

[0019] 107 Ethylene feed line

[0020] 108 Gas feed line

[0021] 109 Reactor effluent pipeline

[0022] 110 condenser outlet pipeline

[0023] 111 Recirculation pipeline

[0024] 112 purification pipeline

[0025] 113 Liquid crude product pipeline

[0026] 114 Vinyl-functional chlorosilane pipeline

[0027] 115 By-product export pipeline DETAILED DESCRIPTION

[0028] The starting materials used in the methods introduced above are further described as follows:

[0029] (A) Hydrochlorosilane

[0030] The starting material (A) used in the methods described herein is a hydrosilane, i.e., a siloxane compound having at least one hydrogen atom bonded to silicon (i.e., Si-H group) and at least one chlorine atom bonded to silicon (i.e., Si-Cl group). The hydrosilane can have the general formula R (3-x) HSiCl x , where the subscript x is from 1 to 3, or 1 or 2; and each R is an independently selected alkyl group having 1 to 18 carbon atoms. For example, when the subscript x is 1 or 2, the hydrosilane can be an organohydrosilane. For example, the subscript x can be 1, such that the (A) hydrosilane can be an organohydrosilane, which can include a diorganohydrosilane of the formula R2HSiCl. Alternatively, the subscript x can be 2, such that the organohydrosilane contains an organodichlorosilane of the formula RHSiCl2. Alternatively, the subscript x can be 3, where the (A) hydrosilane can be trichlorosilane (HSiCl3). Alternatively, a combination of hydrosilanes can be utilized, for example, where the subscript x has an average value such that 1 < x < 3. Alternatively, a combination of organohydrosilanes can be utilized, for example where the subscript x has an average value such that 1 < x < 2.

[0031] In the formulae of the above organohydrosilanes, each R is an independently selected alkyl group having 1 to 18 carbon atoms. The alkyl groups suitable for R can independently be straight-chain, branched-chain, 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-chain saturated hydrocarbon groups, such as those having 6 to 18 carbon atoms. Alternatively, the alkyl groups of R can have 1 to 16, alternatively 1 to 14, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, and alternatively 1 to 2 carbon atoms.

[0032] When the subscript x is 1, such that the organohydrosilane is a diorganohydrosilane, each R can be the same as or different from the other Rs in the diorganohydrosilane. Alternatively, each R can be the same as each other R in the diorganohydrosilane. Alternatively, when, for example, the subscript x = 2, one R can be different from the other R in another molecule of the organohydrosilane in the formula shown above. Alternatively, each R can independently be selected from methyl groups and ethyl groups. Alternatively, each R can be methyl. For example, the organohydrosilane can have the formula HSiCl x (CH3) (3-x), wherein the subscript x is 1 or 2, as described above. Alternatively, the organohydrogenated chlorosilane may comprise chlorodimethylsilane (i.e., chlorodimethylsilane of the formula HSiCl(CH3)2), dichloromethylsilane (i.e., dichloromethylsilane of the formula (CH3)HSiCl2), diisopropylchlorosilane (i.e., diisopropylchlorosilane of the formula HSiCl(CH(CH3)2)), or a combination thereof. Alternatively, the organohydrogenated chlorosilane may comprise chlorodimethylsilane, dichloromethylsilane, or a combination thereof. Alternatively, the organohydrogenated chlorosilane may comprise, alternatively may be, chlorodimethylsilane. Organohydrogenated chlorosilanes such as chlorodimethylsilane are known in the art and are commercially available, for example, from Sigma Aldrich of St.Louis, Missouri, USA. Other organohydrochlorosilanes, such as diisopropylchlorosilane, are commercially available from Gelest, Inc. of Morrisville, Pennsylvania, USA.

[0033] (B) Ethylene

[0034] The starting material (B) in the method described herein is ethylene. Ethylene can be used in gaseous form or as starting material (B). Ethylene is not limited and can be used in pure form (i.e., free of, alternatively substantially free of other components or compounds). In other words, starting material (B) can be composed of ethylene, alternatively can be substantially composed of ethylene, or can include a combination of ethylene and other components. Alternatively, the dehydrogenation silylation reaction method described herein may include introducing a reactor fluid comprising ethylene, alternatively substantially composed of ethylene, alternatively composed of ethylene into a reactor comprising at least a starting material (C) heterogeneous metal catalyst. The reactor fluid may include components other than ethylene, such as a carrier medium, as will be understood by those skilled in the art, and the component will generally include (or will be) a substance that is inert (i.e., will not react with starting material (A), (B) or (C)) under the reaction conditions utilized in the dehydrogenation silylation method. Examples of such carrier media include inert gases, such as nitrogen (N2), helium (He), argon (Ar), and combinations thereof. Alternatively, (B) ethylene may be utilized in pure form and consist essentially of ethylene (i.e., and substantially free of a carrier vehicle, alternatively free of a carrier vehicle). Ethylene is known in the art and is commercially available, for example, from Sigma-Aldrich, St. Louis, Missouri, USA.

[0035] Dehydrogenation silylation reaction method can utilize any amount of starting materials (A) and (B), and more specifically, can include different amounts or ratios of (A) hydrochlorosilane and (B) ethylene, it depends on the desired properties (such as conversion rate) of the reaction and / or the characteristics of the starting materials adopted. Usually, starting material (B) ethylene is utilized with a stoichiometric ratio of at least 1:1, based on the number of hydrogen groups bonded to silicon (that is, the number of Si-H groups capable of dehydrogenation silylation reaction) to be vinylized per molecule of starting material (A) hydrochlorosilane. Thus, the amount of (B) ethylene is usually selected based on the amount, type and solubility of starting material (A), as will be understood by those skilled in the art. Excessive or crude excess (B) ethylene can be utilized to maximize the degree of conversion of (A) hydrochlorosilane to vinyl-functional chlorosilane. For example, starting materials (A) and (B) can be utilized with a stoichiometric (molar) ratio (A): (B) of 1:>1. Alternatively, ethylene is utilized in an amount sufficient to provide a molar ratio of (B) to (A) of 1:1 to 100:1, such as 1:1 to 50:1, alternatively 1:1 to 25:1, alternatively 1:1 to 20:1, alternatively 1:1 to 15:1, alternatively 1:1 to 10:1, alternatively 2:1 to 10:1, and alternatively 2:1 to 6:1 (B) ethylene: (A) hydrochlorosilane. Higher or lower ratios may also be used. For example, a crude excess of (B) ethylene (e.g., a molar ratio of >100:1 (B): (A)) may be utilized.

[0036] (C) Heterogeneous Metal Catalysts

[0037] 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 with a Re compound. For example, the Re compound may comprise the formula Re2(CO) 10 Decacarbonyldirhenium, ReCl5, Re3Cl9, NH4ReO4 and HReO4, which can be commercially obtained, for example, from Sigma Aldrich. The Re compound can be dissolved in a solvent such as THF and then mixed with a support. The solvent can then be removed by, for example, heating and / or decompression. After the solvent is removed, further heat treatment allows the removal of organic and volatile inorganic substances from the Re compound, thus leaving the Re metal particles on the support as a heterogeneous catalyst. The support is not critical, and the support can be selected from the group consisting of activated carbon, graphite, silicon carbide, aluminum oxide, cerium dioxide, silicon dioxide, magnesium oxide and calcium oxide, all of which are commercially available. Alternatively, the support can be activated carbon or aluminum oxide.

[0038] Alternatively, the heterogeneous metal catalyst may optionally further comprise an additional metal (i.e., a metal other than rhenium). The additional metal may be selected from the group consisting of silver (Ag), cobalt (Co), nickel (Ni), palladium (Pd), and iridium (Ir). Alternatively, the additional metal may be any one of Ag, Co, Ni, Pd, or Ir. Alternatively, the additional metal may be selected from the group consisting of Ag and Co. A heterogeneous metal catalyst comprising Re and a support and an additional metal may be prepared as described above, for example, by initially wetting the support with a Re compound and an additional metal compound. The solution of the Re compound and the additional metal compound may be mixed with the support in any order, for example, a solvent solution of the above-mentioned Re compound may be mixed with the support, the solvent may be removed by heating, and then the additional metal compound (dissolved in the solvent) may be mixed with the support, and then the solvent may be removed. Alternatively, a solvent solution of the additional metal compound may be mixed with the support, the solvent may be removed, and then the solution of the Re compound may be mixed with the support.

[0039] The amount of (C) heterogeneous metal catalyst is sufficient to catalyze the dehydrogenative silylation reaction of the silicon-bonded hydrogen of (A) hydrochlorosilane and (B) ethylene. The exact amount of (C) heterogeneous metal catalyst depends on various factors, including the reactor type used for the method and the flow rate of (A) hydrochlorosilane and (B) ethylene. For example, the reactor used in the method can be any reactor suitable for contacting gas and solid, such as a fixed bed reactor, a fluidized bed reactor or an autoclave reactor. The heterogeneous metal catalyst can be placed in a fixed bed or fluidized bed reactor, and ethylene and hydrochlorosilane can be fed into the reactor individually or as a mixture. Alternatively, the heterogeneous metal catalyst (C) can be placed in an autoclave reactor, or loaded in a catalyst basket in the autoclave reactor.

[0040] Method steps

[0041] A method for making a reaction product containing a vinyl-functional chlorosilane is described herein. The method comprises:

[0042] Optionally, 1) reducing (C) a heterogeneous metal catalyst comprising rhenium and a support as described above beforehand;

[0043] 1) contacting the starting materials comprising the following in a reactor under conditions for carrying out a dehydrogenative silylation reaction:

[0044] (A) Formula R (3-x) HSiCl x Hydrochlorosilane wherein each R is an independently selected alkyl group having 1 to 18 carbon atoms, and the subscript x is 1 to 3 (as described above);

[0045] (B) ethylene (as defined above); and

[0046] wherein (A) hydrochlorosilane and (B) ethylene are each in the gas phase;

[0047] optionally an inert gas; and

[0048] wherein the dehydrogenative silylation reaction is carried out in the presence of (C) a heterogeneous metal catalyst (as described above);

[0049] Thereby a reactor effluent comprising the vinyl-functional chlorosilane is produced.

[0050] The method may optionally further comprise one or more additional steps. The additional steps may be selected from the group consisting of:

[0051] 2) cooling the reactor effluent after step 1) to condense the material comprising the vinyl-functional chlorosilane and optionally unreacted (A) hydrochlorosilane;

[0052] 3) performing gas / liquid separation after step 2);

[0053] 4) recycling unreacted gaseous ethylene after step 2) or step 3);

[0054] 5) recycling unreacted hydrochlorosilane after any one or more of step 1), step 2), step 3), step 4), and step 6);

[0055] 6) purifying vinyl-functional chlorosilanes; and

[0056] 7) repeating step 1) using the gaseous ethylene from step 4) and / or the unreacted hydrochlorosilane from step 5); and

[0057] Two or more of steps 2) to 7).

[0058] Step 1) reducing the heterogeneous metal catalyst.

[0059] Step 1) in the above method is to reduce the (C) heterogeneous metal catalyst. The reduction of the heterogeneous metal catalyst can be carried out by any convenient means. The reduction may include heating a reactor containing the (C) heterogeneous metal catalyst at a temperature of >100°C to 500°C, alternatively 100°C to 400°C, and alternatively 200°C to 300°C, while being exposed to a mixture of hydrogen or hydrogen and an inert gas (such as nitrogen or argon).

[0060] Step 1)

[0061] In step 1) of the above method, (A) hydrochlorosilane and (B) ethylene are both 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 can be placed in a reactor, and the starting materials comprising (B) ethylene and (A) hydrochlorosilane can be fed into the reactor individually or as a mixture in step 1). Gaseous hydrochlorosilane and ethylene (and any other starting materials, such as the above-mentioned inert gas) can be fed at a flow rate and contact time that effectively causes a dehydrogenative silylation reaction at a selected pressure and temperature. Alternatively, (C) a heterogeneous metal catalyst can be placed in an autoclave reactor, or loaded in a catalyst basket in the autoclave reactor, and the starting materials comprising (A) hydrochlorosilane and (B) ethylene can be loaded and maintained at a selected temperature and pressure to carry out the dehydrogenative silylation reaction in step 1).

[0062] The temperature in step 1) is sufficient to carry out the dehydrogenative silylation reaction and may be >125°C, alternatively at least 200°C, while at the same time the temperature may be <400°C, alternatively up to 300°C. Alternatively, the temperature in step 1) may be >125°C to <400°C; alternatively, the temperature may be 200°C to 300°C.

[0063] The reactor in step 1) can optionally be pressurized with ethylene (e.g., via a gas manifold). Alternatively, starting materials (A) and (B) can be provided in the reactor at ambient pressure, alternatively 90 kPa to 500 psi (3447.4 kPa), alternatively 90 kPa to 690 kPa, 100 kPa ± 10 kPa. Alternatively, higher pressures can be used. When designing equipment to carry out step 1) of the method, those skilled in the art will balance productivity and other factors, such as capital costs. Optionally, an inert gas may be added during step 1). For example, nitrogen or argon may be used to optimize method step 1).

[0064] Additional Steps

[0065] As mentioned above, the above process may further include one or more additional steps, which may be performed in any convenient order. For example, in step 2), the reactor effluent may be cooled to, for example, RT or a temperature <125°C, or to any temperature sufficient to condense the vinyl-functional chlorosilane and / or any unreacted hydrochlorosilane. Unreacted ethylene may be collected via gas / liquid separation in step 3), and unreacted ethylene may optionally be recycled in step 1) of the process.

[0066] The above method may further include step 6) purifying the vinyl-functional chlorosilane from the reactor effluent. Purifying the vinyl-functional chlorosilane refers to increasing the relative concentration of the vinyl-functional chlorosilane compared to other compounds combined with the vinyl-functional chlorosilane (e.g., in the reactor effluent after step 1), or in a purified version thereof (e.g., if the above-mentioned gas / liquid separation and / or recycling steps are performed). As understood in the art, purification can include removing other compounds from this combination (i.e., reducing the amount of impurities / other components combined with the vinyl-functional chlorosilane in the reactor effluent) and / or removing the vinyl-functional chlorosilane itself from the combination. Any suitable purification technique and / or scheme can be utilized, such as distillation, stripping / evaporation, extraction, filtration, washing, distribution, phase separation, and chromatography and combinations thereof, such as sequentially or as part of a single process. Regardless of the specific technique selected, the purification of the vinyl-functional chlorosilane can be performed sequentially with the reaction itself (i.e., performed in sequence), and can therefore be automated. Alternatively, purification can be a separate process performed on the reactor effluent containing the vinyl-functional chlorosilanes.

[0067] The distillation for purifying vinyl-functional chlorosilane can be carried out at a pressure and temperature (i.e., reduced temperature and reduced pressure) lower than atmospheric pressure. The reduced temperature and pressure will be selected by those skilled in the art according to selected reaction conditions and parameters, the starting material utilized, the prepared vinyl-functional chlorosilane. Although any reduced pressure between vacuum and the atmospheric pressure of 101.325kPa can be utilized, the reduced pressure is usually operated as a vacuum. For example, the reduced pressure can be>0kPa to 50kPa, alternatively>0kPa to 40kPa, alternatively>0kPa to 30kPa, alternatively>0kPa to 20kPa, alternatively>0kPa to 10kPa, alternatively>0kPa to 5kPa, alternatively>0kPa to 4kPa, alternatively>0kPa to 3kPa, alternatively>0kPa to 2kPa.

[0068] Any unreacted hydrochlorosilane may also be recovered during the gas / liquid separation during step 3) and / or during the purification (e.g., the above-mentioned distillation step) in step 6), and the method may further include step 5), in which the unreacted hydrochlorosilane may optionally be recycled in step 1) in the method. Step 5) may be performed before or after the above-mentioned step 6). The method may optionally further include step 7) to repeat step (1). In step 7), ethylene recovered via gas / liquid separation in step 3), unreacted hydrochlorosilane recovered as described above, or both ethylene and unreacted hydrochlorosilane may be recycled.

[0069] The product prepared by the above method is of the formula (CH2=CH-)R (3-x) SiCl x A vinyl-functional chlorosilane wherein each R is an independently selected alkyl group of 1 to 18 carbon atoms and the subscript x is 1 to 3, alternatively 1 or 2, as described above. Alternatively, the vinyl-functional chlorosilane may be a vinyl-functional organochlorosilane having a formula selected from the group consisting of (CH2=CH-)R2SiCl, (CH2=CH-)RSiCl2, and combinations thereof. Alternatively, the vinyl-functional organochlorosilane may include vinyldimethylchlorosilane, vinylmethyldichlorosilane, or a combination thereof. The vinyl-functional chlorosilane prepared according to the above method may be used in a variety of end-use applications, for example as a discrete component in a composition such as a curable composition, for example a hydrosilylation reaction curable composition.

[0070] Suitable equipment for carrying out the above method is as follows Figure 1 Schematic diagram of the process equipment 100. The process equipment 100 includes an evaporator 101 upstream of a fixed bed reactor 102, upstream of a condenser 103, and upstream of a distillation unit 104. Hydrochlorosilane can be fed to the evaporator 101 as a liquid via a hydrochlorosilane feed line 105. Hydrochlorosilane, such as dimethylchlorosilane, is heated and evaporated by the evaporator 101. Hydrochlorosilane (now in the gas phase) leaves the heater via a gaseous hydrochlorosilane outlet line 106. Ethylene is introduced via an ethylene feed line 107. Ethylene and hydrochlorosilane, both in the gas phase, are fed into the reactor 102 via a gas feed line 108. The reactor 102 defines a cavity 102a, which contains a heterogeneous metal catalyst 102b. Gaseous hydrochlorosilane and ethylene contact a heterogeneous metal catalyst 102b in the reactor 102, and a dehydrogenative silylation reaction occurs, as illustrated in the following Scheme 1, wherein the hydrochlorosilane is dimethylchlorosilane. One or more of hydrogen, ethane, and ethyldimethylchlorosilane may be produced as a byproduct of the dehydrogenative silylation reaction.

[0071]

[0072] Scheme 1 - Dehydrogenative silylation

[0073] The reactor effluent is transferred out of the reactor 102 via the reactor effluent line 109 and enters the condenser 103. The reactor effluent contains unreacted ethylene, byproduct ethane, and vinyl-functional chlorosilane products (e.g., vinyldimethylchlorosilane in Scheme 1 above). When the reactor effluent is cooled in the condenser 103, the unreacted ethylene and byproduct ethane can be separated out via the condenser outlet line 110 and recycled to the reactor 102 via the recycle line 111 or discarded via the purge line 112. The liquid crude product leaves the condenser via the liquid outlet line 113, and the liquid crude product can be fed to the distillation unit 104. Vinyl-functional chlorosilanes and any byproducts, such as ethyl-functional chlorosilanes, can be separated in different distillation cuts. The vinyl-functional chlorosilanes may exit the distillation apparatus 104 via vinyl-functional chlorosilane line 114 , and any remaining byproducts may exit the distillation apparatus 104 via byproduct outlet line 115 .

[0074] Those skilled in the art will recognize that Figure 1 Examples are shown, and other means for practicing the methods described herein are within the scope of the present invention. For example, instead of feeding ethylene into reactor 102 together with gaseous hydrochlorosilane, ethylene can be directly introduced into reactor 102 by moving ethylene feed line 107. Alternatively, ethylene feed line 107 can introduce ethylene upstream or downstream of any recycle line 111. Recycling unreacted ethylene is optional, and therefore, recycle line 111 can be omitted. Fixed bed reactor 102 can be replaced by a fluidized bed reactor, a multi-tubular reactor (which distributes hydrochlorosilane from gas feed line 108 to multiple smaller tubes) or other types of reactors suitable for contacting gas and solids. Alternatively, two or more reactors suitable for contacting gas and solids can be used in series to improve conversion, or in parallel, so that when the heterogeneous metal catalyst in the first reactor is used up, hydrochlorosilane and ethylene can be fed to a second reactor with a fresher catalyst to continue production, while regenerating or replacing the heterogeneous metal catalyst in the first reactor.

[0075] Example

[0076] These examples are intended to illustrate the invention to those skilled in the art and are not to be construed as limiting the scope of the invention described in the claims. The starting materials used in these examples are described in Table 1.

[0077] Table 1 - Starting Materials

[0078]

[0079]

[0080] Catalyst Preparation (CP) Example

[0081] CP Example 1: Preparation of Activated Carbon Supported with 3% Re

[0082] In a glove box, activated carbon (1.00 g, Cabot NORIT 3 EXTRA) was placed in a wide-mouth bottle, and Re2(CO) was added dropwise under gentle shaking. 10 (0.0542 g) was dissolved in THF (1 mL). The carbon was allowed to stand for 30 minutes and then the THF was removed in vacuo at room temperature (RT) for 15 h. A total of 1.110 g was isolated, indicating that some THF was not removed during the evacuation.

[0083] CP Example 2: Preparation of 10% Cu / a-Al2O3

[0084] A 20 mL vial was charged with 6.79 mL of a saturated copper nitrate / water solution (density = 1.67 g / mL) and 7.02 mL of distilled water. The vial was then charged with 1.41 mL of ethylene glycol. The cap was placed on the vial and shaken vigorously for 30 seconds to mix the contents.

[0085] 4.931 g of ALAP C1-5 alpha-alumina support (lot number BL073321, SS070636 TB) was then added to the solution in the vial. The support was allowed to soak in the solution for 3 hours before being removed and placed in a small ceramic dish.

[0086] The pan was transferred to a Lindbreg Blue M furnace purged with air (20 L / min) and heated to 88°C at a rate of 2°C / min, held at 88°C for 10 h, heated to 260°C at a rate of 2°C / min, held at 260°C for 90 minutes, and then allowed to cool to room temperature. Once cooled, a sample was collected and weighed (5.497 g).

[0087] CP Example 3: Preparation of activated carbon loaded with about 3% Ni

[0088] In a glove box, activated carbon (1.00 g, Cabot NORIT 3EXTRA) was loaded into a wide-mouth bottle, and a solution of bis(cyclooctadiene)nickel (0) (0.145 g) dissolved in toluene (2 mL) was added dropwise to the carbon at 60°C under gentle shaking. A small portion of solid Ni(COD)2 that was not dissolved was not added to the carrier. The carbon was allowed to stand for 10 minutes, and then volatiles were removed in vacuum at room temperature for 1 h. A total of 1.31 g was isolated, indicating that some toluene was not removed.

[0089] Comparative Example 1 - Vapor Phase Dehydrogenative Silylation of Ethylene with Chlorodimethylsilane Using 3% Ru on Activated Carbon

[0090] The heterogeneous metal catalyst 3 wt% Ru / C (1.38 g, extrudate, provided by Johnson Matthey) was loaded into the middle of a reactor tube (3 / 8" OD) made of Inconel. The length of the packed catalyst bed was 3 inches long. The catalyst was packed between two quartz bead beds (approximately 6 inches to 8 inches each). The reactor tube was connected to a flow device and the catalyst was reduced under H2 / N2 flow (90 sccm each) at a temperature ranging from 100°C to 300°C for a cumulative 5 hours. Chlorodimethylsilane (HSiMe2Cl) was fed into the reactor via a bubbler using a mass flow controller along with N2 as a carrier gas. A mass flow controller feeds ethylene gas from a cylinder equipped with a pressure regulator into the reactor. Throughout the entire experiment, the ethylene / SiH ratio remains constant at 2 mol / mol. All feed lines to the reactor are preheated to 170°C. Throughout the entire experiment, the temperature of the reactor changes from 200°C to 400°C. The flow rate of the gas is adjusted accordingly to obtain a residence time ranging from about 3 seconds to 5 seconds. The back pressure regulator is bypassed to maintain the atmospheric pressure in the reactor. The reactor outlet is connected to an online GC / TCD / MS through a 3-way valve assembly for periodic sample injection to perform qualitative and quantitative analysis of reagents and products. The feed line of the GC is heated (heat tracing). traced) and maintained at 150 ° C. A dry ice trap was used downstream of the reactor to condense the product. The results are shown in Table 2. This example demonstrates that the dehydrogenative silylation of Me2HSiCl with ethylene, all in the gas phase using Ru / C catalysts, produces a reaction product with a Vi / Et ratio much less than 1, which is different from that shown in patent application publication WO2021-127179 for dehydrogenative silylation using liquid homogeneous Ru catalysts.

[0091] Table 2 - Obtained by dehydrogenative silylation of chlorodimethylsilane with ethylene over Ru / C by online GC analysis Product distribution (weight %) .

[0092]

[0093] a NA means ethylchlorodimethylsilane is below the GC detection limit

[0094] Comparative Example 2 - Recycling Ru / C

[0095] The same catalyst as used in Comparative Example 1 is also used in this Comparative Example 2. See Comparative Example 1 for catalyst loading and preparation. Prior to this experiment, the catalyst was reduced for the second time at a temperature of 500° C. for 1.5 hours under H2 / N2 flow (respectively 90 / 180sccm). Chlorodimethylsilane (HSiMe2Cl) is fed into the reactor via a bubbler with N2 as a carrier gas using a mass flow controller. Ethylene gas is fed into the reactor from a cylinder equipped with a pressure regulator via a mass flow controller. All feed lines of the reactor are preheated to 170° C. Throughout the entire experiment, the temperature of the reactor remains constant at 300° C. The total flow rate of ethylene and chlorodimethylsilane gas is kept constant to obtain a constant residence time of 3 seconds. Throughout the entire experiment, ethylene: SiH ratio changes from 2mol / mol to 5mol / mol. Bypass the back pressure regulator to maintain the atmospheric pressure in the reactor. The reactor outlet is connected to an online GC / TCD / MS by a 3-way valve assembly for periodic sample injection to perform qualitative and quantitative analysis of reagents and products. The feed line to the GC was heated and maintained at 150°C. A dry ice trap was used downstream of the reactor to condense the product. The results are shown in Table 3. This example shows that the use of a Ru / C heterogeneous catalyst does not adequately catalyze the dehydrogenative silylation reaction; even though the ethylene:SiH ratio was varied under the test conditions, each test sample produced a product with a Vi / Et ratio much less than 1.

[0096] Table 3 - Products obtained from the dehydrogenative silylation of Me2HSiCl with ethylene over Ru / C by online GC analysis Material distribution (weight %) .

[0097]

[0098] a NA Use when ethylchlorodimethylsilane is below the GC detection limit

[0099] Comparative Example 3 - Vapor Phase Dehydrogenative Silylation of Ethylene with Chlorodimethylsilane Using 21% Ru on Alumina

[0100] The heterogeneous metal catalyst 21 wt% Ru / Al2O3 (0.96 g, spheres) was loaded into the middle of a reactor tube (3 / 8" OD) made of Inconel. The length of the packed catalyst bed was 3 inches long. The catalyst was packed between two quartz bead beds (approximately 6 inches to 8 inches each). The reactor tube was connected to a flow device and the catalyst was reduced under H2 / N2 flow (60 sccm / 180 sccm, respectively) at a temperature ranging from 100°C to 300°C for a cumulative 5 hours. Chlorodimethylsilane was fed into the reactor through a bubbler using a mass flow controller along with N2 as a carrier gas. Ethylene gas was fed into the reactor from a cylinder equipped with a pressure regulator via a mass flow controller. The reactor was fed with ethylene:SiH. The temperature of the reactor was kept constant at 300°C throughout the experiment. The total flow rate of the gas was kept constant to obtain a constant residence time of 3 seconds. The ethylene:SiH ratio was varied from 2 mol / mol to 10 mol / mol throughout the experiment. The back pressure regulator was bypassed to maintain atmospheric pressure in the reactor. The reactor outlet was connected to an online GC / TCD / MS via a 3-way valve assembly for periodic sample injection for qualitative and quantitative analysis of reagents and products. The feed line to the GC was heated and maintained at 150°C. A dry ice trap was used downstream of the reactor to condense the product. The results are shown in Table 4. This example shows that the chlorodimethylsilane and ethylene reaction attempted using Ru / Al2O3 catalyst Gas Phase Dehydrogenative silylation produced products with Vi / Et ratios less than 1 mol / mol during most of the runs, indicating poor selectivity for the desired product under the conditions tested. Only one initial measurement showed the desired Vi / Et ratio, but this performance was not maintained during additional measurements.

[0101] Table 4 - Dehydrogenative silylation of Me2HSiCl with ethylene over Ru / Al2O3 by online GC analysis Product distribution (weight %) .

[0102]

[0103] a NA Use when ethylchlorodimethylsilane is below the GC detection limit

[0104] Comparative Example 4 - Liquid Phase Reaction of Ethylene with Chlorodimethylsilane Using Ru / C

[0105] The heterogeneous metal catalyst 3 wt% Ru / C (506 mg, extrudate, provided by Johnson Matthey) was loaded into the middle of a reactor tube (3 / 8" OD) made of Inconel. The reactor tube was connected to a flow device and the catalyst was reduced under H2 / N2 flow (90 sccm each) at a temperature ranging from 100°C to 300°C for a cumulative 5 hours. The reactor was then purged with excess N2, sealed and transferred to an inertized glove box. In the glove box, toluene (30.15 g) and chlorodimethylsilane (13.5 sccm) were prepared in a glass screw-top container. 4g) of 50mL solution. 1.13g of nonane was also added as an internal standard for gas chromatography analysis. 1g of the solution was weighed out in a separate glass vial and combined with 4g of toluene to measure the starting concentration of chlorodimethylsilane by gas chromatography. The remaining solution was then transferred to a 100mL Parr reactor. The catalyst was then loaded into the reaction 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 pipeline was purged with nitrogen for 10 minutes. The reactor was then purged with 100psig of ethylene three times and the pressure was maintained at 400°C. Stir for 1 minute. After purging, the reactor was pressurized with 200 psig of ethylene under continuous stirring at 350 rpm. Ethylene was fed into the reactor until the pressure stabilized at 200 psig. After saturation, the reactor was sealed and heated to 40°C under stirring at 350 rpm. After a 10 minute stabilization period, the reactor was further heated to 100°C under a controlled temperature ramp 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 cooled with an external fan. Once cooled to room temperature, The reactor is decompressed and then purged three times with 100psig nitrogen. After a final decompression, the reactor is connected to a nitrogen stream of 10psig, and the reactor solution is transferred to a stainless steel sample cylinder using this pressure. The cylinder is sealed and then transported to an inert glove box, where the solution is collected in a glass vial. 1g of aliquots are collected in separate vials, diluted with 4g of toluene and analyzed by gas chromatography to determine the composition of the solution after the dehydrogenation coupling reaction. The resulting reaction solution shows a SiH conversion of 66% and a selectivity of 12% (mol Si) Me2ViSiCl. This product mixture is then reused for additional reactions identical to those described above, except that the reactor temperature is maintained at 200°C for 120 minutes. The resulting reaction solution shows a SiH conversion of 100% and a selectivity of 48% (mol Si) Me2ViSiCl. This embodiment shows that Me2ViSiCl can be prepared by using a Ru / C catalyst in Liquid Phase(Slurry) is produced by dehydrogenative silylation of ethylene and chlorodimethylsilane. The use of heterogeneous Ru catalyst and liquid phase reactants provides different results from using the same metal (Ru) as catalyst and gaseous reactants (see Comparative Example 1). Without wishing to be bound by theory, it is believed that dehydrogenative silylation is carried out differently in the gas phase than in the liquid phase, and therefore, those skilled in the art will not have a reasonable expectation of successfully implementing the present invention based on the literature on liquid phase hydrosilane reactants, and the literature cannot predict the performance of the present invention, in which ethylene and organic hydrochlorosilane are both gas phases during the dehydrogenative silylation reaction.

[0106] Working Example 1: Vapor Phase Dehydrogenative Silylation of Ethylene with Chlorodimethylsilane Using Activated Carbon Supported with 3% Re :

[0107] A sample of Re / C catalyst prepared according to CP Example 1 above (0.5 g) was sized to 30 / 50 mesh and loaded into a 1 / 4" diameter reactor tube and held in place between quartz wool plugs, with the remaining reactor volume filled with quartz chips. The reactor was heated to 100°C with a nitrogen flow (200 seem) and held for 1 h. The catalyst was then reduced by heating to 350°C under a 5% hydrogen flow in argon and held for 3 h. The reactor was cooled to 125°C with a nitrogen flow. The nitrogen flow was stopped and an approximately 5:1 mixture of ethylene and chlorodimethylsilane was delivered to the reactor. This was accomplished by bubbling 5% nitrogen in argon (8 seem) through neat chlorodimethylsilane at ambient temperature and combining the resulting vapor with ethylene (60 seem). After 3.33 h, the reactor was heated to 200°C for 3 h, then at 300°C for 4 h, and at 400°C for 4 h with a continuous flow of reactant gas. Throughout the experiment, the reactor was heated to 125°C by a 100°C reactor equipped with a Restek 1000 reactor. The product mixture was analyzed by an online Agilent 7890A GC with a CC1263 column and a TCD detector. The test methods and calculations were performed as described below. The chlorodimethylsilane conversion, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for producing silicon-containing materials at a given temperature as determined by GC are shown in Table 5 below.

[0108] Table 5 - Results using Re / C catalyst

[0109]

[0110] The data in Table 5 show that at temperatures between 200°C and 300°C, reaction products having Vi / Et ratios ≥ 1 were prepared using a heterogeneous catalyst comprising Re and a support under the conditions tested.

[0111] Comparative Example 5: No Metal .

[0112] The procedure in Working Example 1 was followed, except that instead of the catalyst, the activated carbon support was used directly without any metal impregnation. The chlorodimethylsilane conversion, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for producing silicon-containing species at a given temperature were determined by GC and are shown in Table 6 below.

[0113] Table 6 - Results using activated carbon support alone

[0114]

[0115] a N / A = Ethylchlorodimethylsilane not detected

[0116] Comparative Example 6: Vapor Phase Dehydrogenative Silylation of Ethylene with Chlorodimethylsilane Using Activated Carbon Supported with 3% Ru :

[0117] The procedure of Working 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 determined by GC, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for the production of silicon-containing species at a given temperature are shown in Table 7 below.

[0118] Table 7 - Results using Ru / C

[0119]

[0120] Comparative Example 7 :

[0121] The procedure of Working Example 1 was followed, except that the catalyst used was 10% Cu supported on α-Al2O3.

[0122] The chlorodimethylsilane conversion, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane and the selectivity for producing silicon-containing species at a given temperature were determined by GC for the inventive and comparative catalysts. The results of this comparative example 7 are shown in Table 8 below.

[0123] Table 8

[0124]

[0125] a N / A = Ethylchlorodimethylsilane not detected

[0126] Comparative Example 8 :

[0127] The procedure in Working Example 1 was followed, except that the catalyst used was 3% Ni on activated carbon and the catalyst was reduced at 350°C.

[0128] The chlorodimethylsilane conversion, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for producing silicon-containing species at a given temperature for the inventive and comparative catalysts were determined by GC as shown in Table 9 below.

[0129] Table 9

[0130]

[0131] a N / A = Ethylchlorodimethylsilane not detected

[0132] Comparative Example 9: Vapor Phase Dehydrogenative Silylation of Ethylene with Chlorodimethylsilane Using 1% Pt on Activated Carbon :

[0133] The procedure in Working Example 1 was followed except that the catalyst used was 1% Pt on carbon and the 125°C temperature soak was omitted.

[0134] The chlorodimethylsilane conversion determined by GC, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for producing silicon-containing species at a given temperature are shown in Table 10 below.

[0135] Table 10

[0136]

[0137] Comparative Example 10: Vapor Phase Dehydrogenation of Ethylene and Chlorodimethylsilane Using 5% Pd on Activated Carbon change :

[0138] The procedure in Working Example 1 was followed except that the catalyst used was 1% Pd on carbon and the 125°C temperature soak was omitted.

[0139] The chlorodimethylsilane conversion determined by GC, the typical ratio of vinylchlorodimethylsilane to ethylchlorodimethylsilane, and the selectivity for producing silicon-containing species at a given temperature are shown in Table 11 below.

[0140] Table 11

[0141]

[0142] Comparative Examples 7-10 demonstrate that not all metals can catalyze the dehydrogenative silylation of ethylene with dimethylsilyl chloride under the conditions tested at a Vi / Et ratio ≥ 1. The use of copper, nickel, platinum or palladium heterogeneous metal catalysts produced reaction products with poor conversion and poor selectivity to the desired dimethylvinylchlorosilane.

[0143] CP Example 4: Re / C Catalyst Preparation via Automated Methods

[0144] 500 mg of support material was added to a round bottom vial. Multiple vials were used to prepare larger batches of a single catalyst. These were placed in a vertical shaker. Using an automated dosing pump, the metal precursor (Re2(CO) 10 ) in THF solvent was metered into each vial in sufficient volume to fill the pores of the support to its incipient point. The concentration of the metal precursor in the solution was determined by the target amount of metal.

[0145] After the solution was added, the shaker was started to ensure that the liquid filled all the pores of the catalytic support material. Next, the catalyst was dried overnight at 120°C under an inert gas flow. After drying, the catalysts were loaded into an oven where they were heated to 120°C for 3 hours and then raised to 500°C for 12 hours. Finally, the catalyst was cooled to 100°C. The entire heating and cooling sequence was carried out with 5% by volume hydrogen in nitrogen at a constant flow rate of 100 sccm to allow the metals to be reduced to their metallic state.

[0146] CP Example 5: 3% Re / C Manual Catalyst Preparation

[0147] 1 g of carrier material (e.g., Cabot NORIT 3 Extra sized using 30-100 mesh) is added to the vial. Dirhenium decacarbonyl (Re2(CO) 10 A solution of ) (0.0542 g) in THF (1 mL) was prepared while mixing with a spatula to distribute evenly throughout. The THF was removed by vacuum oven overnight or by conventional oven at 120°C. The catalyst was then moved to a pre-reduction furnace at 120°C for 3 hours and then at 500°C for 12 hours. Finally, the catalyst was cooled to 100°C.

[0148] CP Example 6: 3% Re / C Manual Catalyst Preparation

[0149] In the glove box, activated carbon (9.7 g, Carbon Resources, previously dried under vacuum at 120°C) was placed in a wide-mouth bottle, and Re2(CO) was added dropwise under gentle shaking. 10 A solution of rhenium salt (0.53 g dissolved in 10 mL of THF) was prepared. The carbon was allowed to stand in the glove box for 2 h and then dried on a hot plate at 120° C. in a fume hood. The composition was calculated to be 3% Re / C (w / w) based on the starting weight of the rhenium salt and the carbon support, which was stored in a sample vial for activity testing.

[0150] CP Example 7: Re multimetallic catalyst synthesis via automated method

[0151] In a typical synthesis, 500 mg of support material is added to a round bottom vial. Multiple vials are used to prepare different catalyst compositions or larger batches of a single catalyst. These are placed in a vertical shaker. Using an automatic metering pump, an aqueous solution of the metal precursor is metered into each vial in sufficient volume to fill the pores of the support to its starting point. The concentration of the metal precursor in the solution is determined by the target amount of metal for the specific catalyst.

[0152] Once the first metal solution has been metered in, the catalyst is dried overnight under an inert gas stream at 120° C. Subsequently, the second metal solution is metered into the dried catalyst as in the first addition, with simultaneous shaking.

[0153] After the second solution addition, the catalysts were loaded into an oven where they were heated to 120° C. for 3 hours and then raised to 500° C. for 12 hours. Finally, the catalysts were cooled to 100° C. The entire heating and cooling sequence was performed with a constant flow rate of 100 sccm of 5 vol% hydrogen in nitrogen to allow the metals to be reduced to their metallic state.

[0154] The total metal loading ranged from 3 wt% to 10 wt%, and the molar ratio between metals (metal 1:metal 2 molar ratio) was 3:1 mol / mol, 1:1 mol / mol, or 1:3 mol / mol. Table 12 lists the metal combinations in the synthesized heterogeneous metal catalysts.

[0155] Table 12: Multimetallic catalysts synthesized following the procedure of CP Example 7

[0156]

[0157]

[0158] Working Example 2: Gas Phase Dehydrogenation of Ethylene and Chlorodimethylsilane Using Parallel Quartz Reactors General process of alkylation :

[0159] A quartz reactor tube with a 152 mm inner diameter and a 3 mm inner diameter is loaded with a heterogeneous metal catalyst (according to the above-mentioned embodiments, such as CP Example 4, CP Example 5 or CP Example 7 preparation) to produce a heated zone of about 40 mm loaded by volume. Quartz sheets and quartz wool are filled at the top and bottom to keep the catalyst bed in place. 16 tubes are loaded into a common manifold for gas delivery and placed in a metal block electrically heated via a clamshell element. The reactor is then heated to 350 ° C under 100 sccm of Ar, which is evenly distributed over 16 tubes via a microfluidic flow chip. The temperature is then raised to 500 ° C for 3 hours under a 50 / 50 mixture of H2 and Ar flowing at a total flow rate of 100 sccm. This is also evenly distributed over 16 tubes. The temperature is then lowered back to the reaction temperature under an argon stream. Once the reaction temperature is reached, chlorodimethylsilane flow and ethylene flow are started. Chlorodimethylsilane was delivered via an ISCO syringe pump at a total flow rate of 0.055 mL / min, and ethylene was fed at a rate of 60 sccm. They were mixed in a quartz chip filled evaporator set at 180°C. The flow was then evenly distributed over each of the 16 tubes via a microfluidic flow chip. The residence time in each reactor tube was approximately 1.7 seconds.

[0160] Working Example 3: Vapor Phase Desorption of Ethylene and Chlorodimethylsilane Using 3% Re / C in Parallel Quartz Reactors Hydrosilylation :

[0161] A catalyst sample prepared according to CP Example 5 was tested according to the conditions of Working Example 2. The resulting properties of this catalyst are listed in Table 13, which is the average of six GC measurements over a six-hour period:

[0162] Table 13: Results using 3% Re / C catalyst

[0163]

[0164] Working Example 4: Vapor Phase Desorption of Ethylene and Chlorodimethylsilane Using 10% Re / C in Parallel Quartz Reactors Hydrosilylation :

[0165] A catalyst sample prepared according to CP Example 5 was tested according to the conditions of Working Example 2. The resulting performance of this catalyst is listed in Table 14, which is the average of six GC measurements over a six-hour period:

[0166] Table 14: Results using 10% Re / C catalyst

[0167]

[0168] Working Example 5 - Vapor Phase Dehydrogenative Silylation of Ethylene with Dimethylchlorosilane Using Re / C Catalyst

[0169] 3 wt% Re / C catalyst (2.5 g, synthesized following CP Example 6) was loaded into the middle of a reactor tube (3 / 8" OD) made of Inconel. The length of the packed catalyst bed was about 2 inches long. The catalyst was packed between two quartz bead beds (about 6 to 8 inches each). The reactor tube was connected to a flow device and the catalyst was reduced at a temperature of 300°C under H2 / N2 flow (50 SCCM / 200 SCCM each) for 4 hours. Dimethylchlorosilane (Me2HSiCl) was fed into the reactor through a bubbler (maintained at ambient temperature) along with N2 as a carrier gas using a mass flow controller. Ethylene gas was fed into the reactor from a cylinder equipped with a pressure regulator via a mass flow controller. The inlet to / from the reactor was kept constant using a heating tape. The inlet and outlet pipes were maintained at 170°C to prevent any condensation of reactants and products. The reaction was carried out at a reaction temperature of 250°C and 300°C using a feed molar ratio of ethylene / Me2HSiCl=4. The reactor outlet was connected to an online GC (TCD)-MS via a 3-way valve assembly for periodic sample injection to perform qualitative and quantitative analysis of reagents and products. The GC feed line was heated 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 a gas-phase dehydrogenative silylation of ethylene using Me2HSiCl and a Re / C catalyst in a reactor different from the reactor tested in Working Example 3.

[0170] Table 15: Results using 3 wt% Re / C :

[0171]

[0172] Working Example 6: Reaction of ethylene with chlorodimethylsilane using Re multimetallic catalyst in parallel quartz reactors Vapor Phase Dehydrogenative Silylation :

[0173] Catalyst samples prepared according to CP Example 7 were tested according to the conditions of Working Example 2. Multiple catalysts were tested in parallel in this experiment, and all contained Re as the first metal deposited. The relative amounts of Re and the second metal were varied. Their catalytic performance under the conditions of Working Example 2 is shown in Table 16 (for 250°C) and Table 17 (for 300°C):

[0174] Table 16: Examples of Re-based multi-metallic catalysts at 250°C showing that the second metal in the composition is a metal 2. M1:M2 represents the molar ratio of metal 1:metal 2 .

[0175]

[0176] Table 17: Examples of Re-based multi-metallic catalysts at 300°C showing that the second metal in the composition is a metal 2. M1:M2 represents the molar ratio of metal 1:metal 2 .

[0177]

[0178] Example 7: Ethylene Oxide in Parallel Quartz Reactors Using a Multimetallic Catalyst Containing Re as the Second Metal Vapor Phase Dehydrogenative Silylation of Olefins with Chlorodimethylsilane :

[0179] Catalyst samples prepared according to CP Example 7 were tested according to the conditions of Working Example 2. Multiple catalysts were tested in parallel in this experiment, and all contained Re as the second metal deposited. The relative amounts of the metals were varied. Their catalytic performance under the conditions of Working Example 1 is shown in Table 18 (for 250°C) and Table 19 (for 300°C):

[0180] Table 18: Multi-metallic catalyst examples at 250°C showing that the first metal in the composition is Metal 1. Metal 2 Re in all samples. M1:M2 represents the molar ratio of metal 1:metal 2 .

[0181]

[0182]

[0183] In Table 18, 1 Any deviation of this sum from 100% is indicated as being due to unquantified siloxane.Table 18 shows that ruthenium can be detrimental to the performance of heterogeneous metal catalysts under certain conditions, since the Vi / Et ratio is <1 when Ru is used as the second metal under the conditions tested in this example.

[0184] Table 19: Multimetallic catalyst examples at 300°C showing the first metal in the composition is Metal 1. Metal 2 Re in all samples. M1:M2 represents the molar ratio of metal 1:metal 2 .

[0185]

[0186] Table 19 also shows that ruthenium can be detrimental to the performance of heterogeneous metal catalysts under certain conditions, as the Vi / Et ratio is <1 when Ru is used as the second metal under the conditions tested in this example. This example shows that the presence of Re in the multi-metallic composition results in a Vi / Et molar ratio >1, even if the Re and second metal are added in a different order during catalyst synthesis. Note: In Table 19, some of these samples have significant siloxane production, so that the sum of the selectivities does not add to 100% in this table; any deviation from 100% is due to the unquantified siloxanes.

[0187] Comparative Example 11: Reaction of ethylene with chlorodimethylsilane using Ru multimetallic catalyst in parallel quartz reactors Vapor Phase Dehydrogenative Silylation :

[0188] Catalyst samples prepared according to CP Example 7 were tested according to the conditions of Working Example 2. Multiple catalysts were tested in parallel in this experiment, and all contained Ru as the first metal deposited. The relative amounts of Ru and the second metal were varied. Their catalytic performance under the conditions of Working Example 1 is shown in Table 20 (for 250°C) and Table 21 (for 300°C):

[0189] Table 20: Examples of Ru-based multimetallic catalysts at 250°C showing that the second metal in the composition is a metal 2. M1:M2 represents the molar ratio of metal 1:metal 2 .

[0190]

[0191] Table 21: Examples of Ru-based multimetallic catalysts at 300°C showing that the second metal in the composition is a metal 2. M1:M2 represents the molar ratio of metal 1:metal 2 .

[0192]

[0193] Industrial Applicability

[0194] The present invention provides a process for preparing vinyl functional chlorosilanes having a Vi / Et ratio ≥ 1 as calculated as described in Table 14 below. The heterogeneous rhenium catalyst used herein provides an unexpected benefit of selectivity to the dehydrogenative silylation reaction to produce the desired vinyl functional chlorosilane product. The use of gaseous reactants in the process described herein provides the benefit of not requiring the following: i) high pressure, ii) solvents, or iii) catalyst recycle / recovery.

[0195] Definition and Use of Terms

[0196] Unless the context of the specification indicates otherwise, the articles 'a', 'an' and 'the / said' all refer to one (kind) or more (kinds). And the singular includes the plural. The Summary of the Invention and the Abstract are hereby incorporated by reference. The terms "comprise" or "contain" are used in their broadest sense herein, meaning and covering the concepts of "including", "consisting essentially of..." and "consisting of...". The use of "for example", "for example", "such as" and "including" to list exemplary examples is not meant to be limited to the listed examples. Therefore, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to" and covers other similar or equivalent examples.

[0197] Abbreviations used herein have the definitions in Table 22.

[0198] Table 22 - Abbreviations

[0199] abbreviation definition ℃ Celsius <![CDATA[HSiMe2Cl or Me2HSiCl]]> Chlorodimethylsilylhydride or Chlorodimethylsilane cm centimeter COD Cyclooctadiene E Ethyl <![CDATA[EtMe2SiCl]]> Ethyldimethylsilyl chloride g gram GC Gas chromatography h Hour Hz hertz m rice Me methyl <![CDATA[Me2SiCl2]]> Dimethyldichlorosilane <![CDATA[Me3SiCl]]> Trimethylchlorosilane <![CDATA[Me3SiH]]> Trimethylsilane min minute mL mL mm Millimeters mol Moore MS Mass spectrometry OD outer diameter RT Room temperature 23℃+ / -2℃ sccm Standard cubic centimeters per minute TCD Thermal conductivity testing μm Micrometer Vi Vinyl <![CDATA[Me2ViCl]]> Vinyldimethylchlorosilane wt weight

[0200] Test methods and calculations

[0201] The above working examples and comparative examples were analyzed as follows: online analysis was completed using an Agilent (7890A) GC instrument equipped with a TCD detector, which was connected to the product vapor line. The response factor and retention time determined by the calibration cylinder containing a known amount of EtMe2SiCl, ViMe2SiCl, Me3SiH, Me3SiCl and Me2SiCl2 were used to complete the quantitative analysis of the reactor effluent gas composition. The sample was transferred to the GC inlet from the reactor product line using a remote sampling system. The details of the GC instrument and the program details are summarized in Table 23.

[0202] Table 23

[0203]

[0204]

[0205] In the above working examples and comparative examples, conversion, Vi / Et ratio and Vi selectivity were calculated as shown in Table 24 below. In Table 24, experimental results were calculated: 'In' = material fed into the reactor; 'Out' = material leaving the reactor; and 'SiH' represents dimethylchlorosilane.

[0206] Table 24 - Calculation

[0207]

[0208] Embodiments of the present invention

[0209] In a first embodiment, a method for preparing a reaction product comprising a vinyl functional organochlorosilane comprises:

[0210] 1) contacting the starting materials comprising the following in a reactor under conditions for carrying out a dehydrogenative silylation reaction, the conditions comprising heating at a temperature of >100°C to <400°C

[0211] (A) an organohydrochlorosilane of the formula R2HSiCl, wherein each R is an independently selected alkyl group having 1 to 18 carbon atoms; and

[0212] (B) ethylene;

[0213] wherein (A) the organohydrochlorosilane and (B) ethylene are each in the gas phase; and

[0214] wherein the dehydrogenative silylation reaction is carried out in the presence of (C) a heterogeneous metal catalyst comprising rhenium and a support;

[0215] Thereby a reactor effluent comprising vinyl-functional organochlorosilane is produced.

[0216] In a second embodiment, the method according to the first embodiment further comprises reducing the (C) heterogeneous metal catalyst before step 1).

[0217] In a third embodiment, in the method according to the second embodiment, reducing the (C) heterogeneous metal catalyst includes heating the reactor containing the (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.

[0218] In a fourth embodiment, in the method according to any one of the first to third embodiments, step 1) comprises heating (A) the organohydrochlorosilane, (B) ethylene and (C) the heterogeneous metal catalyst at a temperature of 200°C to 300°C.

[0219] In a fifth embodiment, the method according to any one of the first to fourth embodiments further comprises an additional step, and the additional step is selected from the group consisting of:

[0220] 2) cooling the reaction effluent after step 1) to condense a material comprising the vinyl-functional organochlorosilane and optionally unreacted (A) organohydrochlorosilane;

[0221] 3) performing gas / liquid separation after step 2);

[0222] 4) recycling unreacted gaseous ethylene after step 2) or step 3);

[0223] 5) recycling unreacted organohydrochlorosilane;

[0224] 6) purifying the vinyl-functional organochlorosilane; and

[0225] 7) repeating step 1) using the gaseous ethylene from step 4) and / or the unreacted organohydrochlorosilane from step 5); and

[0226] Two or more of steps 2) to 7).

[0227] In a sixth embodiment, in the method according to any one of the first to fifth embodiments, the organohydrochlorosilane comprises chlorodimethylsilane (Me2HSiCl).

[0228] In a seventh embodiment, in the method according to any one of the first to sixth embodiments, the support is selected from the group consisting of activated carbon, graphite, silicon carbide, aluminum oxide, ceria, silicon dioxide, magnesium oxide and calcium oxide.

[0229] In an eighth embodiment, the method according to any one of the first to seventh embodiments further comprises, before step 1), depositing Re2(CO) on the substrate via incipient wetness 10 The method is used to prepare (C) heterogeneous metal catalysts.

[0230] In a ninth embodiment, in the method according to any one of the first to eighth embodiments, the vinyl functional organochlorosilane has the formula (CH2=CH-)R2SiCl, wherein each R is an independently selected monovalent hydrocarbon group having 1 to 18 carbon atoms.

[0231] In a tenth embodiment, in the method according to the ninth embodiment, the vinyl functional organochlorosilane comprises vinyldimethylchlorosilane.

Claims

1. A method for preparing a reaction product comprising a vinyl-functional chlorosilane, wherein the method comprises: 1) contacting the starting materials comprising the following in a reactor under conditions for carrying out a dehydrogenative silylation reaction: (A) Formula R (3-x) HSiCl x Hydrochlorosilane, wherein each R is independently selected an alkyl group having 1 to 18 carbon atoms, and the subscript x is 1 to 3; and (B) ethylene; wherein (A) the hydrochlorosilane and (B) the ethylene are each in a gas phase; and wherein the dehydrogenative silylation reaction is carried out in the presence of (C) a heterogeneous metal catalyst comprising rhenium and a support; Thereby a reactor effluent comprising the vinyl-functional chlorosilane is produced.

2. The method according to claim 1, wherein step 1) comprises heating at a temperature >125°C and <400°C. The method according to claim 2 , wherein the temperature is 200° C. to 300° C.

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

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

6. The method according to any one of claims 1 to 3, wherein the method further comprises an additional step, and the additional step is selected from the group consisting of: 2) cooling the reactor effluent after step 1) to condense the material comprising the vinyl-functional chlorosilane and optionally unreacted (A) hydrochlorosilane; 3) performing gas / liquid separation after step 2); 4) recycling unreacted gaseous ethylene after step 2) or step 3); 5) recycling the unreacted hydrochlorosilane; 6) purifying the vinyl-functional chlorosilane; and 7) repeating step 1) using the gaseous ethylene from step 4) and / or the unreacted hydrochlorosilane from step 5); and Two or more of steps 2) to 7).

7. The method of any one of claims 1 to 3, wherein the organohydrochlorosilane has the formula R2HSiCl, wherein each R is an independently selected monovalent hydrocarbon group having 1 to 18 carbon atoms.

8. The method of claim 7, wherein the hydrochlorosilane comprises chlorodimethylsilane of the formula (CH3)2HSiCl.

9. The method according to any one of claims 1 to 3, wherein the method further comprises, before step 1), preparing (C) the heterogeneous metal catalyst by a method comprising depositing a rhenium compound on a substrate via incipient wetness.

10. The method of claim 9, wherein the rhenium compound comprises Re2(CO) 10 .

11. The method according to any one of claims 1 to 3, wherein the support is selected from the group consisting of activated carbon, graphite, silicon carbide, aluminum oxide, ceria, silicon dioxide, magnesium oxide and calcium oxide.

12. The method of claim 11, wherein the support is selected from the group consisting of activated carbon and alumina.

13. The method according to any one of claims 1 to 3, wherein the vinyl-functional chlorosilane has the formula (CH2=CH-)R (3-x) SiCl x , wherein each R is an independently selected monovalent hydrocarbon group having 1 to 18 carbon atoms, and the subscript x is 1 to 3.

14. The method of claim 13, wherein the vinyl-functional organochlorosilane comprises vinyldimethylchlorosilane.

15. The method according to any one of claims 1 to 14, wherein (C) 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).

Images