CATALYST PARTICLES AND METHODS FOR DEHYDROGENATING SILYLATION - Patent application

Abstract

A method for preparing catalyst particles ("Preparation Method") is disclosed. The Preparation Method includes combining a Ru(0) complex with a carrier fluid to form a mixture and heating the mixture at an elevated temperature to nucleate the Ru(0) complex and obtain catalyst particles in the carrier fluid. The Preparation Method optionally includes isolating the catalyst particles from the carrier fluid. A method for preparing organosilicon compounds via dehydrogenative silylation using catalyst particles ("Synthesis Method") is also disclosed. The Synthesis Method includes reacting (A) an organohydridochlorosilane compound with (B) an alkene compound in the presence of (C) a catalyst, thereby preparing an organosilicon compound. The Catalyst (C) of the Synthesis Method comprises catalyst particles prepared by the Preparation Method.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and all benefits of U.S. Provisional Patent Application No. 62 / 949,881, filed December 18, 2019, the contents of which are incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present disclosure relates generally to catalysts and methods for preparing organosilicon compounds, and more specifically to methods for preparing catalyst particles for dehydrogenative silylation reactions, as well as methods for the preparation and use of catalyst particles for preparing vinylsilanes via dehydrogenative silylation. [Background technology]

[0003] Hydrosilylation reactions are generally known in the art and involve an addition reaction between silicon-bonded hydrogen and aliphatic unsaturation. Hydrosilylation reactions are utilized in a variety of applications, such as crosslinking components of curable compositions. Hydrosilylation reactions can also be utilized to prepare individual components or compounds, such as components for inclusion in such curable compositions. Typically, hydrosilylation reactions are carried out in the presence of platinum metal-based catalysts due to their superior catalytic activity and stability. Platinum metals are generally much more expensive than other metals with lower catalytic activity, while non-platinum catalysts suffer from instability when exposed to ambient conditions. In particular, non-platinum catalysts are prone to undesirable side reactions with ambient oxygen and water, which may limit their use and potential end uses.

[0004] Like hydrosilylation reactions, dehydrogenative silylation reactions are also known in the art and similarly involve a reaction between silicon-bonded hydrogen and aliphatic unsaturation. However, in dehydrogenative silylation, there is no addition reaction, but instead the aliphatic unsaturation is bonded to silicon in a vinyl form. Thus, dehydrogenative silylation reactions can be utilized to prepare unsaturated compounds (e.g., olefin-functional compounds) that can further undergo additional functionalization (e.g., via hydrosilylation) and / or coupling reactions.

[0005] Unfortunately, catalysts for dehydrogenative silylation reactions suffer from many of the same shortcomings associated with hydrosilylation catalysts, such as sensitivity to oxygen, water, and even light.In addition, although recent advances in hydrosilylation catalysts have overcome such shortcomings, many catalytic systems suitable for hydrosilylation reactions are not practical for use in dehydrogenative silylation reactions.For example, many such catalysts exhibit selectivity in favor of addition reactions, especially with minimally substituted olefins, thus resulting in unselective reactions with undesirable product mixtures and low yields.In addition, many conventional dehydrogenative silylation conditions are not functional group tolerant, thus limiting their use. Summary of the Invention

[0006] The present disclosure provides a method of preparing catalyst particles ("preparation method"). The preparation method includes combining a Ru(0) complex with a carrier fluid to form a mixture and heating the mixture at an elevated temperature to nucleate the Ru(0) complex to obtain catalyst particles in the carrier fluid. The Ru(0) complex may include a triruthenium complex or derivative thereof, a phosphorus ligand, or a combination thereof. The preparation method optionally includes isolating the catalyst particles from the carrier fluid.

[0007] The present disclosure also provides a method for preparing an organosilicon compound using the catalyst particles ("synthetic method"). The synthetic method includes reacting (A) an organohydridochlorosilane compound with (B) an alkene compound via dehydrogenative coupling in the presence of (C) a catalyst comprising the catalyst particles, thereby preparing an organosilicon compound. The organohydridochlorosilane compound (A) has the general formula HSiCl x R 3-x where subscript x is 1 or 2, and each R is an independently selected unsubstituted hydrocarbyl group having 1 to 18 atoms, and alkene compound (B) may have the formula R 1 CHCH2, where R 1 is H or a hydrocarbyl group, and the organosilicon compound is represented by the formula (R 1 CHCH)SiCl x R 3-x where the subscripts x, R, and R 1 is as defined above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] A method for preparing catalyst particles ("preparation method") is provided. The catalyst particles can be utilized in at least dehydrogenative silylation / coupling reactions, and exhibit high conversion rates, selectivities, and yields. The catalyst particles have excellent physical properties and can be used in a variety of heterogeneous and / or homogeneous conditions, providing broad applicability. Considering the diverse end-use applications of the catalyst particles, as well as their catalytic activity, a method for preparing organosilicon compounds using the catalyst particles (i.e., via dehydrogenative silylation reactions) is also provided, which is described in more detail below.

[0009] The preparation method includes combining a Ru(0) complex with a carrier fluid to form a mixture and heating the mixture at an elevated temperature to obtain particles (i.e., "catalyst particles") that include the Ru(0) complex. As will be understood from the following description, the preparation method prepares the catalyst particles in a heterogeneous composition that includes the catalyst particles and the carrier fluid. Thus, the preparation method may further include additional steps, such as isolating the catalyst particles from the carrier fluid, purifying the catalyst particles, etc., as described below.

[0010] As introduced above, the preparation method utilizes a Ru(0) complex, i.e., a complex that contains ruthenium (Ru) in a neutral oxidation state. The Ru(0) complex is not particularly limited and can be any Ru(0) complex that is capable of forming particles and catalyzing dehydrogenative silylation reactions according to the methods described herein.

[0011] Examples of suitable Ru(0) complexes include {Ru(η 4 -1,5-COD)(η 6 -1,3,5-COT)}, {Ru(PPh3)3(CO2)}, {Ru(η 4 -1,5-COD)(η 6 -triphenylene)}, {[Ru(η 4 -1,5-COD)]2(η 12 -triphenylene)}, {Ru(η 4 -1,5-COD)(η 4 -1,3-COT)PR'3}, {Ru(η 6 -1,3,5-COT)PR'3}, {Ru(η 4 -1,5-COD)(PR'3)3}, {Ru(η 4 -1,5-COD)(tBuNC)3}, {[Ru(η 4 -1,5-COD)]3(η 18 -triphenylene)}, [Ru3(CO) 10 (MeCN)2], Ru3(CO) 12and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will recognize that cyclooctadiene and cyclooctatriene are ligands represented by COD and COT, respectively. Ligands represented by the general formula PR'3 are tertiary phosphorus compounds (e.g., phosphines, phosphites, etc.), where each R' is a hydrocarbyl group independently selected, as exemplified by those described below for the variable substituent R. However, as a non-limiting example, each R' can be independently selected from substituted or unsubstituted alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, and combinations thereof, as exemplified by those described herein.

[0012] In certain embodiments, the Ru(0) complex comprises a triruthenium complex or a derivative thereof. An example of a triruthenium complex is {[Ru(bda)-(pic)2(μ-O)]2Ru(pic)2(H2O)2} 2+ , {[Ru3(μ-H)(μ-η 3 -dpa-C,N,N)(CO)}, {(Ru(acac)2)3(diquinoxaline[2,3-a:2',3'-c]phenazine)}, {[Cp * Ru(μ-H)]3(μ3-η 2 -(II)-PhCCH)(μ3-BH)}, [Ru3(dmbpy)6(μ-HAT)] 6+ , [Ru(η 4 -1,5-COD)]3(η 18 -triphenylene)}, [Ru3(CO) 10 (MeCN)2], Ru3(CO) 12 and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will recognize that bda, pic, dpa, acac, Cp *It will be understood that the ligands represented by , dmbpy, and HAT are 2,2-bipyridine-6,6-dicarboxylate, 2-picolylamine, dipicolylamine, acetylacetonate, 1,2,3,4,5-pentamethylcyclopentadienyl, 4,4'-dimethyl-2,2'-bipyridine, and 1,4,5,8,9,12-hexaazatriphenylene, respectively, or deprotonated forms thereof.

[0013] Examples of derivatives / modifications of Ru(0) complexes generally include ligand-exchanged versions of the above complexes, e.g., Ru3(CO) 12 Derivatives of may be prepared via ligand exchange of CO with phosphorus ligands, amine ligands, etc. Thus, in certain embodiments, Ru(0) complexes are prepared from triruthenium dodecacarbonyl (i.e., of the formula Ru(CO) 12 (Triruthenium dodecacarbonyl) or a derivative thereof. In some such embodiments, the triruthenium dodecacarbonyl derivatives are further defined as ligand-exchanged derivatives of triruthenium dodecacarbonyl having one or more phosphorus ligands and / or one or more amine ligands, such as those described below. It is understood that such ligand-exchanged derivatives may also be prepared from ruthenium compounds / complexes other than triruthenium dodecacarbonyl, and are included within the scope of the Ru(0) complexes herein, whether prepared or otherwise obtained from triruthenium dodecacarbonyl or another ruthenium compound / complex.

[0014] Thus, as will be understood from the exemplary complexes above, as well as the further description and examples below, Ru(0) complexes can include phosphorus ligands. Examples of phosphorus ligands include phosphines, phosphites, phosphates, phosphine oxides, phosphoramidites, phosphinium salts, phosphinoamines, chlorophosphines, phosphinoimines, phosphorodiamidites, phosphinites, phosphonates, phosphonites, triaminophosphines, trisilylphosphines, and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will understand that such ligands can be utilized in ionic form (e.g., from protonation / deprotonation) as encompassed by the examples herein and shown in various embodiments. Specific examples of phosphorus ligands include phosphine, trimethylphosphine, triphenylphosphine, methyldiphenylphosphine, trifluorophosphine, trimethylphosphite, triphenylphosphite, tricyclohexylphosphine, dimethylphosphinomethane (DMPM), dimethylphosphinoethane (DMPE), diphenylphosphinomethane (DPPM), diphenylphosphinoethane (DPP), oethane (dppe), S,S-chiraphos, ethane-1,2-diylbis[(2-methoxyphenyl)phenylphosphane] (DIPAMP), 1,1'-bis(diphenylphosphino)ferrocene (dppf), tri(orthotoluyl)phosphine, (2,4,6-triisopropylphenyl)dicyclopentylphosphine, and the like, as well as derivatives, modifications, and combinations thereof. Those skilled in the art will appreciate that such phosphorus ligands include phosphite versions of the above phosphines, as well as homo- and hetero-substituted phosphines and phosphites having any one or more of the phosphorus binding groups exemplified herein.

[0015] For example, in certain embodiments, the Ru(0) complex comprises a phosphorus ligand having the general formula PR″3, where each R″ is independently of the formula —R′ or —OR′, and each R′ is as defined above (i.e., an independently selected hydrocarbyl group, as exemplified by those described below for the variable substituent R). However, as a limited example in this particular context, each R′ can be independently selected from substituted or unsubstituted alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, and combinations thereof, as exemplified by those described herein. In certain embodiments, each R is independently a branched or cyclic hydrocarbyl group. For example, each R′ can be independently selected from isopropyl groups, isobutyl groups, t-butyl groups, other branched alkyl groups, aryl groups, alkaryl groups, aralkyl groups, substituted aryl groups (e.g., pentafluorophenyl, etc.), and the like. As will be understood by one of skill in the art, each R″ (including its specific R′) can be independently selected based on steric hindrance, electronic factors (e.g., electron donating, inductive, or abstracting effects such as when R″ is of the formula -OR′), or the like, or a combination thereof. For example, each R′ can be selected to impart chirality or symmetry to the catalyst. In these or other embodiments, R′ can be independently selected to enhance the reactive regioselectivity of the catalyst particles prepared, such as anti-Markovnikov selectivity. Thus, each R″ (including its specific R′) in the phosphorus ligand can be the same or different from any other R″ in the phosphorus ligand.

[0016] In certain embodiments, each R" has the formula -R', and thus the phosphorus ligand can be further defined as an organophosphine ligand. In some such embodiments, each R' is an independently selected substituted or unsubstituted aryl, aralkyl, or cycloalkyl group. Examples of such organophosphine ligands include substituted and unsubstituted triarylphosphines, tricycloalkylphosphines, bis(diarylphosphino)alkanes, bis(dicycloalkylphosphino)alkanes, and combinations thereof. In other such embodiments, at least one R' is a phosphorus-containing (i.e., substituted) hydrocarbyl group, and thus the phosphorus ligand is a multidentate ligand having two or more phosphorus atoms. Specific examples of such phosphorus ligands include 1,3-bis(dicyclohexylphosphino)propane and 1,3-bis(diphenylphosphino)propane.

[0017] In certain embodiments, each R" has the formula -OR', such that the phosphorus ligand may be further defined as an organophosphite ligand. In such embodiments, each R' is generally as described above and may independently include or be any of the specific groups described for R' of the organophosphine ligands. Particular examples of organophosphate ligands include those in which each R' is an aryl group, i.e., the organophosphite ligand may be further defined as a triarylphosphite ligand (e.g., triphenylphosphite).

[0018] Additional examples of suitable phosphorus ligands include those with moderate Tolman Electronic Parameters (TEP) and / or moderate Tolman Cone Angle (TCA). For example, in some embodiments, the Ru(0) complex of catalyst (C) has a Tolman Electronic Parameter (TEP) of 2,060-2,090, or alternatively, 2,065-2,085 cm -1 2,050~2,100cm -1In these or other embodiments, the Ru(0) complex includes a phosphorus ligand having a TCA of 100-200°, such as 115-185°, or alternatively 130-170°. As will be appreciated by one of skill in the art, the TEP of the phosphorus ligand can be determined from measurements of the vibrational spectrum (i.e., infrared (IR) or Raman) of the complex according to the relationship: TEP=ω(CO,Ni;A1)=2056.1+pL, where pL is the ligand-specific increment for the CO stretching frequency (ω), based on A1, the symmetrical CO stretching frequency (ω) of a standard nickel tricarbonyl complex that includes the ligand (i.e., of formula (R'3P)Ni(CO)3, where ligand PR'3 is a phosphorus ligand and is as defined above). Typically, P(tBu)3 is used as the reference material and pL(P(tBu)3) is set to 0, so that ω(CO,A1) = 2056.1 cm -1 As will also be appreciated by those skilled in the art, the TCA of a phosphorus ligand in a transition metal complex is the solid angle formed by the apex and the metal at the outermost edge / perimeter of a cone minimally dimensioned around the van der Waals sphere of the ligand atom, and can be determined using computational space-filling models and / or empirical bond characterization. Methods and materials for such determination of TEP and / or TCA are described in some detail in Tolman, Chemical Reviews, 1977, vol77(3) pp313-348, the characterization methods and phosphorus ligands of which are incorporated herein by reference.

[0019] As introduced above, in certain embodiments, the Ru(0) complex comprises a nitrogen ligand. Examples of suitable nitrogen ligands generally include tertiary amines, secondary imines, and the like (e.g., neutral trisubstituted / linked nitrogen compounds having a free lone pair on the nitrogen atom), as well as combinations thereof (e.g., substituted amide imines (i.e., amidines), such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Such nitrogen ligands are exemplified by triorganoamines, pyridines, bipyridines, quinolines, phenanthrolines, and the like, as well as combinations thereof. Examples of triorganoamines include those of the formula NR'3, where R' is as described above (i.e., hydrocarbyl groups independently selected as exemplified by those described below for the variable substituent R). However, as a limited example in this particular context, each R' may be independently selected from substituted or unsubstituted alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups, and combinations thereof, as exemplified by those described herein.

[0020] The Ru(0) complexes may include other ligands aside from those described above, such as those including and / or derived from ketones, diones, olefins, nitriles, carbenes, etc., as well as combinations thereof. The additional ligands may be prepared and / or exchanged in situ (i.e., during the preparation process) with those of the Ru(0) complexes, such as via solvent exchange.

[0021] The Ru(0) complexes utilized in the preparation methods may be prepared or obtained otherwise (i.e., as prepared compounds / complexes). Methods for preparing many of the above Ru(0) complexes are known in the art and can be utilized in conjunction with known compounds to also prepare the above ligand-exchanged derivatives, for example, using compounds commercially available from a variety of sources.

[0022] In certain embodiments, the Ru(0) complex is prepared as part of a preparation method, i.e., the preparation method includes preparing a Ru(0) complex. In such embodiments, the Ru(0) complex may be prepared prior to combining with the carrier fluid, or may be prepared in situ, i.e., in the carrier fluid, via reaction / complexation of components disposed in the carrier fluid, etc. Typically, preparing a Ru(0) complex includes combining a catalyst precursor compound with a ligand precursor compound, optionally in the presence of a carrier vehicle, to obtain a Ru(0) complex (e.g., via ligand exchange), which may be combined directly with the carrier fluid, or may be purified, processed, combined with another carrier vehicle, or otherwise modified with another carrier vehicle, before combining with the carrier fluid or otherwise utilizing to prepare catalyst particles. It will be understood that preparing a Ru(0) complex may include any number of additional steps / processes / procedures not described in further detail below, such as oxidizing or reducing ruthenium complexes / compounds with different oxidation states to obtain a Ru(0) complex.

[0023] Examples of catalyst precursor compounds generally include Ru(0) and triruthenium complexes, including those described above, as well as derivatives, modifications, and combinations thereof. For example, in certain embodiments, the catalyst precursor compound is triruthenium dodecacarbonyl. Examples of ligand precursor compounds include those suitable for preparing the phosphorus and nitrogen ligands described above, including protonated and / or salt forms thereof. For example, in certain embodiments, the ligand precursor compound is a tertiary phosphorus compound. In some such embodiments, the tertiary phosphorus compound is an organophosphine compound having the formula P(R')3, where R' is as defined above. Examples of such organophosphine compounds include triarylphosphines, tricycloalkylphosphine bis(diarylphosphino)alkanes, and bis(dicycloalkylphosphino)alkanes. In other such embodiments, the tertiary phosphorus compound is an organophosphite compound having the formula P(OR')3, where R' is as defined above. Examples of such organophosphite compounds include triarylphosphites. In other embodiments, the ligand precursor compound is a tertiary amine compound, such as an organic amine compound having the formula N(R')3, where R' is as defined above.

[0024] The catalyst and ligand precursor compounds may be provided, prepared, or otherwise obtained (e.g., from a commercial source). In certain embodiments, preparing the Ru(0) complex further comprises preparing the catalyst and / or ligand precursor compound prior to and / or during complexing of the ruthenium of the catalyst precursor compound with the ligand precursor compound to obtain the Ru(0) complex. As understood in the art, the catalyst and ligand precursor compounds may be prepared or synthesized via a number of routes or techniques.

[0025] The amounts of catalyst and ligand precursor compounds utilized to prepare the Ru(0) complex can vary and will be selected by one of skill in the art based on, for example, the ruthenium metal present in the catalyst precursor compound, its ligands, the amount of solvent / carrier vehicle (if any) utilized, the number of electrons and / or lone pairs available for bonding / coordination with the ruthenium metal of the catalyst precursor compound, etc. For example, the ligand precursor compound can be utilized in an amount that provides a molar ratio of ligand (L) to ruthenium metal (Ru) in the catalyst precursor compound (L:Ru) of 1:10 to 100:1 (i.e., 0.1 to 100 equivalents (equivalents) such as 1:1 to 10:1 (i.e., 1 to 10 equivalents), or alternatively 2:1 to 4:1 (i.e., 2 to 4 equivalents)). Amounts outside these ranges can also be utilized.

[0026] As introduced above, the Ru(0) complex may be prepared in a carrier vehicle, such as any of those described herein. For example, the Ru(0) complex may be prepared in a carrier fluid utilized in the preparation method, or in a vehicle / solvent that is miscible with the carrier fluid. In certain embodiments, the Ru(0) complex is prepared in the presence of an aromatic solvent (e.g., an aromatic organic solvent), such as benzene, toluene, xylene (e.g., o-, m-, and / or p-xylene), mesitylene (i.e., 1,3,5-trimethylbenzene), or the like, or a combination thereof. Depending on various options, when the Ru(0) complex is prepared and / or placed in a carrier vehicle or solvent, the vehicle or solvent, or a portion thereof, may complex with Ru(0), for example, to become a ligand or other component of the Ru(0) complex.

[0027] Typically, the catalyst and ligand precursor compound are combined in a vessel or reactor with any carrier / solvent utilized to prepare the Ru(0) complex. The vessel or reactor may be heated or cooled in any suitable manner, for example, via a jacket, mantle, exchanger, bath, coil, etc. For example, in some embodiments, the catalyst and ligand precursor compound are combined in an aromatic solvent at an elevated temperature to obtain the Ru(0) complex. The elevated temperature for preparing the Ru(0) complex is selected and controlled depending on the particular catalyst and / or ligand precursor compound selected, the particular aromatic solvent and / or other carrier vehicle utilized, the reaction vessel selected (e.g., open at ambient pressure, sealed under reduced pressure, etc.), etc. Thus, the elevated temperature for preparing the Ru(0) complex will be selected by one of skill in the art in view of the reaction conditions and parameters selected, and the description herein. The elevated temperature for preparing the Ru(0) complex is typically from ambient to 300° C., such as from 50 to 250, alternatively from 60 to 200, alternatively from 70 to 175, alternatively from 75 to 150, alternatively from 80 to 125° C. High temperatures outside these ranges can also be utilized.

[0028] As introduced above, the preparation method utilizes a carrier fluid, which is combined with a Ru(0) complex to prepare a mixture. The carrier fluid is not particularly limited and can be or include a solvent, a diluent, etc., or a combination thereof.

[0029] Examples of specific carrier fluids and components suitable for use in the carrier fluid are described below. However, it should be understood that the specific solvents, carriers, diluents, etc. utilized in or as the carrier fluid, and the respective amounts thereof used, will be independently selected by those skilled in the art based on, for example, the solubility of the Ru(0) complex, the catalyst and / or ligand precursor compound (if utilized), and the catalyst particles to be prepared. In certain embodiments, the Ru(0) complex is prepared in the carrier fluid via ligand exchange between the catalyst precursor compound and the ligand precursor compound. In such embodiments, the ligand exchange is typically performed under homogeneous conditions (e.g., in solution), and thus the carrier fluid is selected to dissolve one or both of the precursor compound and / or the Ru(0) complex to be prepared from the precursor compound. However, the ligand exchange may be performed heterogeneously, for example, with one or more components suspended but not dissolved in the carrier fluid. Similarly, the preparation of the catalyst particles may be performed under homogeneous or heterogeneous conditions. For example, in certain embodiments, the carrier fluid is selected to dissolve the Ru(0) complex and / or components thereof, but precipitate the catalyst particles prepared in the carrier fluid. In certain embodiments, the carrier fluid is selected to partially dissolve the catalyst particles, e.g., to precipitate only catalyst particles that obtain a certain size. However, it will be understood that the carrier fluid may be selected to carry out one or more reactions / preparations in a solution, emulsion, suspension, slurry, biphasic mixture, or combinations thereof, as well as to carry out the reaction / preparation in any other different state.

[0030] Examples of carrier fluids suitable for use in the preparation method include solvents (e.g., organic solvents, etc.), oils (e.g., organic oils, silicone oils, etc.), fluids (e.g., organic fluids, silicone fluids, etc.), and the like, and combinations thereof. Examples of organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene (e.g., o-, m-, and / or p-xylene), mesitylene (i.e., 1,3,5-trimethylbenzene), and the like, or combinations thereof. Additional examples of organic solvents include aliphatic hydrocarbons (e.g., heptane, hexane, octane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,1,1-trichloroethane, chloroform, etc.), dimethylsulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, white spirits, mineral spirits, naphtha, n-methylpyrrolidone, and the like, as well as derivatives, modifications, and combinations thereof. Examples of organic fluids include organic oils, typically including volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. Common examples of such organic fluids include C6-C 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8 to C 16 Volatile hydrocarbon oils, such as branched esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), as well as derivatives, modifications, and combinations thereof. Additional examples of organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons (e.g., isododecane, isohexadecane, Isopar L (C 11 ~C 13 ), Isopar H(C 11 ~C 12 ), hydrogenated polydecene), alkyl halides, aromatic halides, and combinations thereof. Examples of silicone fluids typically include low viscosity organopolysiloxanes, low viscosity and / or volatile siloxanes such as volatile siloxanes (e.g., volatile methyl, ethyl, and / or methylethyl siloxanes, and the like, and combinations thereof. Exemplary silicone fluids typically have a viscosity of 1 to 1,000 mm at 25°C.2 Specific examples of silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, and heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane. , hexamethyl-3,3, bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone, and the like, as well as derivatives, modifications, and combinations thereof. Additional examples of suitable silicone fluids include those having suitable vapor pressures (e.g., 5×10 -7 ~1.5×10 -6 m 2 Examples of suitable polyorganosiloxanes include polyorganosiloxanes having a vapor pressure of 1000 MPa / sec.

[0031] Other carriers may also be used in or as a carrier fluid other than the above. For example, the carrier fluid may include or be an ionic liquid. Examples of ionic liquids include anion-cation combinations in which the anion is generally selected from alkyl sulfate-based anions, tosylates, sulfonates, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, hexafluorophosphate anions, tetrafluoroborate anions, etc., and the cation is generally selected from imidazolium-based cations, pyrrolidinium-based cations, pyridinium-based cations, lithium cations, etc. However, combinations of multiple cations and anions may also be used. Specific examples of ionic liquids include 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 3-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, N-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyridinium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, 1 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allylimidazolium bis(trifluoromethanesulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, and the like, as well as derivatives, modifications, and combinations thereof.

[0032] In certain embodiments, the carrier fluid comprises or is an aromatic solvent, hi some such embodiments, the carrier fluid comprises or is an aromatic organic solvent, such as benzene, toluene, xylene, mesitylene, and the like, or combinations thereof.

[0033] The preparation method may utilize any amount of Ru(0) complex and carrier fluid. More specifically, the mixture may include Ru(0) complex and carrier fluid in amounts or ratios that vary depending on the desired properties of the particle formation (e.g., nucleation temperature, rate of formation, etc.) and / or the characteristics of the Ru(0) complex and / or carrier fluid used.

[0034] Typically, the Ru(0) complex is utilized in an amount sufficient to provide at least 0.01 wt.% loading (weight / weight) in the carrier fluid. Similarly, the Ru(0) complex is utilized in an amount sufficient to provide a loading below the solubility limit of the Ru(0) complex, such that the mixture can be formed as a solution (e.g., at room temperature or with gentle heating). In certain embodiments, the Ru(0) complex is utilized in an amount of 0.01-25, alternatively 0.01-20, alternatively 0.01-15, alternatively 0.01-10, alternatively 0.01-5, alternatively 0.01-2.5, alternatively 0.01-1, alternatively 0.01-0.5 wt.% based on the weight of the carrier fluid utilized. Higher or lower ratios may also be utilized. In particular, one skilled in the art will appreciate that a higher concentration (i.e., increased loading) of the Ru(0) complex in the carrier fluid may increase the growth rate of the catalyst particles. Similarly, it will also be appreciated that the amount of carrier fluid utilized to prepare a mixture will be a function of the scale and the particular components utilized. For example, a mixture will be prepared utilizing a greater amount of carrier fluid if the Ru(0) complex has low solubility in the selected carrier fluid compared to preparing a mixture containing a Ru(0) complex that exhibits higher solubility in the carrier fluid.

[0035] Typically, the Ru(0) complex and the carrier fluid are combined in a vessel or reactor to prepare the mixture. The vessel or reactor may be heated or cooled in any suitable manner, for example, via a jacket, mantle, exchanger, bath, coil, etc. As will be understood by one of skill in the art, the vessel or reactor is typically heated in a controllable manner such that the mixture may be heated to an elevated temperature without substantially overheating.

[0036] The Ru(0) complex and the carrier fluid may be provided together or separately to the vessel, or may be placed in the vessel in any combination, in any order of addition, depending on the particular parameters of the preparation method used. For example, in certain embodiments, the Ru(0) complex is added to the vessel containing the carrier fluid, for example, as a pre-made complex or as individual components (i.e., precursor compounds) for forming the Ru(0) complex in situ. In some such embodiments, the carrier fluid is added to the vessel, and then the catalyst and ligand precursor compounds are charged to form the Ru(0) complex. The catalyst and ligand precursor compounds may be first combined before addition, or may be added to the vessel sequentially. In other embodiments, the carrier fluid is added to the vessel containing the Ru(0) complex, or a component thereof, optionally in a solvent / carrier vehicle. In general, references herein to a "mixture" generally refer to a mixture comprising the Ru(0) complex and the carrier fluid (e.g., as obtained by combining such components as described above).

[0037] The method may further include stirring the mixture. Stirring may enhance mixing and contacting of the Ru(0) complex and / or particles thereof in the carrier fluid. Such stirring may also enhance mixing and contacting of the catalyst and ligand precursor compounds to form, for example, the Ru(0) complex when the Ru(0) complex is formed in situ or otherwise as part of the preparation method. Such contacting may be performed independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), and may use other conditions.

[0038] As introduced above, the preparation method includes heating the mixture at an elevated temperature to obtain catalyst particles. The elevated temperature is not particularly limited and will be selected based on the loading of Ru(0) complex, the type of Ru(0) complex utilized (e.g., if Ru(0) complex is prepared as part of the preparation method, the particular catalyst and ligand precursor compound utilized), and the like. In general, the elevated temperature is selected to nucleate the Ru(0) complex. However, it will be understood that particle formation can include nucleation, aggregation, and the like, as well as various phases thereof (e.g., primary nucleation, secondary nucleation, and the like), as would be understood by one of ordinary skill in the art. Thus, in terms of preparing catalyst particles, it will be understood that the elevated temperature is typically selected to promote primary nucleation (i.e., formation of the first nuclei from which particles can be formed) and / or secondary nucleation (i.e., formation of particles from the first nuclei comprising the Ru(0) complex) of the Ru(0) complex. Typically, the elevated temperature is 70-250°C. For example, in certain embodiments, the elevated temperature is 80-200° C., such as 90-200, alternatively 90-190, alternatively 100-190, alternatively 100-180, alternatively 110-180, alternatively 120-180, alternatively 120-170, alternatively 130-170, alternatively 130-160, alternatively 140-160. Elevated temperatures outside these ranges may also be utilized.

[0039] In certain embodiments, heating the mixture at an elevated temperature includes multiple heating steps, e.g., at multiple different elevated temperatures. For example, the mixture may be heated stepwise to one or more target temperatures, which may be preselected or selected in real time during the preparation method (e.g., based on observed properties of the mixture, such as particle formation, opacity, etc.). In certain embodiments, stepwise heating is utilized to heat a combination of catalyst precursor compound and ligand precursor compound in a carrier fluid to a first elevated temperature (i.e., to obtain a mixture) to prepare Ru(0) complexes in the carrier fluid, and then to heat the mixture to a second elevated temperature to obtain catalyst particles.

[0040] The time during which the mixture is heated to prepare catalyst particles is a function of scale, reaction parameters and conditions, choice of particular components, etc. At a relatively large scale (e.g., greater than 1, alternatively 5, alternatively 10, alternatively 50, alternatively 100 kg), the reaction may be carried out for several hours, such as 1-48, alternatively 1-36, alternatively 1-24, alternatively 1-12, alternatively 1-6 hours, as would be readily determined by one of ordinary skill in the art (e.g., by monitoring the formation of catalyst particles via chromatographic and / or spectroscopic methods). In certain embodiments, the time during which the particles are formed is greater than 0 to 2 hours, such as 5 minutes to 2 hours, alternatively 10 minutes to 1 hour, alternatively 10 to 45 minutes, alternatively 10 to 30 minutes, after reaching the elevated temperature.

[0041] The particle growth rate, size, and dispersity can be controlled through the selection of the particular Ru(0) complex selected. More specifically, the ligands of the Ru(0) complex will affect the solubility, nucleation, aggregation, etc. of the Ru(0) complex in the selected carrier fluid. Thus, the preparation method can include selectively controlling the average particle size of the catalyst particles through, for example, the selection of the Ru(0) complex, the carrier fluid, the elevated temperature, and / or the heating period (i.e., the time during which the mixture is held at elevated temperature).

[0042] For example, the mixture may include a support material on which the Ru(0) complex can nucleate. Such materials are exemplified by the solid supports described below. Typically, however, the mixture does not include any support material on which the Ru(0) complex can nucleate. Thus, in certain embodiments, the catalyst particles do not include any support material, etc.

[0043] Generally, a product mixture containing catalyst particles, support fluid, and associated compounds (e.g., remaining Ru(0) complex, catalyst and / or ligand precursor compounds, if utilized, etc.) is prepared by heating the mixture at an elevated temperature.

[0044] In certain embodiments, the preparation method includes isolating the catalyst particles from the product mixture. As used herein, isolating the catalyst particles is typically defined as increasing the relative concentration of the catalyst particles compared to the carrier fluid and the compounds combined with the carrier fluid (e.g., the remaining Ru(0) complex, catalyst and / or ligand precursor compounds, if utilized, etc.). Thus, isolation may include removing the catalyst particles from the carrier fluid and / or removing the carrier fluid from the catalyst particles (i.e., partially or completely). Any suitable technique and / or protocol for isolation may be utilized. Examples of suitable isolation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, and the like. As will be appreciated by those skilled in the art, any of these techniques may be used in combination (i.e., sequentially) with any other technique to isolate the catalyst particles.

[0045] In some embodiments, the preparation method further comprises purifying the catalyst particles. Purifying the catalyst particles may include one or more of the same techniques utilized to isolate the catalyst particles from the carrier fluid, as well as alternative and / or additional techniques compared to those utilized to isolate the catalyst particles. Regardless of the particular technique selected, the isolation and / or purification of the catalyst particles may be performed continuously (i.e., in-line) with the formation of the catalyst particles and may therefore be automated. In other cases, purification may be a separate procedure that is applied to a mixture of catalyst particles in the carrier fluid. In certain embodiments, purifying the catalyst particles comprises size-selecting certain particles, i.e., reducing / reducing / narrowing the particle-side distribution of the catalyst particles (i.e., by removing small particles during purification).

[0046] In certain embodiments, precipitating the catalyst particles from the carrier fluid and isolating the catalyst particles from the product mixture includes filtering the catalyst particles from the carrier fluid. In some embodiments, suspending the catalyst particles in the carrier fluid (e.g., as a colloid) and isolating the catalyst particles from the product mixture includes centrifuging the product mixture to obtain a precipitate comprising the catalyst particles and a supernatant comprising the carrier fluid, and then separating the precipitate from the supernatant, thereby isolating the catalyst particles. In some such embodiments, the isolated catalyst particles are purified and / or size selected via washing and differential centrifugation. More specifically, the method may include washing the isolated catalyst particles by suspending the catalyst particles in a washing solvent (e.g., one utilized in / as the carrier fluid, or a similar such solvent, etc.), centrifuging the resulting suspension to precipitate the washed catalyst particles from the washing solvent, and removing the washing solvent as the supernatant. A particular washing solvent may be selected to size select the catalyst particles (e.g., via the solubility / insolubility of certain sized catalyst particles in the washing solvent). Similarly, the method may include repeating the washing / differential centrifugation process any number of times to further purify and / or size select the catalyst particles.

[0047] The preparation method prepares catalyst particles. More specifically, as will be understood in light of the description of the mixture and the parameters of the preparation method, the method prepares catalyst particles (i.e., Ru(0) catalyst particles) from a Ru(0) complex. Thus, the particular particles prepared will depend on the Ru(0) complex utilized and may include any of the features described above for the Ru(0) complex itself (e.g., with respect to ruthenium content, ligand type and / or structure, etc.).

[0048] In certain embodiments, the catalyst particles may comprise an average particle size of 1 nm to 100 μm, such as 10 nm to 100 μm, alternatively 100 nm to 100 μm, alternatively 100 nm to 100 μm, alternatively 250 nm to 100 μm, alternatively 500 nm to 100 μm, alternatively 750 nm to 100 μm, alternatively 1 to 100 μm. In some embodiments, the catalyst particles may comprise an average particle size of 100 nm to 50 μm, such as 100 nm to 25 μm, alternatively 250 nm to 20 μm, alternatively 500 nm to 15 μm, alternatively 750 nm to 10 μm, alternatively 1 to 10 μm.

[0049] As introduced above, the catalyst particles are prepared in a product mixture that includes a carrier fluid, but may be isolated and / or purified. Thus, the catalyst particles may be disposed in a fluid or carrier, such as a carrier fluid utilized in the preparation method (i.e., a carrier vehicle, solvent, etc., such as those described herein), or alternatively may be free or substantially free of any carrier vehicle or solvent. Similarly, the catalyst particles may be disposed in or on a solid carrier. Examples of such solid carriers include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate), and the like. In certain embodiments, however, the catalyst particles are free or substantially free of solid carriers or other such support materials.

[0050] As introduced above, the catalyst particles prepared according to the preparation method can be utilized to catalyze coupling reactions, particularly dehydrogenative silylation reactions.Therefore, a method for preparing organosilicon compounds using catalyst particles ("synthetic method") is provided herein.As will be understood in light of the description of the synthetic method herein, the organosilicon compounds prepared are alkenyl or vinyl functional, and therefore are useful in curable compositions, as well as compositions and methods for preparing and / or crosslinking various components of curable compositions, such as those based on one or more silicones, as starting materials, reagents, building blocks, functionalizing compounds, etc.

[0051] The synthesis method includes reacting (A) an organohydridochlorosilane compound with (B) an alkene compound in the presence of a catalyst (C) including the catalyst particles described above, thereby preparing an organosilicon compound. As will be understood from the following description, the synthesis method prepares an organosilicon compound and molecular hydrogen (H2) through a dehydrogenative coupling reaction of (A) and (B) (i.e., dehydrogenative silylation of an alkene compound (B) with an organohydridochlorosilane compound (A)) ("reaction") catalyzed by the catalyst (C).

[0052] The organohydridochlorosilane compound (A), alkene compound (B), and catalyst (C) are in turn described herein below as "components" of the synthetic method (i.e., "component (A)," "component (B)," "component (C)," etc., respectively), or in addition, as "starting materials," "compounds," and / or "reagents" (A), (B), and / or (C), etc., or similarly, as would be readily understood by one of ordinary skill in the art, along with additional components that may be utilized in the synthetic method, which may be collectively referred to by function and / or functionality as "hydridosilane (A)," "alkene (B)," and / or "catalyst (C)."

[0053] As introduced above, component (A) is an organohydridochlorosilane compound, 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). The organohydridochlorosilane compound (A) is not otherwise particularly limited.

[0054] In certain embodiments, the organohydridochlorosilane compound (A) has the general formula HSiCl x R 3-xwhere subscript x is 1 or 2 and each R is an independently selected hydrocarbyl group. For example, in some such embodiments, subscript x is 1, such that organohydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane having the formula HSiClR2. In other such embodiments, subscript x is 2, such that organohydridochlorosilane compound (A) is further defined as an organohydridodichlorosilane having the formula HSiCl2R2. Of course, it will be understood that mixtures of such organohydridodichlorosilanes, for example, where subscript x is an average value of 1 to 2, may also be utilized.

[0055] With respect to the formula of component (A) above, each R is an independently selected hydrocarbyl group. Suitable hydrocarbyl groups can be substituted or unsubstituted. With respect to such hydrocarbyl groups, the term "substituted" describes a hydrocarbon moiety in which one or more hydrogen atoms are replaced with atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, bromine, etc.), or a carbon atom in the hydrocarbon chain is replaced with an atom other than carbon (i.e., R can include one or more heteroatoms (oxygen, sulfur, nitrogen, etc.) in the carbon chain), or both. Thus, it will be understood that R can include or be an ether, ester, etc., since R can include or be a hydrocarbon moiety with one or more substituents in and / or on its carbon chain / main chain (i.e., attached to and / or integral to its carbon chain / main chain).

[0056] In general, suitable hydrocarbyl groups for R may be independently linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups, and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups may be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and the like, as well as derivatives, variants, and combinations 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), hexyl, and branched saturated hydrocarbon groups, for example, having 6 to 18 carbon atoms. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl.Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of halogenated aryl groups include the above-mentioned aryl groups, in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups. Typically, each R is an independently selected substituted or unsubstituted hydrocarbyl group. For example, in some embodiments, each R is independently selected from unsubstituted hydrocarbyl groups, such as linear or unbranched unsubstituted hydrocarbyl groups. Such linear or unbranched unsubstituted hydrocarbyl groups include those having 1 to 20 carbon atoms, such as 1 to 18, alternatively 1 to 16, alternatively 1 to 14, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, or alternatively 1 to 6 carbon atoms.

[0057] When the subscript x is 1 and the organohydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane, each R can be the same as or different from the other R in the organohydridochlorosilane compound (A). In certain embodiments, each R is the same as each other R in the organohydridochlorosilane compound (A). In other embodiments, one R is different from the other R in the organohydridochlorosilane compound (A). In some embodiments, each R is an independently selected hydrocarbyl group having 1 to 18, alternatively 1 to 12, alternatively 1 to 6 carbon atoms. In some such embodiments, each hydrocarbyl group is unsubstituted. In certain embodiments, each R is independently selected from unsubstituted alkyl groups, such as methyl groups, ethyl groups, and the like. In certain embodiments, each R is methyl. For example, in some such embodiments, the organohydridochlorosilane compound (A) has the formula HSiCl x (CH3) 3-x where subscript x is as defined above. In certain such embodiments, component (A) comprises chlorodimethylsilane (i.e., of the formula HSiCl(CH3)2), dichloromethylsilane (i.e., of the formula HSiCl2CH3), or a combination thereof.

[0058] As introduced above, component (B) is an alkene compound. More specifically, the alkene compound (B) contains at least one unsaturated aliphatic hydrocarbon group per molecule. The alkene compound (B) can include or be any unsaturated compound having at least one aliphatic unsaturated group, and is not particularly limited. As will be understood by those skilled in the art, the unsaturated aliphatic hydrocarbon group contains a carbon-carbon (C=C) double bond, or can be referred to as an alkenyl group (or alkene), an olefin, an aliphatic unsaturation, an ethylenic unsaturation, etc., depending on the specific form of the hydrocarbon group having unsaturation.

[0059] In certain embodiments, the alkene compound (B) comprises an organic compound. In other embodiments, the alkene compound (B) comprises a siloxane compound. In yet other embodiments, the alkene compound (B) comprises a silicon-organic hybrid and / or an organosilicon compound (i.e., where the alkene compound (B) comprises at least one organic segment comprising an unsaturated aliphatic hydrocarbon group and at least one silicon segment comprising a silane and / or a siloxane). Examples of the alkene compound (B) are illustrated by the embodiments and compounds described below.

[0060] In some embodiments, the alkene compound (B) comprises an alkenyl group. "Alkenyl group" refers to an acyclic, branched, or unbranched hydrocarbyl group (i.e., a monovalent hydrocarbon group when attached to another group / moiety of the alkene compound (B)) having one or more carbon-carbon (C=C) double bonds. For example, the alkenyl group can have 2 to 30 carbon atoms, alternatively 2 to 24 carbon atoms, alternatively 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms. Alkenyl groups are exemplified by, but not limited to, vinyl, allyl, propenyl, and hexenyl. In certain embodiments, the alkene compound (B) comprises an average of at least two unsaturated aliphatic hydrocarbon groups per molecule, each independently selected. The unsaturated aliphatic hydrocarbons of the alkene compound (B) can each be terminal, or such that the alkene compound (B) can contain terminal unsaturation, internal unsaturation, pendant unsaturation, or unsaturation at any combination of such positions.

[0061] In certain embodiments, the alkene compound (B) has the formula ZA, where Z is selected from monovalent organic moieties, silicon moieties containing silane and / or siloxane groups, and combinations thereof, and A is an alkenyl group. In other embodiments, the alkene compound (B) has the formula A-Z'-A, where each A is an independently selected alkenyl group, and Z' is a divalent linking group. In such embodiments, the divalent linking group Z' is typically selected from organic moieties, silicon moieties containing silane and / or siloxane groups, and combinations thereof.

[0062] In certain embodiments, the alkene compound (B) has the formula R 1 CHCH2, wherein R 1 is a hydrocarbyl group or H. Suitable hydrocarbyl groups include those described above for the variable substituent R. For example, R 1 can be substituted or unsubstituted, linear, branched or cyclic, saturated or unsaturated, and if unsaturated, can be non-conjugated, conjugated, or aromatic, and combinations thereof. For example, in some embodiments, R 1 is selected from unsubstituted hydrocarbyl groups, such as linear or unbranched unsubstituted hydrocarbyl groups. Such linear or unbranched unsubstituted hydrocarbyl groups include those having 1 to 16 carbon atoms, such as 1 to 14, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, or alternatively 1, 2, or 3 carbon atoms. Examples of such compounds include linear alpha-olefins, such as propene, 1-butene, 1-heptene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and the like. In other embodiments, R 1 is selected from cyclic and / or aromatic hydrocarbyl groups. For example, in certain embodiments, R 1 is phenyl (CH), so the alkene compound (B) is styrene. Therefore, (for example, when it is part of an aryl group) R 1It will also be understood that may contain one or more unsaturated aliphatic groups which may be internal, conjugated, etc., or combinations thereof.

[0063] In certain embodiments, R 1 is H, so that the alkene compound (B) is ethylene. In such embodiments, ethylene is not limited and may be used in a pure form (i.e., free or substantially free of other components / compounds). In other words, component (B) may consist of ethylene, or may consist essentially of ethylene, or may include ethylene in combination with other components. For example, in some embodiments, the synthesis method includes introducing a reactor fluid that includes, consists essentially of, or consists of ethylene to a vessel or reactor that contains at least components (A) and (C). In such embodiments, the reactor fluid may include components other than ethylene, such as a carrier vehicle, which will typically be or include a material that is inert (i.e., will not react with components (A), (B), or (C)) under the reaction conditions utilized in the synthesis method, as will be understood by those skilled in the art. Examples of such carrier vehicles include inert gases, such as nitrogen (g) (N2), helium (g) (He), argon (g) (Ar), and the like, as well as combinations thereof. ). In certain embodiments, however, component (B) is utilized in pure form and consists essentially of ethylene (ie, substantially free or free of carrier vehicle).

[0064] Ethylene may be utilized in or as component (B) in gaseous form. It will therefore be appreciated that in certain embodiments, the synthesis method is carried out in a vessel that may be optionally pressurized with ethylene (e.g., via a gas manifold). For example, the vessel may be pressurized with ethylene at a pressure greater than atmospheric pressure, which may further drive the reaction. In some embodiments, ethylene is used at a pressure of 100 to 200,000 kPa, such as 100 to 20,000, alternatively 100 to 10,000, alternatively 100 to 5,000, alternatively 100 to 2,000, alternatively 100 to 1,000, alternatively 250 to 1,000, alternatively 250 to 750 kPa. The temperature within the vessel may be increased as well, as described below.

[0065] The synthesis method may utilize any amount of components (A) and (B), and more specifically, may include organohydridochlorosilane compound (A) and alkene compound (B) in varying amounts or ratios depending on the desired properties of the reaction (e.g., conversion rate, etc.) and / or the characteristics of the starting materials used. Typically, component (B) is utilized in a stoichiometric ratio of at least 1:1 based on the number of silicon-bonded hydrogen groups (i.e., the number of Si-H groups that can undergo dehydrogenative coupling reactions) of component (A) to be vinylized. Thus, as would be understood by one skilled in the art, the amount of alkene compound (B) is typically selected based on the amount, type, solubility, etc. of organohydridochlorosilane compound (A). To maximize the degree of conversion of organohydridochlorosilane compound (A) to an organosilicon compound, an excess or total excess of alkene compound (B) may be utilized. For example, components (A) and (B) may be utilized in a stoichiometric ratio (A):(B) of 1:≧1. In certain embodiments, ethylene is utilized in an amount sufficient to provide a molar ratio of alkene compound (B) to organohydridochlorosilane compound (A) (B):(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, alternatively 2:1 to 6:1. Higher or lower ratios may also be utilized. An overall excess of alkene compound (B) may be utilized (e.g., with a molar ratio of (B):(A) of >100:1), such as when alkene compound (B) is in gaseous form (e.g., ethylene, propene, etc.), such as when utilized as a support vehicle in the reaction.

[0066] As introduced above, component (C) includes the Ru(0) complex-containing catalyst particles described above. Catalyst (C) is not otherwise particularly limited.

[0067] The particular catalyst particles may be selected based on the other components utilized in the reaction of the synthesis method. In particular, the particular phosphorus ligand utilized in the Ru(0) complex to form the catalyst particles of catalyst (C) may be selected based on the particular organohydridochlorosilane compound (A) utilized. For example, in certain embodiments, the organohydridochlorosilane compound (A) is a diorganohydridochlorosilane having the formula HSiClR2, and the catalyst particles of catalyst (C) include a Ru(0) complex with an organophosphine ligand. In other embodiments, the organohydridochlorosilane compound (A) is an organohydridodichlorosilane having the formula HSiCl2R, and the Ru(0) complex of catalyst (C) includes an organophosphite ligand.

[0068] The catalyst particles may be utilized in any form, such as pure (i.e., absent solvent, carrier vehicle, diluent, etc.) or may be disposed in a carrier vehicle, such as a solvent or dispersant (e.g., any of those listed and / or described herein, including carrier fluids utilized to prepare the catalyst particles), that would be independently selected by one of skill in the art (e.g., taking into consideration the particular components (A) and (B) selected, the solubility of the catalyst particles, etc.). Thus, in certain embodiments, component (C) consists essentially of the catalyst particles or consists of the catalyst particles. In other embodiments, component (C) may include one or more additional components, such as when the catalyst particles are not isolated and / or purified, as described above. In some embodiments, component (C) may include a carrier vehicle, diluent, solvent, or other carrier, such as a carrier fluid utilized to prepare the catalyst particles.).

[0069] Catalyst (C) can be used in any amount that would be selected by a person skilled in the art based on, for example, the specific catalyst particles selected (e.g., the concentration / amount of its active Ru species), the nature / type of components (A) and / or (B) selected, the reaction parameters used, the scale of the reaction, etc. (e.g., the total amount of component (A) used, the ratio of components (A):(B) used, etc.). The molar ratio of catalyst (C) to components (A) and / or (B) used in the reaction can affect the rate and / or amount of dehydrocoupling / silylation to prepare organosilicon compounds. Thus, the amount of catalyst (C) compared to components (A) and / or (B) and the molar ratio therebetween can vary. Typically, these relative amounts and molar ratios are selected to maximize the reaction of components (A) and (B) while minimizing the loading amount of catalyst (C) (e.g., to increase the economic efficiency of the reaction, increase the ease of purification of the reaction product formed, etc.).

[0070] In certain embodiments, catalyst (C) is utilized in an amount sufficient to provide catalyst particles in an amount of 0.000001 to 50 weight percent based on the total amount (i.e., weight / weight) of component (A) utilized. For example, catalyst (C) may be used in an amount sufficient to provide catalyst particles in an amount of 0.000001 to 25, alternatively 0.00001 to 10, alternatively 0.0001 to 5 weight percent based on the total amount (A) utilized. In some embodiments, catalyst (C) is utilized in an amount sufficient to provide a ratio of Ru(0) complex to organohydridochlorosilane compound (A) in the catalyst particles of (C):(A) of 1:10 to 1:1,000,000, alternatively 1:50 to 1:1,000, alternatively 1:100 to 1:500. Such ratios may be weight ratios (i.e., weight / weight of (C):(A) or active components thereof), or molar ratios of (C):(A) or active components thereof. It will be understood that amounts and ratios outside the ranges recited above can be utilized as well. For example, catalyst (C) can be utilized in a stoichiometric amount (i.e., the catalytic amount above) based, for example, on the total amount of component (B) (i.e., its alkenyl groups) utilized in the synthetic process.

[0071] In certain embodiments, the synthesis method includes reacting components (A) and (B) (e.g., via dehydrogenative coupling / silylation) in the presence of (D) an olefinic compound. In general, the olefinic compound (D) includes an unsaturated aliphatic hydrocarbon group, which may also be referred to as aliphatically unsaturated, ethylenically unsaturated, etc., depending on the particular form of the hydrocarbon group having the unsaturation (e.g., C-C double and / or triple bonds). When utilized, the olefinic compound (D) is different from the alkene compound (B). The particular aliphatically unsaturated group and / or compound utilized in or as the olefinic compound (D) is typically selected based on hydrogenation and / or silylation rates. For example, in certain embodiments, the olefinic compound (D) is selected to readily undergo hydrogenation but slowly undergo hydrosilylation.

[0072] The aliphatically unsaturated groups of the olefinic compound (D) may be alkenyl and / or alkynyl groups. As would be understood by one of ordinary skill in the art, the term "alkenyl group" refers to a group having one or more carbon-carbon double bonds (e.g., an alkene) and the term "alkynyl group" refers to a group having one or more carbon-carbon triple bonds (e.g., an alkyne). Any of such groups may be cyclic or acyclic, branched or unbranched, substituted or unsubstituted, and combinations thereof. Such groups, apart from the olefinic portion, are generally not limited in size and / or overall structure and may contain, for example, 2 to 30 carbon atoms, such as 2 to 24 carbon atoms, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 6 carbon atoms. Particular alkenyl groups are exemplified by vinyl, vinylidene, allyl, propenyl, and hexenyl groups. Suitable alkenyl groups include internal, external, terminal (e.g., alpha-olefins), polysubstituted (e.g., cis and trans di-, tri-, and quaternary substituted alkenes), and combinations thereof. Examples of specific alkynyl groups include ethynyl, propynyl, and butynyl groups. As will be understood from the description herein, the olefinic compound (D) contains at least one aliphatically unsaturated group per molecule. However, in certain embodiments, the olefinic compound (D) contains an average of at least two aliphatically unsaturated groups per molecule. Of course, the olefinic compound (D) can contain any number of additional aliphatically unsaturated groups as well. Each aliphatically unsaturated group of the olefinic compound (D) can be, for example, terminal, pendant, or both such positions in the olefinic compound (D), depending on its structure.

[0073] In certain embodiments, the olefinic compound (D) comprises or is an organic compound. In other embodiments, the olefinic compound (D) comprises or is a siloxane. In yet other embodiments, the olefinic compound (D) comprises or is a silicone-organic hybrid or an organosilicon compound.

[0074] Examples of compounds suitable for use as the olefin compound (D) include butenes (e.g., isobutene, cyclobutene, etc.), pentenes (e.g., 4-methyl-1-pentene, 3-methyl-1-pentene, cyclopentene, 2-methylcyclopentene, 4-methylcyclopentene, etc.), hexenes (e.g., cyclohexene, 3,5,5-trimethyl-1-hexene, vinylcyclohexene, etc.), linear alpha-olefins (e.g., 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-oct ... dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, etc.), cyclic olefins (e.g., cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, disiloxane, norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, vinylnorbornene, etc.), polyolefins (e.g., 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1,3-divinylcyclopentane, dicyclopentadiene, norbornene, cyclohexane, etc.), branched acyclic olefins (e.g., 5-methyl-1-nonene), olefin-substituted cyclic compounds (e.g., vinylcyclohexane, etc.), linear and cyclic alkyne compounds, diene compounds (e.g., 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,19-eicosadiene, etc.), diyne and ene-yne ​​compounds (e.g., 1,3-butadiene, 1,and alkenyl compounds (e.g., compounds having at least one alkenyl group) such as 5-hexadiyne, 1-hexen-5-yne, etc., as well as derivatives, modifications, and combinations thereof. In certain embodiments, the olefin compound (D) comprises, consists essentially of, or is norbornene or a derivative or analog thereof.

[0075] The synthesis method may utilize any amount of component (D), and more specifically, may include the olefinic compound in any amount and / or ratio depending on the desired properties of the reaction (e.g., conversion rate, etc.) and / or the characteristics of the starting materials used. Typically, component (D) is utilized in an amount sufficient to provide the olefinic compound in a stoichiometric ratio of at least 1:1 based on the number of silicon-bonded hydrogen groups (i.e., the number of Si-H groups capable of undergoing dehydrogenative coupling reactions) of component (A) to be vinylized. Thus, as would be understood by one skilled in the art, the amount of component (D) is typically selected based on the amount and type of organohydridochlorosilane compound (A). An excess or total excess of component (D) may be utilized. For example, components (A) and (D) may be utilized in a stoichiometric ratio (A):(D) of 1:≧1. In certain embodiments, component (D) is utilized in an amount sufficient to provide a molar ratio of olefin compound (B) to organohydridochlorosilane compound (A)(D):(A) of 1:1 to 100:1, such as 1:1 to 10:1, alternatively 2:1 to 10:1, alternatively 3:1 to 5:1. Higher or lower ratios may also be utilized.

[0076] The components utilized in the synthesis method (i.e., organohydridochlorosilane compound (A), alkene compound (B), catalyst (C), and / or olefin compound (D) (if utilized)) may be provided "as is," i.e., ready for reaction to prepare the organosilicon compound. Alternatively, any one or more or all of components (A), (B), (C), and / or (D) may be formed prior to or during the reaction (e.g., as described above, where the method includes preparing catalyst particles (C)). In some embodiments, the synthesis method further includes preparing the organohydridochlorosilane compound (A). In these or other embodiments, the synthesis method further includes preparing the alkene compound (B). In these or other embodiments, the synthesis method further includes preparing the catalyst particles and / or component (C) from the catalyst particles. In these or other embodiments, the synthesis method further includes preparing the olefin compound (D).

[0077] Typically, components (A), (B), (C), and optionally (D) are reacted in a vessel or reactor to prepare the organosiloxane compound. As described below, when the reaction is carried out at elevated or reduced temperatures, the vessel or reactor may be heated or cooled in any suitable manner, for example, via a jacket, mantle, exchanger, bath, coil, etc.

[0078] Components (A), (B), (C), and optionally (D) may be fed together or separately to the vessel, or may be placed in the vessel in any order of addition and in any combination. For example, in certain embodiments, components (A), (B), and (D) are added to a vessel containing component (C), for example, as a pre-made catalyst composition including catalyst particles, or as individual components to form catalyst particles (C) in situ. For example, in certain embodiments, catalyst (C) is prepared in a vessel according to the preparation method above, and then components (A), (B), and optionally (D) are charged. In some embodiments, components (A) and (D) may be first combined before addition, or may be added to the vessel sequentially (e.g., (A) then (D)). In other embodiments, component (D) is added to a vessel containing components (A) and (C). In general, references herein to a "reaction mixture" generally refer to a mixture containing components (A), (B), (C), and, if utilized, optionally (D) (e.g., as obtained by combining such components as described above).

[0079] The method may further include stirring the reaction mixture. Stirring can improve the mixing and contact of components (A), (B), (C), and optionally (D) when they are combined in the reaction mixture, for example. Such contacting can be performed independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), using other conditions. Other conditions can be adjusted to improve the contact and thus the reaction (i.e., dehydrogenative coupling) of the organohydridochlorosilane compound (A) with the alkene compound (B) to prepare the organosilicon compound. Other conditions can be effective conditions to improve the reaction yield or to minimize the amount of certain reaction by-products included in the reaction product along with the organosilicon compound.

[0080] Components (A) and (B) can be reacted in the presence of a carrier vehicle (e.g., a solvent, diluent, fluid, or combination thereof), so that the reaction can be carried out in a solution, emulsion, suspension, slurry, colloid, biphasic mixture, or combination thereof. The particular solvent, carrier, and / or diluent employed, and the amount of each of them used, will be independently selected by one of skill in the art based on, for example, the particular organohydridochlorosilane compound (A), alkene compound (B), catalyst (C), and / or olefin compound (D) (if utilized), the particular organosilicon compound being prepared, and the like. For example, the reaction can be carried out under homogeneous conditions (e.g., in solution). However, the reaction can be carried out heterogeneously, for example, with one or more components suspended but not dissolved in the carrier vehicle. For example, the reaction can be carried out heterogeneously with catalyst particles of component (C) suspended in the carrier vehicle. When component (B) is ethylene, ethylene is typically utilized in a gaseous state. The other components, however, may be used as a heterogeneous mixture (i.e., a suspension, colloid, etc.) or as a homogeneous mixture / solution (i.e., dissolved and / or disposed in the carrier vehicle prior to forming a reaction mixture with the other components).

[0081] If utilized, the carrier vehicle is typically selected based on the particular organohydridochlorosilane compound (A), alkene compound (B), catalyst particles (C), and / or olefin compound (D) (if utilized) selected, as well as the particular organosilicon compound to be prepared. For example, in some embodiments, the carrier vehicle includes or is an oil (e.g., organic oil and / or silicone oil), fluid, solvent, etc., or a combination thereof. Examples of suitable carrier vehicles include those described herein, such as those described above with respect to the carrier fluid of the preparation method. Thus, in certain embodiments, the carrier vehicle is the same as the carrier fluid utilized in the preparation method. Thus, in these or other embodiments, the carrier vehicle includes or is an aromatic solvent. In some such embodiments, the carrier vehicle includes or is an aromatic organic solvent, such as benzene, toluene, xylene, mesitylene, etc., or a combination thereof.

[0082] If utilized, portions of the support vehicle or solvent may be added separately to the organohydridochlorosilane compound (A), alkene compound (B), catalyst (C), and / or olefin compound (D) (if utilized), or may be otherwise combined with the overall mixture of components (A), (B), (C), and / or (D), or with the reaction mixture as a whole. The total amount of support vehicle / solvent present in the reaction mixture will be selected by one of skill in the art based, for example, on the particular components (A), (B), (C), and / or (D) selected, the reaction parameters employed, etc.

[0083] In some embodiments, the reaction is carried out at an elevated temperature. The elevated temperature will be selected and controlled depending on the particular organohydridochlorosilane compound (A), alkene compound (B), catalyst (C), and / or olefin compound (D) selected, the reaction vessel utilized (e.g., open at ambient pressure or sealed under positive pressure (e.g., positive pressure of ethylene when utilized as alkene compound (B)), the presence and boiling point of the carrier vehicle, and the like. Thus, the elevated temperature will be readily selected by one of ordinary skill in the art in view of the reaction conditions and parameters selected, and the description herein. The elevated temperature for preparing the organosilicon compound is typically above ambient to 300°C, such as 40 to 250, alternatively 50 to 200, alternatively 60 to 175, alternatively 60 to 150, alternatively 60 to 125°C.

[0084] The dehydrocoupling reaction can be carried out at elevated pressure (e.g., superatmospheric pressure). For example, the reaction can be carried out at pressures from above ambient pressure to 200,000 kPa, such as from greater than 101.3 to 20,000, alternatively from 110 to 10,000, alternatively from 150 to 5,000, alternatively from 200 to 2,000, alternatively from 200 to 1,000, alternatively from 250 to 1,000, alternatively from 250 to 750 kPa.

[0085] It should be understood that the high temperature and / or high pressure may also differ from the ranges set forth above, especially when both high temperature and high pressure are utilized. In certain embodiments, the high temperature and high pressure are collectively selected to provide supercritical conditions for one or both of components (A) and (B). It should also be understood that reaction parameters may be modified during the reaction of components (A) and (B). For example, temperature, pressure, and other parameters may be independently selected or modified during the reaction. Any of these parameters may independently be ambient parameters (e.g., room temperature and / or atmospheric pressure) and / or non-ambient parameters (e.g., low or high temperatures and / or reduced or elevated pressures). Any parameter may also be dynamically modified, changed in real time, i.e., during the process, or static (e.g., for the duration of the reaction or any portion thereof).

[0086] The time during which the reaction of components (A) and (B) to prepare the organosilicon compound is carried out is a function of scale, reaction parameters and conditions, choice of particular components, etc. At a relatively large scale (e.g., greater than 1, alternatively 5, alternatively 10, alternatively 50, alternatively 100 kg), the reaction may be carried out for several hours, such as 2 to 48, alternatively 3 to 36, alternatively 4 to 24, alternatively 6, 12, 18, 24, 36, or 48 hours, as would be readily determined by one of ordinary skill in the art (e.g., by monitoring the conversion of organohydridochlorosilane compound (A), the formation of organosilicon compound, etc., via chromatographic and / or spectroscopic methods). In certain embodiments, the time during which the reaction is carried out is greater than 0 to 48 hours, such as 1 to 36, alternatively 1 to 24, alternatively 1 to 12, alternatively 2 to 12, alternatively 2 to 10 hours, after combining components (A) and (B) in the presence of catalyst (C), optionally after reaching elevated temperature and / or pressure.

[0087] Generally, the reaction of components (A) and (B) produces a reaction product that contains an organosilicon compound. In particular, over the course of the reaction, the reaction mixture that contains components (A) and (B) will contain an increasing amount of the organosilicon compound and a decreasing amount of components (A) and (B). When the reaction is complete (e.g., one of components (A) or (B) is consumed and no additional organosilicon compound is produced), the reaction mixture can be referred to as a reaction product that contains an organosilicon compound. In this manner, the reaction product typically includes any remaining amounts of components (A), (B), (C), and optionally (D), as well as their decomposition and / or reaction products (e.g., by-products and / or other materials), and any carrier vehicle or solvent that is utilized.

[0088] In certain embodiments, the synthesis method further includes isolating and / or purifying the organosilicon compound from the reaction product. As used herein, in the context of the synthesis method, isolating the organosilicon compound refers to increasing the relative concentration of the organosilicon compound (e.g., in the reaction product or a purified version thereof) compared to other compounds combined with the organosilicon compound. Thus, as understood in the art, isolation / purification can include removing other compounds from such combinations (i.e., reducing the amount of impurities / other components combined with the organosilicon compound in the reaction product, for example), and / or removing the organosilicon compound itself from the combination. Any suitable technique and / or protocol for isolation can be utilized, including those described above for preparation methods (e.g., distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, etc.), and combinations thereof (e.g., sequentially, as part of a single procedure, etc.). It is understood that isolation can include purification of the organosilicon compound, and thus can be referred to as purification of the organosilicon compound. However, purification of the organosilicon compound may involve alternative and / or additional techniques compared to those utilized for the isolation of the organosilicon compound. Regardless of the particular technique selected, isolation and / or purification of the organosilicon compound may be performed in series (i.e., in-line) with the reaction itself and thus may be automated. In other cases, purification may be an independent procedure applied to the reaction product containing the organosilicon compound. In certain embodiments where the alkene compound (B) is gaseous (e.g., when ethylene is utilized as the alkene compound (B)), the organosilicon compound is purified by venting and / or purging the reaction vessel and reaction product, thus removing any remaining alkene compound (B) and hydrogen (H2) prepared during the reaction from the reaction product. In some such embodiments, the reaction product is cooled before and / or during the venting and / or purging.

[0089] In certain embodiments, the synthesis method includes isolating the organosilicon compound from the reaction product via distillation, where the organosilicon compound is removed as a distillate from one or more components of the reaction product (e.g., catalyst (C)). The distillation is typically carried out at sub-atmospheric pressure and sub-ambient temperature (i.e., low temperature and reduced pressure). The reduced pressure and low temperature will be selected by one of skill in the art, taking into consideration the reaction conditions and parameters selected, the components utilized, the organosilicon compound being prepared, and the like. The reduced pressure is typically operated as a vacuum, although any reduced pressure between vacuum and atmospheric pressure (i.e., 101.325 kPa) can be utilized. For example, the reduced pressure can be greater than 0 to 50, alternatively greater than 0 to 40, alternatively greater than 0 to 30, alternatively greater than 0 to 20, alternatively greater than 0 to 10, alternatively greater than 0 to 5, alternatively greater than 0 to 4, alternatively greater than 0 to 3, alternatively greater than 0 to 2 kPa (e.g., measured by mmHg).

[0090] Typically, the reaction product prepared by the reaction of components (A) and (B) includes a catalyst residue comprising a ruthenium complex. The ruthenium complex of the catalyst residue may be the same as, or substantially the same as, the Ru(0) complex utilized in or as the catalyst particle of component (C) in the reaction. Alternatively, the ruthenium complex of the catalyst residue may be formed in the reaction (i.e., during the reaction itself) from the catalyst particle (i.e., from the Ru(0) complex of the catalyst particle) utilized in or as component (C).

[0091] In certain embodiments, the synthesis method includes isolating catalyst residue from the reaction mixture, for example by using one or more of the above techniques.In some embodiments, isolating the organosilicon compound from the reaction product via distillation separates the catalyst residue by removing other components of the reaction product as distillate from the reaction product.In other embodiments, such as when the reaction is carried out under heterogeneous conditions, the synthesis method includes filtering the reaction mixture, thus isolating the catalyst residue from the reaction mixture as filtrate, and the remaining components of the reaction mixture are separated from the reaction mixture as filtrate.

[0092] The isolated catalyst residue may be utilized to catalyze another dehydrocoupling reaction of components (A) and (B), for example, optionally in the presence of component (D), as described above. Thus, in certain embodiments, the synthesis method includes using the catalyst residue (i.e., reusing catalyst (C)) to catalyze a further dehydrocoupling reaction, which may be the same or different from the initial reaction used to prepare the catalyst residue. It will be understood that reusing catalyst (C) in this manner may be performed any number of times in any number of independently selected successive dehydrocoupling reactions, each of which may be the same or different from any other of the dehydrocoupling reactions (e.g., with respect to the particular types and / or amounts of components (A), B), and / or (D) selected, the parameters used, etc.). In certain embodiments, catalyst (C) is reused at least once, alternatively at least twice, alternatively at least 3, 4, 5, 6, 7, 8, 9, or 10 times.

[0093] The synthesis method utilizing catalyst particles can prepare organosilicon compounds in high yields with very high conversion rates and excellent selectivity.For example, in certain embodiments, the synthesis method according to the above parameters provides a conversation rate of at least 95, alternatively at least 98, alternatively at least 99% based on the amount of organohydridochlorosilane compound (A) utilized (e.g., as measured via gas chromatography (GC) according to the procedure described below).In these or other embodiments, the synthesis method provides a yield of organosilicon compounds of at least 65, alternatively at least 70, alternatively at least 75, alternatively at least 80, alternatively at least 85% based on the amount of organohydridochlorosilane compound (A) utilized (e.g., as measured via gas chromatography (GC) according to the procedure described below). In these or other embodiments, the synthetic methods provide a selectivity of dehydrogenative silylation (DHS) to hydrosilylation (DS) (DHS:DS) of at least 70:30, alternatively at least 75:25, alternatively at least 80:20, alternatively at least 85:15.

[0094] As introduced above, the synthetic method prepares an organosilicon compound. More specifically, as will be understood in view of the structure of components (A) and (B) and the description of the parameters of their reaction, the method prepares an organosilicon compound as a dehydrogenative coupling product of an organohydridochlorosilane compound (A) and an alkene compound (B). As will be understood by those skilled in the art, the specific organosilicon compound prepared correlates with the specific organohydridochlorosilane compound (A) utilized in the synthetic method. More specifically, the organohydridochlorosilane compound (A) forms the organochlorosilane backbone of the organosilicon compound, and the alkene compound (B) forms the alkenyl group bonded to the silicon atom of the organochlorosilane backbone. Thus, the organosilicon compound can be further defined as an organoalkenylchlorosilane compound.

[0095] In certain embodiments, the organosilicon compound has the general formula (R 1 CHCH)SiCl x R 3-x wherein each R, R 1 and subscript x is as defined above. For example, in some embodiments where the organohydridochlorosilane compound (A) is further defined as a diorganohydridochlorosilane (e.g., where subscript x is 1 so that compound (A) has the formula HSiClR2), the synthetic method can provide a compound of the formula (R 1 CHCH)SiClR2 (wherein each R and R 1 In other embodiments where the organohydridochlorosilane compound (A) is further defined as an organohydridodichlorosilane (e.g., where the subscript x is 2 so that compound (A) has the formula HSiClR), the synthetic method prepares the organosilicon compound as a diorganochloroalkenylsilane compound having the formula (R 1 CHCCH)SiClR (wherein each R and R 1 The organosilicon compounds are prepared as organodichloroalkenylsilane compounds having the formula (I) where I is as defined above.

[0096] As introduced above, in certain embodiments, the alkene compound (B) is ethylene. In such embodiments, R 1 is H, so organosilicon compounds have the general formula (HCCH)SiCl x R 3-xwhere each R subscript x is as defined above. In some embodiments, each R is an alkyl group, so the organosilicon compound is further defined as a dialkylchlorovinylsilane or an alkyldichlorovinylsilane. In certain embodiments, each R is methyl (i.e., -CH3), so the organosilicon compound is further defined as a dimethylchlorovinylsilane or a methyldichlorovinylsilane. Similarly, it will be understood that the organosilicon compound may include a combination of such compounds, i.e., when more than one of the organohydridochlorosilane compounds (A) is utilized in the synthesis method.

[0097] The organosilicon compounds prepared according to the synthesis method can be utilized in a variety of end-use applications, for example as separate components in compositions, including curable compositions, personal care or cosmetic compositions, etc. Since the organosilicon compounds contain at least one aliphatically unsaturated group per molecule (e.g., silicon-bonded alkenyl groups prepared from alkene compound (B)), the organosilicon compounds can be utilized in further reactions, for example, hydrosilylation reactions. For example, the organosilicon compounds can be components in hydrosilylation curable compositions.

[0098] The following examples are intended to illustrate the embodiments described herein and are not to be construed as limiting the scope of the invention in any way. Feature evaluation procedure

[0099] Gas Chromatography (GC)

[0100] Gas chromatography (GC) data is obtained using an Agilent 7890A gas chromatograph equipped with a Thermo Scientific TG-5HT column. Detection of eluting species is achieved using a flame ionization detector (FID). Samples (1 μL) are injected onto the column and held at 40° C. for 8 minutes from the time of injection, after which the temperature is increased to 300° C. at a rate of 15° C. / min. Elution times were determined by injection of standards, and quantification of products was determined by integration of the eluted signal area. Exemplary standards (with elution times) include chlorodimethylsilane (1.90 min), dichloromethylsilane (1.93 min), chlorodimethylvinylsilane (2.44 min), dichloromethylvinylsilane (2.79 min), chlorodimethyl(ethyl)silane (2.62 min), and dichloromethyl(ethyl)silane (3.05 min).

[0101] Ultraviolet-Visible, UV-Vis

[0102] Ultraviolet-visible (UV-Vis) absorbance spectra are recorded using a Shimadzu UV-1800 double-beam spectrophotometer equipped with deuterium and tungsten-halogen lamps, and a silicon photodiode detector. Samples and blanks (pure solvent) are filled into matching quartz cuvettes, and absorbance is recorded from 320 to 1000 nm in 1 nm increments.

[0103] Certain specific ingredients utilized in the examples are set forth in Table 1 below.

[0104] [Table 1]

[0105] Examples 1-4: Preparation of Ru(0) catalyst particles

[0106] Various Ru(0) catalyst particles are prepared to give Examples 1-4. In particular, the Ru(0) complex (R), ligand precursor (L), and carrier fluid (F) are combined in a round-bottom flask to form a mixture, which is then stirred at room temperature for 20 minutes. The mixture is then warmed to 40° C. with stirring and held for 20 hours. The mixture is then gradually warmed to target temperatures (heat increments: 20° C., hold time: 20 minutes, target temperatures: 60, 80, 100, 120, 140, and 160° C.) with stirring and held to give a reaction product containing Ru(0) catalyst particles, while collecting samples from the mixture at the end of each hold time at each target temperature. The samples are evaluated for opacity (visual) and absorbance (UV-Vis) to confirm particle formation / nucleation, and the nucleation onset temperature is reported as the lowest temperature at which a significant change in the absorbance spectrum of the visible particles or mixture is observed. The reaction product is then centrifuged (4,000 rpm, 10 min) to evaluate the isolation / concentration of the reaction product Ru(0) catalyst particles (pellets) from the soluble components (supernatant). Certain parameters, characteristics, and evaluation results of Examples 1-4 are listed in Table 2 below.

[0107] [Table 2]

[0108] In each of Examples 1-4, Ru(0) catalyst particles are prepared in a heterogeneous reaction product that appears as an opaque suspension. Particle nucleation is evidenced by a significant change in the absorbance spectrum of the mixture upon heating, with visible particles forming at temperatures as low as 100° C. (see, e.g., Example 1). Depending on the particular parameters used, the exemplary methods prepare Ru(0) catalyst particles of sufficient size for easy isolation (see, e.g., Examples 3-4).

[0109] Examples 5-7: Preparation of Ru(0) catalyst particle compositions

[0110] Various compositions containing Ru(0) catalyst particles are prepared. In particular, Ru(0) complex (R), ligand precursor (L), and carrier fluid (F) are combined in a round-bottom flask to form a mixture. The mixture is heated to 160° C. with stirring, held for 20 minutes, and then cooled to room temperature to yield reaction products (catalyst compositions (C1)-(C3)) containing Ru(0) catalyst particles as an opaque suspension. Specific parameters for Examples 5-7 are set forth in Table 3 below.

[0111] Example 8: Preparation of isolated Ru(0) catalyst particle composition

[0112] A composition comprising isolated Ru(0) catalyst particles is prepared. In particular, the Ru(0) complex (R), the ligand precursor (L), and the carrier fluid (F) are combined in a round-bottom flask to form a mixture. The mixture is heated to 160° C. with stirring and held for 20 minutes to obtain a reaction product comprising the Ru(0) catalyst particles as an opaque suspension, which is then cooled to room temperature. The suspension is then centrifuged (4,000 rpm, 10 minutes) to pellet the Ru(0) catalyst particles, and the resulting supernatant is removed. The Ru(0) catalyst particles are then washed by suspending the pellet in solvent (S-1) (12 mL), the resulting mixture is centrifuged (4,000 rpm, 10 minutes) to re-pellet the Ru(0) catalyst particles, the supernatant is removed from the resulting pellet of Ru(0) catalyst particles, and the supernatant is evaluated via UV-Vis. The washing process is repeated until the supernatant is essentially colorless (total washes: 4) to isolate the Ru(0) catalyst particles, which are then suspended in solvent (S-1) (12 mL) to obtain an opaque suspension (catalyst composition (C4)). The specific parameters for Example 8, as well as those for Examples 5-7 above, are listed in Table 3 below.

[0113] [Table 3]

[0114] Examples 9-12: Preparation of chlorodimethylvinylsilane (ClSi(CH3)2(CHCH2))

[0115] Ru(0) catalyst particles are utilized to catalyze the dehydrogenative silylation reaction to prepare vinylsilanes (i.e., as organosilicon compounds). In particular, the catalyst composition prepared in one of Examples 5-8 above is transferred via cannula to a Schlenk tube and charged with hydridosilane (A). The resulting mixture is then transferred via cannula to a Fischer-Porter tube equipped with a stir bar and a manifold for introducing ethylene (i.e., alkene compound (B-1)). The tube is then pressurized to 5 bar with ethylene and then vented. The tube is pressurized with ethylene and subsequently vented four more times to substantially purge the tube of nitrogen. The tube is then pressurized to 5 bar with ethylene and the resulting reaction mixture is warmed to 100° C. with stirring and held for 2 hours to obtain a reaction product. The reaction product is then cooled to −78° C. and the tube is vented to remove ethylene. The reaction product is then transferred via cannula to a Schlenk tube and then transferred to a distillation apparatus equipped with a collection vessel and cooled to −78° C. The reaction product is then distilled at subatmospheric pressure and at a temperature below 25° C. to remove a volatile product mixture containing the organosilicon compound as a distillate from the catalyst residue. The distillate is then warmed to room temperature and analyzed by gas chromatography to evaluate the conversion of hydridosilane (A) and the yield of organosilicon compound. The specific parameters and evaluation results for Examples 9-12 are set forth below in Table 4.

[0116] [Table 4]

[0117] As shown in Table 4 above, the catalyst compositions prepared in Examples 5-8 successfully catalyze the dehydrocoupling reaction (see, e.g., Examples 9-12). Moreover, the exemplary processes provide nearly complete conversion of the hydridosilane starting material along with good yields of the dehydrocoupling product. In each of Examples 9-12, chlorodimethylethylsilane is identified as the major by-product, demonstrating hydrosilylation as a competing reaction under the conditions utilized.

[0118] The above description relates to the general and specific embodiments of the disclosure. However, various modifications and changes may be made without departing from the spirit and broader aspects of the disclosure as defined in the appended claims, which are to be interpreted in accordance with the principles of patent law, including the doctrine of equivalents. Thus, the disclosure is presented for illustrative purposes and should not be construed as an exhaustive description of all embodiments of the disclosure or to limit the scope of the claims to the specific elements illustrated or described in connection with these embodiments. For example, any reference to a singular element using the articles "a," "an," "the," or "the" is not to be construed as limiting the element to the singular. Furthermore, it should be understood that the terms "right angle," "orthogonal," "vertical," and "parallel" are generally used herein in a relative, rather than absolute sense. Furthermore, it will be understood that terms such as "substantially," "about," and "essentially" indicate a slight deviation of the property being modified. Such deviation may be 0-10%, alternatively 0-5%, or alternatively 0-3% of the particular property.

Claims

1. 1. A method for preparing an organosilicon compound, the method comprising: combining a Ru(0) complex with a carrier fluid to form a mixture; heating the mixture at an elevated temperature to nucleate the Ru(0) complexes to obtain catalyst particles in the carrier fluid; Optionally, isolating the catalyst particles from the support fluid; and (C) reacting (A) an organohydridochlorosilane compound with (B) an alkene compound via dehydrogenative coupling in the presence of a catalyst, thereby preparing the organosilicon compound; The catalyst (C) contains the catalyst particles, The method, wherein the Ru(0) complex comprises phosphorus and / or amine ligands.

2. 2. The method of claim 1, wherein: (i) the Ru(0) complex comprises a triruthenium complex.

3. the Ru(0) complex comprises the phosphorus ligand, (i) the phosphorus ligand has the general formula PR″ ３ wherein each R″ is independently of the formula —R′ or —OR′, and each R′ is an independently selected substituted or unsubstituted aryl, aralkyl, or cycloalkyl group; or (ii) the phosphorus ligand has a molecular weight of 2,060 to 2,090 cm －１ or (iii) the phosphorus ligand comprises a Tolman cone angle of 115 to 185°; or (iv) any combination of (i)-(iii).

4. 4. The method of any one of claims 1 to 3, wherein the method further comprises preparing the Ru(0) complex, and preparing the Ru(0) complex comprises combining a triruthenium complex with a ligand precursor compound to obtain the Ru(0) complex.

5. (i) The triruthenium complex is Ru ３ (CO)12; (ii) combining said triruthenium complex with said ligand precursor compound in the presence of said carrier fluid to obtain said Ru(0) complex combined with said carrier fluid, thereby preparing said mixture; or (iii) the method of claim 4, comprising both (i) and (ii).

6. 6. The method of claim 4 or 5, wherein the ligand precursor compound comprises (i) a phosphorus compound, (ii) an amine compound, or (iii) both (i) and (ii).

7. 7. The method of claim 6, wherein the ligand precursor compound comprises the phosphorus compound, and (i) the phosphorus compound comprises an organophosphine or organophosphite, (ii) the phosphorus compound is selected from substituted or unsubstituted triarylphosphines, tricycloalkylphosphines, bis(diarylphosphino)alkanes, bis(dicycloalkylphosphino)alkanes, triarylphosphites, and combinations thereof, or (iii) comprises both (i) and (ii).

8. 8. The method of any one of claims 1 to 7, wherein the alkene compound (B) is ethylene; (i) the organohydridochlorosilane compound (A) comprises chlorodimethylsilane and the organosilicon compound comprises chlorodimethylvinylsilane; (ii) the organohydridochlorosilane compound (A) comprises dichloromethylsilane and the organosilicon compound comprises dichloromethylvinylsilane; or (iii) both (i) and (ii).

9. 9. The process according to any one of claims 1 to 8, wherein the dehydrocoupling is carried out (i) at an elevated temperature above 60°C, (ii) at an elevated pressure from above atmospheric pressure to 10 bar, (iii) at a molar ratio of alkene compound (B) to organohydridochlorosilane compound (A)(B):(A) of 1 to 10, (iv) in the presence of a solvent, or (v) any combination of (i) to (iv).

10. 10. The method of any one of claims 1 to 9, comprising: (i) a conversion of said organohydridochlorosilane compound (A) of at least 95%, (ii) a yield of said organosilicon compound of at least 75%, (iii) a dehydrogenative silylation (DHS) to hydrosilylation (DS) (DHS:DS) selectivity of at least 70:30, or (iv) any combination of (i)-(iii).

Images