Methods for preparing and using silyl ester compounds

Abstract

A method for preparing a silyl ester compound is disclosed. The silyl ester compound may be a silane monomer or a siloxane oligomer. The silyl ester compound is hydrosilylated with a polyorganohydrogensiloxane to form a silyl ester-protected product, which can then be deprotected with water to prepare a carboxy-functional polyorganosiloxane.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 082485, filed September 26, 2020. U.S. Provisional Patent Application No. 63 / 082485 is incorporated herein by reference.

[0002] An efficient method for preparing silyl ester compounds via hydrosilylation of silyl hydrides and allyl (alkyl) acrylates with less than 1% Si-C by-products is disclosed. The silyl ester compounds may be silane monomers or siloxane oligomers. The silyl ester compounds can be used in methods for preparing carboxy-functional organosilicon compounds, such as carboxy-functional polyorganosiloxanes. [Background technology]

[0003] Carboxylic acid-functional siloxanes are excellent rheology and wetting modifiers for polyesters. When reacted with inorganic bases or amines, they function as antistatic surfactants and lubricants. Existing methods for preparing carboxylic acid-functional (carboxy-functional) polyorganosiloxanes include transesterification processes, but these can require multiple steps involving purification (e.g., distillation and / or extraction) and separate unit operations, which can be time-consuming and expensive. Summary of the Invention

[0004] A method for preparing a silyl ester compound is provided. The method comprises 1) combining starting materials comprising (A) a silyl hydride, (B) an allyl(alkyl)acrylate, and (C) a rhodium catalyst, thereby producing (D) a silyl ester compound. The method may further comprise 2) combining starting materials comprising (D) the silyl ester compound and (E) an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule, thereby forming (G) a silyl ester-protected product. The method may further comprise 3) combining starting materials comprising (G) the silyl ester-protected product and (H) water, thereby forming a carboxy-functional organosilicon compound. DETAILED DESCRIPTION OF THE INVENTION

[0005] In the above method, step 1) comprises combining starting materials including (A) a silyl hydride, (B) an allyl(alkyl)acrylate, and (C) a rhodium catalyst, thereby producing (D) a silyl ester compound. Alternatively, the starting materials used in step 1) may consist essentially of (A), (B), and (C). Alternatively, the starting materials used in step 1) may consist of (A), (B), and (C). Optionally, a solvent may be added to facilitate the addition of the rhodium catalyst (C). Optionally, a (meth)acrylate polymerization inhibitor may be added during step 1).

[0006] The starting materials used in step 1) can be combined by any convenient means, such as mixing. Starting materials including (A) a silyl hydride can be metered into a reactor containing starting materials including (B) an allyl (meth)acrylate and (C) a rhodium catalyst. The starting materials in the reactor may further include a solvent and / or a polymerization inhibitor, as described above. The starting materials for step 1) can be heated to a temperature of at least 50°C, alternatively at least 60°C. Concurrently, the starting materials for step 1) can be heated to a temperature of up to 125°C, alternatively up to 80°C, alternatively up to 75°C, alternatively up to 70°C, or alternatively up to 60°C. Without wishing to be bound by theory, it is believed that lower temperatures, e.g., 50°C to 60°C, may be desirable to minimize propene hydrogenation. Step 1) can be carried out in batch or semi-batch mode. Step 1) can be carried out under an inert atmosphere, e.g., under nitrogen. Without being bound by theory, it is believed that the use of a stirred batch reactor with an inert gas sweep through the reaction mixture therein may improve yields by removing the by-product propene before it can react. A detailed description of the starting materials used in the present process is as follows:

[0007] (A) Silyl hydride The starting material (A) used in step 1) of the method described herein is a silyl hydride. A silyl hydride has one silicon-bonded hydrogen atom per molecule. The silyl hydride may be a silane monomer and / or a siloxane oligomer. For example, a siloxane oligomer may have the unit formula (A1):(R 1 3SiO 1 / 2 ) a (R 1 2HSiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 HSiO 2 / 2 ) d (In the formula, each R 1are independently selected from the group consisting of alkyl groups of 1 to 8 carbon atoms and halogenated alkyl groups of 1 to 8 carbon atoms, subscript a is 0 to 2, subscript b is 0 to 2, the amount (a+b)=2, subscript c is 0 or 1, subscript d is 0 or 1, the amount (b+d)=1, and 4≧(a+b+c+d)≧2. Alternatively, 3≧(a+b+c+d)≧2.

[0008] R 1 Examples of suitable alkyl groups for R include, but are not limited to, 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 of 6 carbon atoms. 1 Suitable halogenated alkyl groups for are exemplified by, but not limited to, the alkyl groups described above in which one or more hydrogen atoms have been replaced with a halogen atom, such as F or Cl. For example, 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, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples of suitable halogenated alkyl groups. Alternatively, each R 1 is independently methyl, ethyl or propyl. 1 may be the same or different in each occurrence. Alternatively, each R 1 can be a methyl group.

[0009] Alternatively, the starting material (A) is (A2) [ka] , (A3) [ka] (In the formula, R 1 is as above, and R 2 is H and R 1 and wherein each molecule is selected from the group consisting of: 2 is H, and one R per molecule 2 is R 1 (A1) and a combination of both (A2) and (A3).

[0010] Alternatively, the starting material (A) is a compound of formula (A4): [ka] (In the formula, R 1 The organohydrogensiloxane oligomer may be an organohydrogensiloxane oligomer of the formula (wherein R is as defined above).

[0011] Suitable organohydrogensiloxanes for starting material (A) are known in the art and are commercially available.For example, suitable organohydrogensiloxane oligomers for starting material (A) can be selected from the group consisting of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,3-pentamethyldisiloxane, and combinations thereof, and these oligomers are available from, for example, Sigma-Aldrich, Inc. (St. Louis, Missouri, USA) (Sigma).

[0012] Alternatively, the silyl hydride starting material (A) used in the methods described herein may comprise a silane monomer in addition to or in place of the siloxane oligomers described above. The silane monomer has the formula (A5): HSiR 1 3 (wherein, R 1is as defined above). Suitable silane monomers for starting material (A) are known in the art and are commercially available, for example, from Gelest Inc. (Morrisville, Pennsylvania, USA). For example, the silane monomer for starting material (A) may be selected from the group consisting of trimethylsilane (HSiMe), triethylsilane (HSiEt), tripropylsilane (HSiPr), tributylsilane (HSiBu), trihexysilane, trioctylsilane, and combinations thereof.

[0013] (B) Allyl(alkyl)acrylate The starting material (B) useful in the methods described herein is an allyl(alkyl)acrylate. The starting material (B) has the formula (B1): [ka] (In the formula, R 4 is hydrogen and alkyl groups of 1 to 8 carbon atoms (e.g., R 1 Alternatively, R 4 The alkyl group may be a methyl group. Examples of starting material (B) include allyl acrylate and allyl methacrylate. Alternatively, starting material (B) may be allyl methacrylate.

[0014] The starting material (A), a silyl hydride, and the starting material (B), an allyl(alkyl)acrylate, are used in step 1) of the process in a relative molar amount of starting material (B):starting material (A) of 1 or greater, i.e., a molar ratio of (B):(A) ≥ 1:1. Alternatively, (B):(A) may range from 5:1 to 1:1, alternatively from 2:1 to 1:1, alternatively from 1.5:1 to 1:1, alternatively from 1.1:1 to 1:1.

[0015] (C) Rhodium catalyst The starting material (C) of the process described herein is a rhodium catalyst. The rhodium catalyst may be used in an amount of at least 0.0000001 mol%, based on the amount of starting material (A), silyl hydride, used in step 1) of the process described herein. Alternatively, the amount of rhodium catalyst may be at least 0.0001 mol%, alternatively at least 0.001 mol%, alternatively at least 0.001 mol%, alternatively at least 0.01 mol%, alternatively at least 0.1 mol% rhodium catalyst, on the same basis. At the same time, the rhodium catalyst may be used in an amount of up to 100 mol%, alternatively at most 10 mol%, alternatively at most 5 mol%, alternatively at most 2 mol%, alternatively at most 1 mol%, alternatively at most 0.1 mol%, alternatively at most 0.01 mol%, on the same basis.

[0016] The rhodium catalyst (C) may be cationic or neutral. The rhodium may have a charge state (z) of 0, 1, 2, 3, 4, 5, or 6; alternatively, 0, 1, 2, or 3; or alternatively, 0, 1, or 3. The rhodium may be stabilized by 0 to 6 ligands. The rhodium catalyst may be monomeric, dimeric, trimeric, oligomeric, clustered, colloidal, nanoparticle, or on a support such as alumina or carbon. The rhodium catalyst may comprise a rhodium-ligand complex. The rhodium-ligand complex may be represented by the formula (C1): [Rh z (R 3 x ] y where the subscript y is 1 to 100, the subscript x is 0 to 6, and R 3 R may have a ligand. 3 R may be monodentate, chelating or bridged. 3are halogens such as F, Cl, Br, and I; alkyl groups; 1,5-cyclooctadiene (COD); bicyclo[2.2.1]hept-2-ene; 2,5-norbornadiene (i.e., bicyclo[2.2.1]hepta-2,5-diene); 1,3,7-cyclooctatriene; 1,3,5,7-cyclooctaterene; allyl; nitrate, ammonium, or ammonia; oxide; dihydrogen monoxide; trifluorosulfonic acid; benzene; dimethylformamide; dimethyl sulfoxide; dialkyl or cyclic ethers; acetonitrile; ethylene, It can be carbon monoxide, trisubstituted (aryl or alkyl) phosphines; disubstituted (alkyl, aryl, or cyclic) phosphinoalkanes; dialkylaminoalkanes or diphenylaminoalkanes; trisubstituted (alkyl, phenyl) or cyclic amines; acetylacetonate (acac); dinitrogen; 1,3-bis(dialkyl or diphenyl)imidazol-2-ylidene, 1,3-bis(dialkyl or diphenyl)imidazolin-2-ylidene, or 1,3-bis(dialkyl or diphenyl)benzimidazol-2-ylidene NHC. Alternatively, R 3 Alternatively, R may be a multidentate ligand which may combine one or more of the groups listed above. 3 may be the same or different, or may be of the formula -(CH2) x The rhodium-ligand complex may be a combination of the above selected ligands linked by a divalent group such as a group of the formula: (wherein x is as defined above). Alternatively, the rhodium-ligand complex may be, for example, a rhodium diphosphine complex, a rhodium cyclic diene complex, or a combination thereof. Without being bound by theory, it is believed that all of the above Rh-ligand combinations, with or without the ligand present, can be converted into generally active catalysts that do not confer selectivity benefits to the Si-C hydrosilylation product on the silyl ester (D).

[0017] Alternatively, the starting material (C) added during step 1) may comprise a chelated rhodium diphosphine complex. The chelated rhodium diphosphine complex may be represented by the formula (C2): {[(R 8 2P)R 7 (R 82P)]Rh(uR 9 In formula (C2), each R 7 are independently a divalent hydrocarbon group, and each R 8 are independently a monovalent hydrocarbon group, and each R 9 are independently negatively charged ligands. 7 The divalent hydrocarbon group may be an alkanediyl group, such as an alkanediyl group of 1 to 6 carbon atoms. 7 may be methane-diyl, ethane-1,2-diyl, or hexane-1,6-diyl, or R 7 may be ethane-1,2-diyl.

[0018] R 8 The monovalent hydrocarbon group in R may be an alkyl group or an aryl group. 8 and R may together form a heterocyclic group containing a P atom in the ring. 8 Examples of suitable alkyl groups are exemplified by, but not limited to, 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 of 6 carbon atoms. 8 The alkyl group in R may be methyl, ethyl or propyl. 8 Suitable aryl groups for R are exemplified by, but not limited to, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl. 8 may be an ethyl group or a phenyl group.

[0019] R 9Examples of suitable negatively charged ligands include halogen atoms, alkoxy ligands, and hydride ligands. Examples of suitable halogen atoms include bromine (Br), chlorine (Cl), and iodine (I). Alternatively, the halogen atom may be Cl. Examples of alkoxy ligands include methoxy, ethoxy, and propoxy. Alternatively, the alkoxy ligand may be methoxy.

[0020] Examples of suitable rhodium diphosphine complexes for starting material (C) include, but are not limited to, [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium], [1,2-bis(diethylphospino)ethane]dichlorodirhodium], and mixtures thereof. Rhodium diphosphine complexes are commercially available from Strem Chemicals, Inc. (Newburyport, Massachusetts, USA).

[0021] Alternatively, starting material (C) may comprise a rhodium catalyst having no phosphine ligand. For example, starting material (C) may comprise a rhodium catalyst having the formula (C3): [R 5 h Rh]R 10 , (C4):[Rh(R 5 ) h (uR 9 ) f ] g (wherein the subscript h is 1 to 4, and each R 5 are independently selected from the group consisting of 1,5-cyclooctadiene ligands, 2,5-norbornadiene ligands, ethylene ligands, cyclooctene ligands, and acetylacetonate ligands; R 10 is an anion and R 9 is a negatively charged bridging ligand as described above, where subscript f is 1 or 2 and subscript g is 1 or 2), or (C5) which is a combination of both (C3) and (C4). Alternatively, R 10The anions include, but are not limited to, perchlorate, trifluoromethylsulfonate, tetrafluoroborate, tetrakisphenylborate, tetrakis(pentafluorophenyl)borate, methyl tris(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, hexafluoroantimonate, hexafluorophosphate, [Al(C(CF3)3)4]-, [HCB 11 The starting anion may be what is referred to by those skilled in the art as a "weakly coordinating anion" or a "non-coordinating anion," including carboranes such as MeBr. For example, the starting material (C) may include rhodium 1,5-cyclooctadiene chloride dimer, commercially available from Sigma-Aldrich, Inc.

[0022] The rhodium catalyst may optionally be delivered in a solvent. The solvent may solubilize the catalyst but not essentially react with the starting materials of step 1). The solvent may be selected based on the solubility of the catalyst selected for use in step 1) and the volatility of the solvent and starting materials. "Solubility" refers to the solvent being sufficient to dissolve and / or disperse the catalyst. "Volatility" refers to the vapor pressure of the solvent. If the solvent is too volatile (vapor pressure is too high), it may not adequately promote mixing of the (C) rhodium catalyst with starting materials (A) and / or (B). However, if the solvent is not sufficiently volatile (vapor pressure is too low), it may be difficult to remove after the process is completed.

[0023] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as 0.5-1.5 cSt DOWSIL™ 200 fluid and DOWSIL™ OS fluid, commercially available from Dow Silicones Corporation (Midland, Michigan, USA). Alternatively, the solvent may comprise an organic solvent. The organic solvent may be an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a halogenated hydrocarbon such as chloroform, 1,1,1-trichloroethane, or methylene chloride; an alcohol such as methanol or ethanol; a linear or cyclic ether such as diethyl ether, 1,4-dioxane, tetrahydropyran, or tetrahydrofuran; or a combination of two or more thereof. If used, the amount of solvent is not critical and may be up to 0.5% by weight based on the weight of the starting materials (A), (B) and (C) above.

[0024] The starting material used in step 1) may optionally further contain a (meth)acrylate polymerization inhibitor. Without being bound by theory, it is believed that the (alkyl)acrylate moieties in starting material (B) may polymerize under the conditions used in step 1). A polymerization inhibitor may be used in step 1) to minimize or eliminate undesired polymerization of the (alkyl)acrylate moieties. For example, starting material (B), an allyl (alkyl)acrylate, may be combined with a polymerization inhibitor before or during step 1). The polymerization inhibitor may be a conventional (meth)acrylate polymerization inhibitor, such as hydroquinone (HQ), hydroquinone methyl ether (MEHQ); a sterically hindered hydrophenol such as 2,6-di-tert-butyl-4-methylphenol (also known as butylated hydroxytoluene, BHT); and / or a sterically hindered quinone such as di-tert-butylhydroquinone. Such polymerization inhibitors are known in the art and commercially available. The amount of polymerization inhibitor varies depending on various factors, including the amount of rhodium catalyst and the temperature selected for step 1), but the amount may be 0.0001:1 to 0.1:1 (parts by weight of inhibitor: parts by weight of starting material (B)).

[0025] The inventors have surprisingly found that when silyl hydrides and allyl(alkyl)acrylates are hydrosilylated using the rhodium catalysts described herein, beta hydride elimination occurs, propene is released, and products containing Si-O-C bonds (i.e., silyl ester compounds, branched isomers) are formed with greater than 99% selectivity. Without being bound by theory, the inventors believe that this reaction is independent of the rhodium source, while other metal sources (such as platinum) produce mixtures (low selectivity).

[0026] (D) Silyl ester compounds The product of step 1) of the methods described herein is a (D) silyl ester compound, which has at least one silyl group per molecule of the formula: [ka] (In the formula, R 4 is as defined above). For example, when the starting material (A) is an organohydrogensiloxane oligomer (A1), the silyl ester compound has a silicon-bonded group of the unit formula (D1): (R 1 3SiO 1 / 2 ) a (R 1 2nd Round 11 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 11 SiO 2 / 2 ) d (In the formula, R 1 and subscripts a, b, c, and d are as defined above, and R 11 is the expression: [ka] where R 4 When the starting material (A) is an organohydrogensiloxane oligomer of formula (A4) above, the (D) silyl ester compound may comprise a silyl ester compound of formula (D2): [ka] (In the formula, R 1 and R 4 is as above).

[0027] Alternatively, when the starting material (A) is a silane monomer of formula (A5) above, the silyl ester compound may be a silyl ester compound of formula (D3): R 11 SiR 1 3 (wherein, R 11 and R 1 is as defined above).

[0028] Method for preparing silyl ester protected products The silyl ester compound prepared in step 1) can be used as follows. The above method including step 1) may further include 2) combining the above (D) silyl ester compound with starting materials including an (E) organosilicon compound having at least one silicon-bonded hydrogen atom per molecule. Step 2) may optionally further include adding a (F) hydrosilylation reaction catalyst. The (F) hydrosilylation reaction catalyst may be an additional amount of the (C) rhodium catalyst used in step 1). Alternatively, the (F) hydrosilylation reaction catalyst added in step 2) may be different from the (C) rhodium catalyst used in step 1). In step 2), the silicon-bonded hydrogen atoms of starting material (E) and the unsaturated moiety (group R) of starting material (D) are reacted to form a silyl ester compound. 11 (G) a silyl ester protected product.

[0029] In step 2), the starting materials, including (D) and (E) (and (F), if present), can be combined by any convenient means, such as mixing. The starting materials can be combined in any order, but without being bound by theory, it is believed that, to control the reaction rate, the starting material, including the (E) organosilicon compound having at least one silicon-bonded hydrogen atom per molecule, can be in the reactor, and the starting material (D), a silyl ester compound, can be added thereto in a manner that controls the exothermic heat of the hydrosilylation reaction, for example, by metering in over time or by metering in portions after a time interval. If a starting material (F) hydrosilylation reaction catalyst is used, it can be combined with the (D) silyl ester compound in the reactor before adding the starting material (D) as described above. Without being bound by theory, if the (D) silyl ester compound is not purified after step 1), the starting material (D) for step 2) will be in a mixture with a residual amount of (C) rhodium catalyst, which can catalyze the hydrosilylation reaction of the alkenyl moiety of starting material (D) with the silicon-bonded hydrogen atoms of starting material (E) with or without a (F) hydrosilylation reaction catalyst different from the (C) rhodium catalyst used in step 1).

[0030] Step 2) can be carried out in the same reactor as step 1). Alternatively, step 2) can be carried out in a different reactor. Without being bound by theory, it is believed that this method provides the advantage that purification of the silyl ester compound prior to step 2) is not required. The silyl ester compound prepared in the reactor during step 1) can remain in the reactor and be used in step 2) without further purification. For example, step 2) can be carried out without removing the (C) rhodium catalyst and any unreacted (B) allyl(alkyl)acrylate. However, without being bound by theory, excessive use of one reactant can result in the formation of undesirable by-products. Therefore, to minimize or eliminate the formation of by-products, step 1) can be carried out at a molar ratio of (B):(A) of 1.01:1 to 1:1, or excess (B) allyl(alkyl)methacrylate can be removed prior to step 2).

[0031] The temperature in step 2) is not critical. Step 2) may be carried out at RT. Alternatively, step 2) may be carried out at a temperature up to 200° C. Step 2) may be carried out under inert conditions as described above for step 1).

[0032] (E) Organosilicon compounds having at least one SiH group per molecule The starting material (E) used in step 2) of the process described herein is an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule. The organosilicon compound (E) may be linear, branched, cyclic, resinous, or a combination thereof. Starting material (e) includes, but is not limited to, HR 15 2SiO 1 / 2 , R 15 3SiO 1 / 2 , H.R. 15 SiO 2 / 2 , R 15 2SiO 2 / 2 , R 15 SiO 3 / 2 , HSiO 3 / 2 and SiO 4 / 2In the above formula, each R 15 are independently selected from the group consisting of monovalent hydrocarbon groups free of aliphatic unsaturation and monovalent halogenated hydrocarbon groups free of aliphatic unsaturation. Monovalent hydrocarbon groups free of aliphatic unsaturation are exemplified by alkyl and aryl groups. Alkyl groups are exemplified by, but not limited to, 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), cyclopentyl, cyclohexyl, hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon groups of 6 or more carbon atoms. Aryl groups are exemplified by, but not limited to, cyclopentadienyl, phenyl, tolyl, xylyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, anthracenyl, and naphthyl. The monovalent halogenated hydrocarbon group suitable for R15 is a monovalent hydrocarbon group in which one or more hydrogen atoms bonded to a carbon atom are replaced with a halogen atom. Halogenated hydrocarbon groups include haloalkyl groups and haloaryl groups. Haloalkyl groups include fluorinated alkyl groups (e.g., trifluoromethyl (CF), fluoromethyl, trifluoroethyl, 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, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl), and chlorinated alkyl groups (e.g., chloromethyl, 3-chloropropyl, 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl). Alternatively, R 15 The alkyl and aryl groups in R 1 may be as described above.

[0033] Methods for preparing linear, branched, and cyclic organohydrogenpolysiloxanes suitable for use herein, such as the hydrolysis and condensation of organohalosilanes, are well known in the art. Methods for preparing organohydrogenpolysiloxane resins suitable for use herein are also well known in the art, as exemplified in U.S. Patent Nos. 5,310,843, 4,370,358, and 4,707,531.

[0034] Alternatively, the starting material (E) may have the unit formula (E1): (R 12 2HSiO 1 / 2 ) k (R 12 2SiO 2 / 2 ) i (R 12 HSiO 2 / 2 ) j (R 12 3SiO 1 / 2 ) (2-k) wherein the subscript i has an average value ranging from 0 to 1000, the subscript j has an average value ranging from 0 to 1000, and the subscript k is 0, 1, or 2, and the amount (k+j)≧1. 12 are independently 15 As described above for , is selected from the group consisting of alkyl groups, aryl groups, halogenated alkyl groups, and halogenated aryl groups.

[0035] Examples of polyorganohydrogensiloxanes of the starting material (E) include those represented by the formula (E2): [ka] (In the formula, R 12 and subscript i is as defined above. Alternatively, subscript i can be 0 to 150, alternatively 50 to 150, alternatively 75 to 125, or alternatively 100.

[0036] The starting material (E) polyorganohydrogensiloxane is a) α,ω-dimethylhydrogensiloxy-terminated polydimethylsiloxane, b) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), c) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane; d) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane); e) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane; f) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated polydimethylsiloxane; g) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), h) α-dimethylhydrogensiloxy, ω-trimethylsiloxy-terminated polymethylhydrogensiloxane; i) H(CH3)2SiO 1 / 2 Units and SiO 4 / 2 a resin consisting essentially of units; and j) exemplified by a combination of two or more of these.

[0037] Starting material (E), an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule, and starting material (D), a silyl ester compound, are used in step 2) of the process such that the relative molar amount of silicon-bonded hydrogen atoms in starting material (D) to silicon-bonded hydrogen atoms in starting material (E) is 1 or greater, i.e., a molar ratio of (D):(SiH in E) ≥ 1:1. Alternatively, (D):(SiH in E) may range from 5:1 to 1:1, alternatively from 2:1 to 1:1, alternatively from 1.8:1 to 1:1, alternatively from 1.1:1 to 1:1. Without being bound by theory, it is believed that a molar excess of starting material (D) relative to the silicon-bonded hydrogen atoms in starting material (E) can minimize unreacted SiH.

[0038] (F) Hydrosilylation reaction catalyst The starting material (F) is optional and is a hydrosilylation catalyst. Suitable hydrosilylation catalysts for use in step 2) of the method described herein are known in the art and commercially available. The starting material (F) may be a metal selected from the group consisting of platinum (Pt), rhodium (Rh), ruthenium (Ru), palladium (Pd), and iridium (Ir). Alternatively, the (F) hydrosilylation catalyst may comprise Pt metal. Alternatively, the (F) hydrosilylation catalyst may comprise a compound of the above metals, such as chloroplatinic acid (Speier's catalyst), chloroplatinic acid hexahydrate, platinum dichloride, chloridetris(triphenylphosphane)rhodium(I) (Wilkinson's catalyst), and combinations thereof. Alternatively, the (F) hydrosilylation catalyst may comprise a complex of the compound (above) with an alkenyl-functional organopolysiloxane, such as [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene][1,3-divinyl-1,1,3,3-tetramethyldisiloxane]platinum(0). Alternatively, the (F) hydrosilylation catalyst may comprise a compound and / or complex microencapsulated in a matrix or core-shell structure. Complexes of platinum with alkenyl-functional organopolysiloxanes include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex (Karstedt catalyst). These complexes may be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst may comprise a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex. Exemplary hydrosilylation catalysts are described in U.S. Patent Nos. 3,159,601, 3,220,972, 3,296,291, 3,419,593, 3,516,946, 3,814,730, 3,989,668, 4,784,879, 5,036,117, and 5,175,325, and European Patent No. 0 347 895(B). Microencapsulated hydrosilylation catalysts and methods for their preparation are known in the art, as exemplified in U.S. Patent Nos. 4,766,176 and 5,017,654.Platinum hydrosilylation catalysts are commercially available, for example, SYS-OFF™ 4000 catalyst and SYL-OFF™ 2700, available from Dow Silicones Corporation (Midland, Michigan, USA).

[0039] The amount of (F) hydrosilylation reaction catalyst may be sufficient to provide at least 0.1 ppm of Pt metal, based on the total weight of the starting materials, including (D), (E), and (F), used in step 2). Alternatively, the amount of starting material (F) may be sufficient to provide, on the same basis, at least 0.1 ppm of Pt metal, alternatively at least 1 ppm of Pt metal, alternatively at least 2 ppm of Pt metal, alternatively at least 3 ppm of Pt metal, or alternatively at least 10 ppm of Pt metal. At the same time, the amount of starting material (F) may be sufficient to provide up to 1000 ppm, alternatively at most 750 ppm, alternatively at most 600 ppm, alternatively at most 500 ppm, alternatively at most 250 ppm, or alternatively at most 100 ppm of Pt metal, based on the total weight of starting materials (D), (E), and (F).

[0040] (G) Silyl ester protected product In the method described herein, step 2) produces a (G) silyl ester protected product, which comprises a silyl ester moiety attached to an organosilicon moiety via a divalent hydrocarbon moiety. For example, the (G) silyl ester protected product has at least one silyl ester moiety of the formula (G1) per molecule: [ka] (In the formula, R 4 For example, when starting material (D) has formula (D2) above and starting material (E) has formula (E2) above, the silyl ester protected product formed in step 2) has the moiety of formula (G2): [ka] (In the formula, R 1 , R4 , R 12 and subscript i is as above).

[0041] Method for producing carboxy-functional organosilicon compounds The above method including steps 1) and 2) may further include 3) combining starting materials including the (G) silyl ester-protected product formed in step 2) and (H) water or an alcohol such as methanol or ethanol, thereby forming a carboxy-functional organosilicon compound. In step 3), the (G) silyl ester-protected product formed in step 2) is deprotected (desilylated), thereby releasing by-products including the carboxy-functional organosilicon compound and hydroxyl-functional silane monomers and / or siloxane oligomers. Step 3) can be carried out by any convenient means, such as mixing. The same reactor used in steps 1) and / or 2) above may be used. For example, water and / or alcohol may be added to the reactor after step 2). The temperature is not critical and may range from -20°C to 150°C. Step 3) may be carried out under the inert conditions described above for step 1). An acid may optionally be added during step 3). For example, para-toluenesulfonic acid may be added to facilitate the deprotection in step 3). A solvent such as tetrahydrofuran can also be optionally added during step 3. Suitable conditions for step 3) may be as described in U.S. Pat. No. 7,307,178 to Kiyomori et al., column 10, lines 18-41.

[0042] The method may optionally further comprise 4) recovering the carboxy-functional organosilicon compound formed in step 3). Step 4) may be carried out by any convenient means, such as stripping, distillation, and / or extraction. The method may optionally further comprise 5) recovering one or both of the (C) rhodium catalyst and the (F) hydrosilylation catalyst (if used). However, without being bound by theory, it is believed that step 5) is not required and can be eliminated, particularly when low levels of the (C) rhodium catalyst and / or the (F) hydrosilylation catalyst are used in the method (e.g., when catalyst levels are 15 ppm or less, or alternatively 10 ppm or less, of metal).

[0043] Carboxy-functional organosilicon compounds The above method requires at least one molecule of the formula [ka] (In the formula, R 4 (wherein R is as defined above) to produce a carboxy-functional organosilicon compound having silicon-bonded groups. Alternatively, the carboxy-functional organosilicon compound may be a polyorganosiloxane, such as a polydiorganosiloxane. For example, when the silyl ester-protected product of formula (G2) is used in step 3) of the process, the resulting carboxy-functional organosilicon compound has the formula: [ka] (In the formula, R 1 , R 4 , R 12 and the subscript i is as above). [Example]

[0044] These examples are provided to illustrate the invention to one of ordinary skill in the art and should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials used in the examples are listed in Table 1 below. [Table 1]

[0045] In this Example 1, 10 g of allyl methacrylate and 20 mg of BHT were added to a 250 mL two-neck flask. 17.6 g (1 molar equivalent) of HMTS was added to the addition funnel. A temperature probe was inserted into the other port of the flask, and the reaction mixture was then placed under N2 while being heated to 50°C. 100 μL of [Rh(COD)Cl]2 (0.025 M in toluene) was added, and then the addition of HMTS was initiated. After the addition was complete, the yield of the silyl ester was greater than 95%. 1 H NMR (CDCl3, ppm) 6.09 (1H), 5.57 (1H), 1.91 (3H), 0.25 (3H), 0.1 (18H). The NMR results confirmed that neither the linear isomer nor the propene hydrosilylation product was formed under the conditions of this Example 1.

[0046] In this Example 2, 10 g of allyl methacrylate and 20 mg of BHT were added to a 250 mL, two-neck flask. To the addition funnel, 9.22 g (1 molar equivalent) of triethylsilane was added. A temperature probe was inserted into the other port of the flask, and the reaction mixture was then placed under N2 while being heated to 50°C. 10 μL of [Rh(COD)Cl]2 (0.025 M in toluene) was added, and then the addition of triethylsilane was started. The reaction was heated for 2.5 hours, yielding 80% conversion of the silyl ester. 1 H NMR (CDCl3, ppm) 6.13 (1H), 5.59 (1H), 1.94 (3H), 1.01 (9H), 0.82 (6H). The NMR results confirmed that neither the linear isomer nor the propene hydrosilylation product was formed under the conditions of this Example 2.

[0047] In this Example 3, Example 1 was repeated, except that [Rh(DPPE)Cl] was used as the catalyst instead of [Rh(COD)Cl]. The reaction proceeded to a yield of greater than 95%. NMR results confirmed that neither linear isomers nor propene hydrosilylation reaction products were formed under the conditions of this Example 2.

[0048] The reaction schemes in Examples 1 and 2 were considered to be as follows: [ka]

[0049] In this Comparative Example 1, 30 g (1 equivalent) of allyl methacrylate and 50 mg of BHT were added to a two-neck flask. 53 g (1 equivalent) of HTMS was added to the dropping funnel. The contents of the flask were heated to 50°C using a heating mantle, and then 20 μL of Karstedt's catalyst (2% in xylene) was injected. The heating mantle was removed, and the reaction mixture was allowed to exotherm to 62°C. The temperature was maintained with air cooling until the addition of the HMTS was complete. Then, 1 A H NMR spectrum was taken. Heating was removed and the resulting reaction mixture was stirred overnight. Significant propene hydrosilylation also occurred. [Table 2]

[0050] Examples 1, 2, and 3 demonstrate that different rhodium catalysts produce the desired branched isomers (silyl ester compounds) with good selectivity and yield, even when different silyl hydrides are used. Comparative Example 1 demonstrates that platinum catalysts do not provide the desired selectivity and yield under the conditions tested. The catalyst in Example 3 is formed from the catalysts in Examples 1 and 2. Due to the similar reactivity in Examples 1 and 3, the ligands of these catalysts are believed to be less important in forming silyl ester compounds, with the choice of metal governing selectivity.

[0051] In this Comparative Example 2, Comparative Example 1 was repeated several times, each with a reaction time of 2 hours, except that methacrylic acid was used instead of the allyl(alkyl)acrylate described herein, a different silyl hydride, a different catalyst, and a different temperature. The starting materials, reaction temperatures, and results are shown in Table 3 below. [Table 3]

[0052] Table 3 shows that methacrylic acid (MA) cannot be directly hydrosilylated with silyl hydrides to produce silyl ester compounds (as in Examples 1-3) using the methods described herein. For each reaction with methacrylic acid, significant side reactions and / or low yields were observed.

[0053] In this Example 3, the protected silyl ester (abbreviated as MDM-MA in the scheme above) prepared as described above in Examples 1 and 2 was hydrosilylated as follows: 10 g of SiH-terminated PDMS was added to a 250 mL, two-neck flask. 2.41 g of MDM-MA (1.8 equivalents) was added to the addition funnel. A temperature probe was inserted into the other port of the flask, and the reaction mixture was then placed under N2 while being heated to 50°C. Next, 10 μL of 2% Karstedt's catalyst (dissolved in 98% xylene) was added at 50°C, and then the addition of MDM-MA was initiated. A slight exotherm was observed during the addition, with the temperature rising as high as 60°C. After the addition was complete, the heat was removed. NMR samples were collected after the addition. 1 H NMR indicated complete reaction of the olefin groups on MDM-MA. 13 C NMR showed that the silyl ester moiety was still intact in the resulting protected product (175 ppm). The reaction scheme for this Example 3 was believed to be as follows: [ka]

[0054] In this Example 4, the silyl ester protected product prepared in Example 3 was deprotected by heating in a 1:1 mixture of THF:siloxane and excess water at 50° C. for 16 hours. 13 C NMR showed a shift of the silyl ester at 175 ppm to 183 ppm (COOH). The reaction scheme for this Example 4 was thought to be as follows: [ka]

[0055] Industrial Applicability The present invention provides a novel method for preparing the above-described (D) silyl ester compound. The method may further comprise preparing a carboxy-functional organosilicon compound using the silyl ester compound. This method offers an advantage over previous methods for preparing carboxy-functional organosilicon compounds in that steps 1), 2), and 3) can all be performed in the same reactor. Furthermore, an intermediate purification step between steps 1) and 2) (e.g., to remove rhodium catalyst and / or unreacted allyl(alkyl)methacrylate) or between steps 2) and 3) is not required. Furthermore, due to the low catalyst loading effective in this method, a catalyst recovery step is not required.

[0056] This process offers the additional benefit of minimizing the formation of by-products. Without being bound by theory, it is believed that an alkene such as propene is formed as a by-product in step 1), as illustrated in the reaction schemes shown above for Examples 1 and 2. However, propene is relatively easily removed and is not hydrogenated (to a by-product by reaction with (A) silyl hydride, which would adversely affect the yield and stoichiometry of the processes described herein) under the conditions used in step 1) of the processes described herein.

[0057] Definitions and Use of Terms The Summary and Abstract are incorporated herein by reference. All amounts, ratios, and percentages are by weight unless the context of the specification dictates otherwise. The articles "a," "an," and "the" each refer to one or more unless the context of the specification dictates otherwise. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in Sections §2111.03 I, II, and III of the Manual of Patent Examining Procedure, Ninth Edition, Revision 08.2017, Last Revised January 2018. Abbreviations used herein have the definitions in Table 4. [Table 4]

[0058] Test Method- 1 H NMR A single pulse excitation was applied to observe the 1H NMR response. Measurements were performed at 400 MHz or 600 MHz 1H NMR frequencies. The prepulse relaxation time (d1) was greater than 10 seconds, and the postpulse observation (aq or at) was greater than 2 seconds. Data were acquired on an Agilent MR400 or Bruker Avance III HD console. 13 C NMR

[0059] A single pulse excitation was applied to observe the 1H NMR response. Measurements were performed with 13C{1H} NMR at a frequency of 125 MHz. The prepulse relaxation time (d1) was 3 seconds. Postpulse observation (aq or at) was greater than 2 seconds. Data were acquired on an Agilent MR400 or Bruker Avance III HD console.

[0060] The present invention has been described in an illustrative manner, and it should be understood that the terminology used is intended to be in the nature of descriptions rather than limitations. With respect to any Markush group on which the description of individual features or aspects herein relies, different, particular, and / or unexpected results may be obtained from each element of the respective Markush group, independently of all other elements of the Markush group. Each element of a Markush group may be relied upon individually and / or in combination to provide appropriate support for particular embodiments within the scope of the appended claims.

[0061] Furthermore, any ranges and subranges relied upon in describing the present invention are understood to be independently and inclusively within the scope of the appended claims and to describe and contemplate the entire range encompassing all and / or partial values ​​therein, even if such whole and / or partial values ​​are not expressly set forth herein. Those skilled in the art will readily recognize that the recited ranges and subranges fully describe and enable various embodiments of the present invention, and that such ranges and subranges may be further delineated into related halves, thirds, quarters, fifths, etc. As merely an example, the range "50-80" may be further delineated as the lower third, i.e., 50 to 60, the middle third, i.e., 60 to 70, and the upper third, i.e., 70 to 80, which are individually and collectively within the scope of the appended claims and may individually and / or collectively be relied upon and provide appropriate justification for specific embodiments within the scope of the appended claims. Furthermore, with respect to words defining or modifying ranges, such as "at least," "greater than," "less than," "less than," etc., such words should be understood to include subranges and / or upper or lower limits.

[0062] Embodiments of the present invention In a first embodiment, a method for producing a silyl ester compound comprises: 1) a starting material, (A) silylhydride-functional silane monomers and / or silylhydride-functional siloxane oligomers; Formula (B) [ka] (In the formula, R 4 is selected from the group consisting of hydrogen and alkyl groups of 1 to 8 carbon atoms), and (C) combining the starting materials, including a rhodium catalyst in an amount sufficient to provide 0.0000001 mole % to 10 mole % of rhodium metal based on the amount of silyl hydride in the starting material (A), thereby producing (D) a silyl ester compound.

[0063] In a second embodiment, in the method of the first embodiment, the starting material (A) is a compound having the unit formula (A1): (R 1 3SiO 1 / 2 ) a (R 1 2HSiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 HSiO 2 / 2 ) d (In the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 8 carbon atoms and halogenated alkyl groups of 1 to 8 carbon atoms, subscript a is 0 to 2, subscript b is 0 to 2, the amount (a+b)=2, subscript c≧0, subscript d≧0, the amount (b+d)=1, and 4≧(a+b+c+d)≧2.

[0064] In a third embodiment, in the method of the second embodiment, subscripts a=2, d=1 and b=c=0, and starting material (A) has the formula: [ka] (In the formula, R 1 is as defined above).

[0065] In a fourth embodiment, in the method of the first embodiment, the starting material (A) is selected from the group consisting of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3,3-pentamethyldisiloxane, and combinations thereof.

[0066] In a fifth embodiment, in the method of the first embodiment, the starting material (A) is a compound of the formula: HSiR 1 3 (in the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms.

[0067] In a sixth embodiment, in the method of the fifth embodiment, the starting material (A) is selected from the group consisting of trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, trihexysilane, trioctylsilane, and combinations thereof.

[0068] In a seventh embodiment, in the method of the first embodiment, the starting material (B) comprises allyl (meth)acrylate.

[0069] In an eighth embodiment, in the method of the first embodiment, the starting material (C) comprises a rhodium diphosphine complex.

[0070] In a ninth embodiment, in the method of the eighth embodiment, the rhodium diphosphine complex is represented by the formula (C1): {[(R 8 2P)R 7 (R 8 2P)]Rh(μ-R 9 )}2(In the formula, each R 7 are independently selected divalent hydrocarbon groups, and each R 8 are independently selected monovalent hydrocarbon groups, and each R 9 are independently selected negatively charged bridging ligands, and each R 10 are independently selected anions).

[0071] In a tenth embodiment, in the method of the ninth embodiment, the rhodium diphosphine complex is selected from the group consisting of [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium and [1,2-bis(diethylphospino)ethane]dichlorodirhodium, and combinations thereof.

[0072] In an eleventh embodiment, in the process of the first embodiment, the starting material (C) comprises a rhodium complex that does not contain a phosphine ligand.

[0073] In a twelfth embodiment, in the method of the eleventh embodiment, the starting material (C) is (C3): [R 5 h Rh]R 10 , (C4): [Rh(R 5 ) h (uR 9 ) f ] g (The subscript h is 1 to 4, and each R 5 are independently selected from the group consisting of 1,5-cyclooctadiene ligands, 2,5-norbornadiene ligands, ethylene ligands, cyclooctene ligands, and acetylacetonate ligands; R 10 is an anion and R 9 is a negatively charged bridging ligand, the subscript f is 1 or 2, and each R 6 is a ligand that can be activated away from the complex, and subscript g is 1 or 2), or (C5) a combination of both (C3) and (C4).

[0074] In a thirteenth embodiment, in the method of the twelfth embodiment, the starting material (C) comprises rhodium 1,5-cyclooctadiene chloride dimer.

[0075] In a fourteenth embodiment, in the method of the first embodiment, combining the starting materials in step 1) includes heating at a temperature of 50°C to 60°C and mixing the starting materials.

[0076] In a fifteenth embodiment, the method of the first embodiment comprises administering to the subject a compound of formula: [ka] (In the formula, R 4 is as defined above) to produce a silyl ester compound having a silicon-bonded group.

[0077] In a sixteenth embodiment, in the method of the fifteenth embodiment, the silyl ester compound is a compound represented by the unit formula (D1): (R 1 3SiO 1 / 2 ) a (R 1 2nd Round 11 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 11 SiO 2 / 2 ) d (In the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms, subscript a is 0 to 2, subscript b is 0 to 2, the amount (a+b)=2, subscript c≧0, subscript d≧0, the amount (b+d)=1, and 4≧(a+b+c+d)≧2; R 11 is the expression: [ka] where R 4 is as above).

[0078] In a seventeenth embodiment, in the method of the sixteenth embodiment, the silyl ester compound prepared has the formula (D2): [ka] (In the formula, R 1 and R 4 is as above).

[0079] In an eighteenth embodiment, in the method of the fifteenth embodiment, the silyl ester compound prepared has the formula (D3): R 11 SiR 1 3 (in the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms; R 11 is an expression [ka] where R 4 is as above).

[0080] In a nineteenth embodiment, the method for producing a silyl ester protected product comprises: 1) a starting material, (A) silylhydride-functional silane monomers and / or silylhydride-functional siloxane oligomers; Formula (B) [ka] (In the formula, R 4 is selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms), and (C) combining the starting materials with a rhodium catalyst in an amount of 0.0000001 mole % to 10 mole % based on the weight of the silyl hydride starting material (A), thereby producing (D) a silyl ester compound; 2) (D) the silyl ester compound formed in step 1), (E) an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule; and and optionally combining starting materials with (F) a hydrosilylation reaction catalyst in an amount to provide 0 to 1,000 ppm metal, thereby producing (G) a silyl ester protected product.

[0081] In a twentieth embodiment, in the method of the nineteenth embodiment, (D) the silyl ester compound has at least one silyl ester of the formula: [ka] (In the formula, R 4 is selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms).

[0082] In a 21st embodiment, in the method of the 20th embodiment, the silyl ester compound is a compound represented by the unit formula (D1): (R 1 3SiO 1 / 2 ) a (R 1 2nd Round 11 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 11 SiO 2 / 2 ) d (In the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 8 carbon atoms and halogenated alkyl groups of 1 to 8 carbon atoms, subscript a is 0 to 2, subscript b is 0 to 2, the amount (a+b)=2, subscript c≧0, subscript d≧0, the amount (b+d)=1, and 4≧(a+b+c+d)≧2; R 11 is the expression: [ka] where R 4 is as above).

[0083] In a 22nd embodiment, in the method of the 21st embodiment, the silyl ester compound has the formula [ka] (In the formula, R 1 and R 4is as above).

[0084] In a 23rd embodiment, in the method of the 20th embodiment, the silyl ester compound has the formula: R 11 SiR 1 3 (in the formula, each R 1 is independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms; R 11 is the expression: [ka] where R 4 is as above).

[0085] In a twenty-fourth embodiment, the method for preparing a carboxy functional organosilicon compound comprises: 1) a starting material, (A) silylhydride-functional silane monomers and / or silylhydride-functional siloxane oligomers; Formula (B) [ka] (In the formula, R 4 is selected from the group consisting of hydrogen and alkyl groups of 1 to 8 carbon atoms), and (C) combining the starting materials with a rhodium catalyst in an amount of 0.000001 to 10 mole % based on the amount of silyl hydride in the starting material (A), thereby producing (D) a silyl ester compound; 2) (D) the silyl ester compound formed in step 1), (E) an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule; and optionally combining starting materials with (F) a hydrosilylation reaction catalyst in an amount providing 0 to 1,000 ppm metal, thereby producing (G) a silyl ester protected product; 3) combining starting materials including (G) the silyl ester protected product formed in step 2) with (H) water and / or alcohol, thereby producing a carboxy-functional organosilicon compound.

[0086] In a 25th embodiment, in the method of the 24th embodiment, (D) the silyl ester compound has at least one silyl ester per molecule of the formula: [ka] (In the formula, R 4 is as defined above).

[0087] In a 26th embodiment, in the method of the 25th embodiment, the silyl ester compound is a compound represented by the unit formula (D1): (R 1 3SiO 1 / 2 ) a (R 1 2nd Round 11 SiO 1 / 2 ) b (R 1 2SiO 2 / 2 ) c (R 1 R 11 SiO 2 / 2 ) d (In the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms, subscript a is 0 to 2, subscript b is 0 to 2, the amount (a+b)=2, subscript c≧0, subscript d≧0, the amount (b+d)=1, and 4≧(a+b+c+d)≧2; R 11 is the expression: [ka] where R 4 is as above).

[0088] In a 27th embodiment, in the method of the 26th embodiment, the silyl ester compound has the formula [ka] (In the formula, R 1 and R 4 is as above).

[0089] In a 28th embodiment, in the method of the 24th embodiment, the silyl ester compound has the formula (D3): R 11 SiR 1 3 (in the formula, each R 1 is independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms; R 11 is the expression: [ka] where R 4 is as above).

[0090] In a twenty-ninth embodiment, the method of the twenty-fourth embodiment further comprises 4) recovering the carboxy-functional organosilicon compound formed in step 3). The present application also relates to the following aspects: (1) 1. A method comprising the steps of: 1) (A) silylhydride-functional silane monomers and / or silylhydride-functional siloxane oligomers; Formula (B) [ka] (In the formula, R 4 is selected from the group consisting of hydrogen and alkyl groups of 1 to 8 carbon atoms), and (C) combining starting materials, including a rhodium catalyst in an amount of 0.0000001 mol % to 10 mol % based on the amount of starting material (A), thereby producing (D) a silyl ester compound. (2) The starting material (A) has the unit formula (A1): (R 1 3 SiO 1 / 2 ) a (R 1 2 HSiO 1 / 2) b (R 1 2 SiO 2 / 2 ) c (R 1 HSiO 2 / 2 ) d (In the formula, each R 1 are independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms, subscript a is 0 to 2, subscript b is 0 to 2, the amount (a+b)=2, subscript c≧0, subscript d≧0, the amount (b+d)=1, and 4≧(a+b+c+d)≧2. (3) The starting material (A) is a compound of the formula: HSiR 1 3 (In the formula, each R 1 are independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms and a halogenated alkyl group having 1 to 6 carbon atoms. (4) The method according to any one of (1) to (3) above, wherein the starting material (B) contains allyl (meth)acrylate. (5) The starting material (C) is a compound of the formula {[(R 8 2 P)R 7 (R 8 2 P)]Rh(μ-R 9 } 2 (In the formula, each R 7 are independently selected divalent hydrocarbon groups, and each R 8 are independently selected monovalent hydrocarbon groups, provided that R 8 may be bonded to form a heterocyclic group containing P, and each μ-R 9 The method according to any one of (1) to (4) above, comprising a rhodium diphosphine catalyst of the formula (I) where I is an independently selected negatively charged bridging ligand. (6) The starting material (C) is (C3)[Rh( 5 ) h (μ-R 9 )] 2 , (C4) [R 5 h Rh]R 10 (wherein the subscript h is 1 to 4, and each R 5 are independently selected from the group consisting of 1,5-cyclooctadiene ligands, 2,5-norbornadiene ligands, ethylene ligands, cyclooctene ligands, and acetylacetonate ligands; R 10 is the anion, μ-R 9 (C5) is a negatively charged bridging ligand, and a rhodium catalyst having a formula selected from the group consisting of a combination of both (C3) and (C4). (7) The method according to any one of (1) to (6), wherein the combining in step 1) includes heating at a temperature of 50°C to 60°C and mixing the starting materials. (8) 2) (D) the silyl ester compound formed in step 1); (E) an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule; and The method according to any one of (1) to (7), further comprising, optionally, combining starting materials with (F) a hydrosilylation reaction catalyst in an amount providing 0 to 1,000 ppm of metal, thereby producing (G) a silyl ester protected product. (9) 3) combining starting materials including (G) the silyl ester protected product formed in step 2) with (H) water and / or alcohol, thereby producing a carboxy-functional organosilicon compound. (10) 4) The method according to (9) above, further comprising recovering the carboxy-functional organosilicon compound formed in step 3).

Claims

1. 1. A method comprising the steps of: 1) (A) silylhydride-functional silane monomers and / or silylhydride-functional siloxane oligomers; (B) Formula 【Chemistry 1】 Allyl(alkyl)acrylates of the formula ４ is selected from the group consisting of hydrogen and alkyl groups of 1 to 8 carbon atoms, and (C) a rhodium catalyst in an amount of 0.0000001 mol % to 10 mol % based on the amount of the starting material (A); mixing the starting materials, thereby forming (D) a silyl ester compound; 2) (D) the silyl ester compound formed in step 1); (E) an organosilicon compound having at least one silicon-bonded hydrogen atom per molecule; and combining starting materials, optionally including (F) a hydrosilylation reaction catalyst in an amount providing 0 to 1,000 ppm metal, thereby producing (G) a silyl ester protected product; The rhodium catalyst is Formula {[(R 8 2 P)R 7 (R 8 2 P)]Rh(μ−R 9 )} 2 wherein each R 7 is an independently selected divalent hydrocarbon group, each R 8 is an independently selected monovalent hydrocarbon group, provided that two R 8 s may be joined to form a heterocyclic group containing P, and each μ-R 9 is an independently selected negatively charged bridging ligand; or Formula (C4): [R 5 h Rh] R 10 , Formula (C3): [Rh(R 5 ) h (μ−R 9 ) f ] g wherein subscript h is 1 to 4; each R 5 is independently selected from the group consisting of 1,5-cyclooctadiene, 2,5-norbornadiene, ethylene, cyclooctene, and acetylacetonate ligands; R 10 is an anion; R 9 is a negatively charged bridging ligand; f is 1 or 2; and g is 1 or 2; and (C5) a rhodium catalyst having a formula selected from the group consisting of a combination of both (C3) and (C4).

2. The starting material (A) has the unit formula (A1): (R １ ３ SiO １／２ ) ａ (R １ ２ HSiO １／２ ) ｂ (R １ ２ SiO ２／２ ) c(R １ HSiO ２／２ ) d (wherein, each R １ are independently selected from the group consisting of alkyl groups of 1 to 6 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms, subscript a is from 0 to 2, subscript b is from 0 to 2, the amount (a+b)=2, subscript c≧0, subscript d≧0, the amount (b+d)=1, and 4≧(a+b+c+d)≧2.

3. The starting material (A) is a compound of the formula: HSiR １ ３ (In the formula, each R １ are independently selected from the group consisting of alkyl groups of 1 to 8 carbon atoms and halogenated alkyl groups of 1 to 6 carbon atoms.

4. The method of claim 1 , wherein starting material (B) comprises allyl (meth)acrylate.

5. 2. The method of claim 1, wherein step 1) comprises heating at a temperature of 50°C to 60°C and mixing the starting materials.

6. (F) The method according to claim 1, wherein the hydrosilylation reaction catalyst is used.

7. 3) combining starting materials including (G) the silyl ester protected product formed in step 2) with (H) water and / or alcohol, thereby producing a carboxy-functional organosilicon compound.

8. 8. The method of claim 7 further comprising: 4) recovering the carboxy-functional organosilicon compound formed in step 3).

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