Process and catalyst composition for preparing organosilicon compounds via isomerization and hydrosilylation of internal olefins

Abstract

A process for producing organosilicon compounds is provided. The process involves isomerization and hydrosilylation starting from internal olefin compounds and silyl hydride compounds. A catalyst composition comprising a platinum hydrosilylation catalyst and an iridium(I) ligand complex can catalyze the isomerization and hydrosilylation reactions.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application asserts the interests of U.S. Provisional Patent Application No. 63 / 451,935, filed on 14 March 2023, pursuant to Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 451,935 is incorporated herein by reference.

[0002] (Field of Invention) Processes and catalyst compositions for preparing organosilicon compounds are disclosed. More specifically, the process includes isomerizing an internal olefin compound to form a terminal olefin compound, and hydrosilylation the terminal olefin compound to form a reaction product containing an organosilicon compound. [Background technology]

[0003] (Introduction) Typical industrial hydrosilylation catalysts, such as Speier and Karstedt catalysts, are generally known to hydrosilylate terminal olefins, but they exhibit significantly lower reactivity when hydrosilylating internal olefins. When hydrosilylating a mixture of terminal and internal olefins, unreacted internal olefins are discarded, potentially leading to inefficiency of the raw materials. While this difficulty can sometimes be mitigated by using high catalyst loads and high reaction temperatures to react the internal olefins, high catalyst loads are not cost-effective, and higher temperatures lead to increased power consumption, further reducing cost-effectiveness. Moreover, high catalyst loads and high temperatures can cause excessive side reactions that reduce quality and yield.

[0004] The steric aspects of the internal double bond and other factors influence the hydrosilylation reaction. Hydrosilylation of octa-1-ene with trichlorosilane using a Karstedt catalyst is fairly rapid, but significant isomerization of the double bond occurs, leading to the significant formation of the corresponding octa-2-ene. See, for example, Meister et al., "Platinum Catalysis Revisited-Unraveling Principles of Catalytic Olefin Hydrosilylation," ACS Catal. 2016, 6, 1274-1284.

[0005] There is an industry need for a process that provides organosilicon compounds via hydrosilylation with high yield and selectivity. [Overview of the project]

[0006] The catalyst composition comprises at least 0.5 ppm of a platinum hydrosilylation catalyst and at least 50 ppm of an iridium(I) complex. This catalyst composition is useful for catalyzing isomerization and hydrosilylation reactions. The catalyst composition can be used in a process for preparing organosilicon compounds, which is a process for preparing organosilicon compounds. 1) A) A-1) An olefin component containing an internal olefin compound, wherein the internal olefin compound is linear or branched, has at least 4 carbon atoms per molecule, and has at least 1 internal double bond per molecule. B) Silyl hydride compounds having at least one silicon-bonded hydrogen atom per molecule, and C) Catalyst composition This involves combining starting materials that include the above. [Modes for carrying out the invention]

[0007] The starting materials A) olefin components, B) silyl hydride compounds, C) catalyst compositions, and optionally D) solvents can be used in the process described above. These starting materials are described in detail below.

[0008] A) Olefin component The starting material (B) in the process described in this specification is an olefin component. The olefin component includes A-1) internal olefin compounds, and the internal olefin compounds are linear or branched, have at least 4 carbon atoms per molecule, and have at least 1 internal double bond per molecule. The internal olefin compound may be an internal olefin hydrocarbon. For example, the internal olefin hydrocarbon has the formula A-1-1):

[0009]

Chemical formula

[0010] Alternatively, A-1) the internal olefin hydrocarbon may be substituted with an oxygen atom. For example, the internal olefin compound may have the formula:

[0011] [ka] (In the formula, R 2 , R 4 , R 8 , and R 10The ether may be an alkenyl ether (as described above). For example, the ether is exemplified by ethyl-1-propenyl ether (cis, trans, or a mixture thereof), which is also available from Millipore Sigma.

[0012] The starting material A) in the process described herein may optionally further include, in addition to the A-1) internal olefin compound, an A-2) terminal olefin compound. The terminal olefin compound may be, for example, a terminal alkene having 2 to 16 carbon atoms per molecule. For example, octene may be provided as a mixture containing 1-octene along with one or more of 2-octene (cis, trans, or a mixture thereof), 3-octene (cis, trans, or a mixture thereof), and 4-octene (cis, trans, or a mixture thereof). Alternatively, the starting material A) may include a mixture of terminal and internal octene from a process used to produce linear low-density polyethylene (LLDPE). The starting material A-1) may be 100% by weight of the starting material A), i.e., the A-2) terminal olefin compound is optional and may be 0 in amount. Alternatively, the starting material A) may contain 99% to 100% by weight of the A-1) internal olefin compound, or less than 99% to 100% by weight of the A-1) internal olefin compound. Alternatively, the starting material A) may contain more than 1% by weight of the terminal olefin compound when a by-product from a process such as an LLDPE production process is used herein. For example, in a by-product from LLDPE production, the weight ratio of the A-1) internal olefin compound to the A-2) terminal olefin compound may be in the range of 1.2 / 1 to 1 / 1.2, or 1.1 / 1 to 1 / 1.1, or 1 / 1.

[0013] The amount of the olefin component of starting material A) depends on various factors, including the selection and amounts of starting materials A) and B), the alkenyl content of starting material A), and the silicon-bonded hydrogen content of starting material B). However, the amounts of the olefin component of starting material A) and the silyl hydride compound of starting material B) can be selected such that the molar ratio of silicon-bonded hydrogen atoms from the silyl hydride compound B) to the double bonds in the olefin component A) (B / A molar ratio) can be 100 / 1 to 1 / 100, or 5 / 1 to 1 / 5, or 1 / 1 to 1 / 5, or 3 / 1 to 1 / 3, or 1 / 1.

[0014] B) Silyl hydride compounds In the process described herein, starting material B) is a silyl hydride compound. The silyl hydride compound may be B-1) silane or B-2) polyorganohydrogensiloxane. Starting material B-1) silane is a compound of formula H x SiR 1 y X z (In the formula, each R 1 X is independently selected from the group consisting of aliphatic saturated monovalent hydrocarbon groups and aliphatic saturated monovalent halogenated hydrocarbon groups, each X is independently selected hydrolyzable substituent (e.g., halogen or alkoxy), the subscript x is an integer with a value of 1 to 3, the subscript y is an integer with a value of 0 to 3, and the subscript z = 4 - xy).

[0015] In the above formula, each R 1This is an aliphatic saturated monovalent hydrocarbon group or an aliphatic saturated monovalent halogenated hydrocarbon group. Suitable monovalent hydrocarbon groups include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl. Examples of suitable monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as 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; chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl and 2,3-dichlorocyclopentyl, and fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl and 3,4-difluoro-5-methylcycloheptyl. Each X may be a halogen atom exemplified by chlorine, fluorine, bromine, and iodine, or it may be chlorine. Alternatively, X is the expression OR 1 (In the formula, R 1 X may have the above characteristics. Alternatively, X may be an alkoxy such as methoxy or ethoxy. Examples of silanes suitable for starting material B) are exemplified by trichlorosilane of formula HSiCl3, dimethylchlorosilane of formula Me2HSiCl, trimethoxysilane of formula HSi(OMe)3, triethoxysilane of formula (HSiOEt)3, or methyldimethoxysilane of formula MeHSi(OMe)2, trimethylsilane of formula HSiMe3, or triethylsilane of formula HSiEt3.

[0016] Alternatively, the silyl hydride compound may contain an organohydrogensiloxane comprising two or more siloxane units selected from B-2) below:HR 1 2SiO 1 / 2 , R 1 3SiO 1 / 2 , HR 1 SiO 2 / 2 , R 1 2SiO 2 / 2 , R 1 SiO 3 / 2 , HSiO 3 / 2 , and SiO 4 / 2 However, this is conditional on each molecule containing at least one unit of silicon-bonded hydrogen atom. In the above formula, each R 1 The organohydrogensiloxane is independently selected from monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, which are free of aliphatic unsaturated groups and are as described above for starting material B-1). The organohydrogensiloxane may be linear, branched, cyclic, resinous, or a combination thereof. Alternatively, the organohydrogensiloxane may be linear or branched. Alternatively, the organohydrogensiloxane may be linear.

[0017] Starting material B-2) Organohydrogensiloxane has the unit formula (I): (R 3 3SiO 1 / 2 ) e (R 3 2HSiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 HSiO 2 / 2 ) h (R 3 SiO 3 / 2 ) i (HSiO 3 / 2 ) j (SiO 4 / 2 ) k (In the formula, each R 3 These are independently selected from the group consisting of aliphatic saturated monovalent hydrocarbon groups, aliphatic saturated monovalent halogenated hydrocarbon groups, and hydrolyzable substituents (monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups are R1 is as described above with respect to X, and the hydrolyzable substituent is as described above with respect to X), e, f, g, h, i, j, and k each represent the average number of units in the unit formula, e≧0, f≧0, g≧0, h≧0, i≧0, j≧0, k≧0, the quantity (f + g + j)≧1, and they may have values such that 2≦(e + f + g + h + i + j + k)≦10,000).

[0018] Alternatively, B-2) polyorganohydrogensiloxane may be of formula (II): (R 1 2HSiO 1 / 2 ) h (R 1 3SiO 1 / 2 ) i (R 1 2SiO 2 / 2 ) j (R 1 HSiO 2 / 2 ) k (where each R 1 is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups that do not contain aliphatic unsaturation and are as described above, and the subscripts h, i, j, and k represent the average number of each unit per molecule, and they may have values such that 0≦h≦2, 0≦i≦2, (h + i)=2, 0≦j<2000, 0<k<2000, 0<(j + k)<2000, and 2≦(h + k)≦2000). Alternatively, h may be 2, or i may be 0. Alternatively, h may be 0, or i may be 2. Alternatively, j may be 0 to 5, or 1 to 4, or 2 to 4, or 3 to 3.5. Alternatively, k may be 1 to 10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6. Alternatively, i and k may be zero, h may be two, and j may be 0 to 1000, or 0 to 500, or 0 to 250, or 0 to 100).

[0019] Alternatively, the starting material (B-2) organohydrogensiloxane may contain formula (III), formula (IV), or a combination of both, Formula (III) is R 13SiO(R 1 2SiO) t (R 1 HSiO) u SiR 1 3, Equation (IV) is R 1 2HSiO(R 1 2SiO )v (R 1 2SiO) w SiR 1 It is 2H.

[0020] In equations (III) and (IV) above, the average value of the subscript t is in the range of 0 to 2000, the average value of the subscript u is in the range of 2 to 2000, the average value of the subscript v is in the range of 0 to 2000, and the average value of the subscript w is in the range of 0 to 2000. 1 The above applies. Alternatively, the subscript t may be 0-1,000, or 0-500, or 0-250, or 0-100. Alternatively, the subscript u may be 2-1,000, or 2-500, or 2-250, or 2-100. Alternatively, the subscript v may be 0-1,000, or 0-500, or 0-250, or 0-100. Alternatively, the subscript w may be 2-1,000, or 2-500, or 2-250, or 2-100.

[0021] The starting material B-2) polyorganohydrogensiloxane is, a) Dimethylhydrogensiloxy-terminated polydimethylsiloxane, b) Dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), c) Dimethylhydrogensiloxy-terminated polymethylhydrosiloxane, d) Trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), e) Trimethylsiloxy-terminated polymethylhydrogensiloxane, f)H(CH3)2SiO 1 / 2 Units and SiO4 / 2 resins consisting essentially of units, and g) combinations thereof, are exemplified by.

[0022] Also, polyorganohydrogensiloxanes are commercially available and are available, for example, from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as HMS-H271, HMS-071, HMS-993, HMS-301 and HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301 (octyl functional), HPM-502 (phenyl functional), and HMS-HM271. Other polyorganohydrogensiloxanes include DOWSIL™ 6-3570 polymer, DOWSIL™ SH1107 fluid, XIAMETER™ MHX-11007 fluid, and XIAMETER™ OFS-5057 fluid, all of which are commercially available from Dow. Methods for preparing linear, branched, and cyclic organohydrogenpolysiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art; see, for example, U.S. Patent Nos. 3,957,713 to Jeram et al. and 4,329,273 to Hardman et al. Methods for preparing organohydrogenpolysiloxane resins suitable for use herein are exemplified, for example, in U.S. Patent Nos. 5,310,843, 4,370,358, and 4,707,531. Also, U.S. Patent No. 2,823,218 to Speier et al. discloses organohydrogensiloxane oligomers and linear polymers, such as 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3-pentamethyldisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, bis-trimethylsiloxy-terminated polymethylhydrogensiloxane homopolymer, bis-trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymer, and cyclic polymethylhydrogensiloxane.

[0023] The amount of starting material B) depends on various factors, including the selection and quantity of starting materials A) and B), the alkenyl content of starting material A), and the silicon-bonded hydrogen content of starting material B).

[0024] C) Catalyst composition The starting material C) is a catalyst composition comprising C-1) a platinum hydrosilylation catalyst and C-2) an iridium(I) complex. The iridium(I) complex may have at least one or at least two olefin moieties, which may be linked or separated. For example, the iridium(I) complex may have at least one ligand per molecule, for example, 1,5-cyclooctadiene or 2,5-norbornadiene. Alternatively, the iridium(I) complex may have two ligands per molecule, for example, cyclooctene or ethylene. Alternatively, the iridium(I) complex may have at least one ligand selected from the group consisting of 1,5-cyclooctadiene, cyclooctene, 2,5-norbornadiene, and ethylene. Alternatively, the catalyst composition C) may essentially consist of C-1) a platinum hydrosilylation catalyst and C-2) an iridium(I) complex. Alternatively, C) the catalyst composition may consist of C-1) a platinum hydrosilylation catalyst and C-2) an iridium(I) complex.

[0025] C-1) Pt Hydrosilylation Reaction Catalyst The starting material C-1) is a platinum hydrosilylation catalyst. The platinum hydrosilylation catalyst promotes the reaction between the alkenyl group in the starting material (A) olefin compound and the silicon-bonded hydrogen atom in the starting material (B) silyl hydride compound. The hydrosilylation catalyst contains platinum. The hydrosilylation catalyst may be (C1-1) a platinum metal, (C1-2) a platinum metal compound, for example, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, (C1-3) a complex of this compound with an alkenyl-functional organopolysiloxane, or (C1-4) a platinum compound microencapsulated in a matrix or core-shell structure. Examples of complexes between platinum and alkenyl-functional organopolysiloxanes include complexes between platinum and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane (Karstedt catalyst), and complexes between platinum and vinyldimethylsiloxane complexes such as the Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby complex). Alternatively, the hydrosilylation reaction catalyst may be the above-mentioned (C1-5) compounds or complexes microencapsulated in a resin matrix. The starting material (C1) may be homogeneous or heterogeneous, and may optionally have a support. Alternatively, the starting material (C1) may be homogeneous. Specific examples of platinum-containing catalysts suitable for use herein include chloroplatinic acid in either hexahydrate or anhydrous form, or platinum-containing catalysts obtained by a method comprising reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane, or the alkene-platinum-silyl complex described in Roy's U.S. Patent No. 6,605,734.These alkene-platinum-silyl complexes can be prepared, for example, by mixing 0.015 moles of (COD)PtCl2 with 0.045 moles of COD and 0.0612 moles of HMeSiCl2, where COD represents a Pt COD complex having an alkenyl-functionalized silylalkyl group, such as a cyclooctadienyl or other platinum complex containing a monoanionic ligand and optionally a neutral ligand, as disclosed in U.S. Patent No. 11,008,353 or No. 11,253,846 by Girolami et al. Other exemplary hydrosilylation catalysts include Speier's U.S. Patent No. 2,823,218, Ashby's No. 3,159,601, Lamoreaux's No. 3,220,972, Chalk et al.'s No. 3,296,291, Willing's No. 3,419,593, Modic's No. 3,516,946, and Karstedt's No. 3,814 This is described in Patent No. 730, Chandra's Patent No. 3,928,629, Lee et al.'s Patent No. 3,989,668, Lee et al.'s Patent No. 4,766,176, Lee et al.'s Patent No. 4,784,879, Togashi's Patent No. 5,017,654, Chung et al.'s Patent No. 5,036,117, and Brown's Patent No. 5,175,325, as well as in European Patent No. 0 347 895(A) by Togashi et al. Suitable hydrosilylation catalysts for the starting material (C-1) are commercially available, for example, SYL-OFF® 4000 catalyst and SYL-OFF® 2700 are available from The Dow Chemical Company (Midland, Michigan, USA).

[0026] Alternatively, the starting material (C-1) may be a platinum(0)-siloxane complex known in the art, for example, described in U.S. Patent No. 3,814,730, which is incorporated herein by reference. This complex is chemically bonded platinum and formula R m R' n R" o SiO (4-m-n-o) / 2(Where each R is an independently selected monovalent hydrocarbon group that does not contain aliphatic unsaturation, each R' is an independently selected monovalent aliphatic unsaturated hydrocarbon group, each R'' is selected from R' groups chemically bonded to platinum, subscript m is from 0 to 2, subscript n is from 0 to 2, subscript o is from 0.0002 to 3, and the amount (m + n + o) is from 1 to 3) may consist essentially of an unsaturated organosiloxane.

[0027] The platinum(0)-siloxane complex can be prepared by combining a platinum halide with an unsaturated organic silicon material of the formula R c R’ d SiO (4-c-d) / 2 (where R and R' are as defined above, subscript c has a value equal to 0 or more and 2 or less, subscript d has a value equal to 0.0002 or more and 3 or less, and the sum of c and d is equal to 1 or more and 3 or less). The platinum halide may be hexachloroplatinic acid or a metal salt such as NaHPtCl6·nH2O, KHPtCl6·nH2O, Na2PtCl6·nH2O, or K2PtCl6·nH2O. The complex can be made by contacting the unsaturated organic silicon material with the platinum halide to produce a mixture having a certain concentration of inorganic halogen, treating the resulting mixture to remove the available inorganic halogen, and recovering the complex.

[0028] Alternatively, the unsaturated organic silicon material has the formula:

[0029]

Chemical formula

[0030] Alternatively, the complex may be a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, for example, containing the following formula.

[0031] [ka]

[0032] The starting material (C-1) may be a single platinum hydrosilylation catalyst, or a combination of two or more of the above platinum hydrosilylation catalysts. Alternatively, the starting material C-1) may be a single platinum hydrosilylation catalyst, such as a Karstedt catalyst. The amount of C-1) platinum hydrosilylation catalyst used in this method depends on various factors, including the selection of starting materials A), B), and C-2), but the amount of C-1) platinum hydrosilylation catalyst is sufficient to catalyze the hydrosilylation reaction of SiH and alkenyl groups, or the amount of catalyst is sufficient to provide at least 0.5 ppm by mass, or at least 2 ppm by mass, or at least 10 ppm by mass, or at least 15 ppm by mass, or at least 20 ppm by mass, or at least 25 ppm by mass, or at least 30 ppm by mass of platinum metal, based on the total amount of starting materials A), B), and C) used in step (1) of the process described herein. At the same time, the amount of catalyst is sufficient to provide, on the same basis, a maximum of 500 ppm by mass, or a maximum of 250 ppm by mass, or a maximum of 200 ppm by mass, or a maximum of 150 ppm by mass, or a maximum of 100 ppm by mass, of platinum metal. Alternatively, the amount of starting material C-1) may be 0.5 ppm to 200 ppm, or 2 ppm to 150 ppm, or 10 ppm to 100 ppm, on the same basis.

[0033] C-2) Iridium(I)-ligand complex Iridium(I) ligand complexes are used in the catalyst compositions and processes described herein. Each iridium(I) ligand complex contains at least one neutral olefin ligand per molecule. For example, an iridium(I) ligand complex may contain at least one ligand from the group consisting of 1,5-cyclooctadiene ligand, cyclooctene ligand, 2,5-norbornadiene ligand, and ethylene ligand. The formula for an iridium(I) ligand complex is [Ir(R 5 ) b (R 6 ) c ] d (In the formula, the subscript b is either 1 or 2, R 5is a 1,5-cyclooctadiene ligand, a cyclooctene ligand, a 2,5-norbornadiene ligand, or an ethylene ligand, where the subscript c is 0, 1, or 2, and R 6 R is a ligand that can be activated from the complex at a temperature below the boiling point of the organohydrogensiloxane oligomer, and may have the subscript d (where d is 1 or 2). 6 Activation of R can be carried out by any convenient means, for example, heating at a temperature below the boiling point of the silyl hydride compound, adding a silver salt, or by photochemical or electrochemical means. 6 Suitable ligands include halogen atoms, beta-ketoester ligands, halogenated beta-ketoester ligands, alkoxy ligands, cyanoalkyl ligands, aryl ligands, and heteroaryl ligands. Suitable halogen atoms include bromine (Br), chlorine (Cl), and iodine (I). Alternatively, the halogen atom may be Cl. An example of a β-ketoester ligand is acetyl acetonate (acac). An example of a halogenated β-ketoester is hexafluoroacetylacetonate (hfacac). Examples of alkoxy ligands include methoxy, ethoxy, and propoxy. Alternatively, the alkoxy ligand may be methoxy. Suitable cyanoalkyl ligands include CH3CN, acetonitrile, and tetrahydrofuran (THF). Suitable aryl ligands include phenyl, benzyl, or indenyl. A suitable heteroaryl ligand is pyridine.

[0034] In the above formula, R 5 is a 1,5-cyclooctadiene ligand, a cyclooctene ligand, a 2,5-norbornadiene ligand, or an ethylene ligand. Alternatively, R 5The ligand may be selected from the group consisting of 1,5-cyclooctadiene ligand, cyclooctene ligand, and 2,5-norbornadiene ligand. Alternatively, R 5 R may be selected from the group consisting of 1,5-cyclooctadiene ligands and cyclooctene ligands. Alternatively, 5 C1) may be a 1,5-cyclooctadiene ligand. The iridium(I) complex may be homogeneous or heterogeneous, and may optionally have a support. Alternatively, the starting materials C1) and C2) may be on the same support. Alternatively, the starting material (C2) may be homogeneous.

[0035] Examples of suitable iridium(I) complexes are shown in Table 1 below. For example, complexes containing a 1,5-cyclooctadiene ligand are exemplified by, but are not limited to, [Ir(I)CODCl]2, Ir(I)CODacac, Ir(I)COD2BARF, [Ir(I)COD(OMe)]2, Ir(I)COD(hfacac), IrCOD(CH3CN)2BF4, Ir(I)COD(pyridine)PF6, Ir(I)COD(indenyl), and mixtures thereof, where COD represents a 1,5-cyclooctadiene group, BARF represents tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, acac represents acetylacetonate, and hfacac represents hexafluoroacetylacetonate. Suitable iridium(I) complexes containing cyclooctene ligands are exemplified by, but are not limited to, [Ir(COE)2Cl]2 (where COE represents a cyclooctene group).

[0036] The amount of C-2) iridium(I) complex is sufficient to isomerize the internal alkenyl groups to terminal alkenyl groups, or the amount of C-2) iridium(I) complex catalyst is sufficient to provide at least 25 ppm by mass, or at least 50 ppm by mass, or at least 55 ppm by mass, or at least 60 ppm by mass, or at least 65 ppm by mass, or at least 70 ppm by mass, based on the total amount of starting materials (A), (B), and (C) used in step (1) of the process described herein. At the same time, the amount of C-2) iridium(I) complex is sufficient to provide up to 500 ppm by mass, or up to 250 ppm by mass, or up to 200 ppm by mass, or up to 150 ppm by mass, or up to 100 ppm by mass, based on the same criteria.

[0037] D) solvent Starting material D) is an optional solvent that may be used to deliver one or more starting materials. The solvent may be added to facilitate the introduction of certain starting materials, such as silyl hydride compounds, such as when B) resins are used, and / or C) catalyst compositions. The solvents that may be used herein are those that help to fluidize the starting materials of the composition but do not react with the starting materials in an essential manner. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility refers to the fact that the solvent is sufficient to dissolve and / or disperse the starting materials. Volatility refers to the vapor pressure of the solvent.

[0038] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as DOWSIL® 200 Fluids and DOWSIL® OS Fluids, which are commercially available from The Dow Chemical Company and have a molecular weight of 0.5 to 1.5 cSt.

[0039] Alternatively, the solvent may include an organic solvent. The organic solvent may be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; or a combination thereof.

[0040] D) The amount of solvent depends on various factors, including the type of solvent selected and the amount and type of other starting materials selected for the composition. However, the amount of solvent may be in the range of 0.5% to 99.5% by weight, or 1% to 99% by weight, or 2% to 90% by weight, based on the total weight of the starting materials A), B), and C). The solvent may be added, for example, before and / or during step 1) to aid in mixing and delivery. All or part of the solvent may be optionally removed after step 1).

[0041] Process steps The above starting materials are used in the process of preparing organosilicon compounds. This process is 1) A) Olefin component, A-1) Internal olefin compounds, and Optionally, A-2) Terminal olefin compounds Contains olefin components, B) A silyl hydride having at least one silicon-bonded hydrogen atom per molecule, C) A catalyst composition, C-1) Platinum hydrosilylation reaction catalyst, and C-2) Iridium(I) complex and, Optionally, D) solvent and Step 1) involves combining the starting materials, the starting materials A), B), C), and D), and their amounts, as described above. Step 1) produces isomerization and hydrosilylation reaction products containing organosilicon compounds.

[0042] Step 1) of the process can be carried out by any convenient means, such as mixing the starting materials A), B), and C), and D), if present. Typically, components A) and B) are reacted in a vessel or reactor to prepare an organosilicon compound. When the reaction is carried out at high or low temperatures as described below, the vessel or reactor may be heated or cooled in any preferred manner, for example, via a jacket, mantle, exchanger, bath, or coil. The starting materials A), B), and C), and optionally (D), may be supplied to the vessel together or separately, or placed in the vessel in any order of addition and in any combination. For example, starting materials A) and C), and optionally D), may be added to the vessel, and starting material B), may be added to it all at once, or starting material B), may be measured into the vessel continuously or intermittently in two or more portions.

[0043] Alternatively, the starting materials A), B), and optionally D) may be combined first before addition, or added sequentially to the container, after which starting material C) may be added to the container containing starting materials A), B), and optionally D). Generally, the term “reaction mixture” as used herein generally refers to a mixture containing starting materials A), B), C), and optionally D) (for example, obtained by combining the starting materials as described above). Each component of the catalyst composition may be added simultaneously or sequentially in any order. Starting materials C-1) and C-2) may optionally be combined by mixing them with solvent D) before adding them to the container. Alternatively, one of starting materials C-1) and C-2) may be combined with solvent D).

[0044] The process in step 1) may further include stirring the reaction mixture. Stirring, when combined with the reaction mixture, can enhance the mixing and contact of the starting materials A), B), and C), and optionally D). Such contact can also be carried out 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 enhance the contact of starting materials A) and B) for forming a reaction product containing an organosilicon compound, and consequently the reaction (i.e., isomerization and hydrosilylation).

[0045] The process in step 1) may further include heating the reaction mixture. The temperature may be 50°C to 150°C or 60°C to 100°C, depending on various factors including the vapor pressure of the starting materials A) and B), and D) if present. Step 1) may be carried out under ambient atmosphere and pressure, or under a low-oxygen atmosphere where, for example, 1-2% is oxygen and the remainder is an inert gas such as nitrogen.

[0046] The processes described herein may optionally further include one or more additional steps. For example, the process may further include step 2): purifying the isomerization and hydrosilylation reaction products prepared in step 1) for example, to remove and / or recover unreacted starting materials. Purification may be carried out by any convenient means, such as optionally stripping and / or distillation under reduced pressure with heating, and / or azeotropic distillation with a solvent, filtration, and combinations thereof. Distillation conditions typically include (i) high temperature, (ii) reduced pressure, or (iii) both high temperature and reduced pressure. High temperature or reduced pressure is defined in comparison to room temperature and atmospheric pressure. As understood in the art, the number of trays used in any distillation may be optimized and may affect the proportion of organosilicon compounds to the distillate produced and / or recovery. Distillation may be continuous or batch and may involve the use of a solvent (e.g., hexane, or toluene, or other solvents as described above as starting material D) so that the distillation may be azeotropic distillation.

[0047] As used herein, purification of isomerization and hydrosilylation reaction products is typically defined as increasing the relative concentration of the organosilicon compound compared to other compounds combined with it (e.g., in the reaction product or its purified version). As understood in the art, purification may include removing other compounds from such combinations (i.e., reducing the amount of impurities / unreacted starting materials combined with the organosilicon compound in the isomerization and hydrosilylation reaction product), and / or removing the organosilicon compound itself from the combination. Any suitable technique and / or protocol for purification may be used. Examples of suitable purification techniques include distillation, stripping, evaporation, extraction, filtration, washing, partitioning, phase separation, adsorption, and chromatography. As understood by those skilled in the art, any of these techniques may be used in combination (e.g., sequentially) with any other technique for purifying isomerization and hydrosilylation reaction products. Regardless of the specific technology chosen, the purification of isomerization and hydrosilylation reaction products can be carried out sequentially (i.e., in-line) with the isomerization and hydrosilylation reactions themselves, and therefore can be automated. Alternatively, the purification may be an independent procedure applied to isomerization and hydrosilylation reaction products containing organosilicon compounds.

[0048] As a result of purifying the isomerization and hydrosilylation reaction products, organosilicon compounds and unreacted olefin components can be recovered. The process may optionally further include step 3): repeating the process and recycling the unreacted olefin components from step 1).

[0049] Process products The products prepared by the processes described herein include organosilicon compounds containing groups derived from starting material A) bonded to silicon atoms from starting material B). For example, organosilicon compounds of formula: R 7 x SiR 1 y X z (In the formula, the subscripts x, y, and z, and R1 And X is as described above, R 7 It may be an organically functional silane that may have an organic group. While not bound by theory, R 7 It is thought that R is formed by isomerizing the internal olefin compound A-1) to form a terminal olefin compound and then hydrosilylating it. For example, when a linear alkene is used as the olefin component A) in the above process, 7 is an n-alkyl group having at least 4 carbon atoms. For example, if the starting material A-1) is one or more of the above internal octenets, then R 7 is an n-octyl group. The product may be, for example, n-octyldimethylchlorosilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldimethoxysilane, n-octyltrimethylsilane, or n-octyltriethylsilane. Alternatively, when using a branched internal olefin hydrocarbon as the starting material A-1), R 7 It is branched. For example, R 7 This may be 2-methyl-2-butyl, 2,3-dimethyl-2-butyl, or other branched alkyl groups derived from the exemplary internal olefin hydrocarbons described above.

[0050] Alternatively, the organosilicon compound prepared by the above process may have any of the formulas described above for B-2) organohydrogensiloxane, where at least one silicon-bonded hydrogen atom is R as described above. 7 It can be replaced by: For example, if B-2) contains 1,1,3,3-tetramethyldisiloxane, the organosilicon compound is of formula: Me2R 7 SiOSiMe2R 7 It may contain. Alternatively, if B-2) contains 1,1,1,3,3-pentamethyldisiloxane, the organosilicon compound is of the formula: Me3SiOSiMe2R 7 It may contain. Alternatively, if B-2) contains 1,1,1,3,5,5,5-heptamethyltrisiloxane, the organosilicon compound has the unit formula MD R7M (in the formula, D R7 is, equation (MeR 7 SiO 2 / 2 ) represents a bifunctional siloxane unit, in which R 7 This may include (as defined above). Additional examples of organosilicon compounds that can be prepared by the processes described herein are listed below. [Examples]

[0051] The following examples are provided to those skilled in the art to illustrate the present invention and are not intended to limit the invention as described in the claims. The starting materials used in the examples are summarized in Table 1 below.

[0052] [Table 1-1]

[0053] [Table 1-2]

[0054] In this Reference Example 1, the samples were prepared as follows: The vials were placed on a heating block in a glove box. Olefin and SiH compounds were added to each vial, the catalyst was added, the vials were capped, and then heated. Next, the vials were heated to 60°C while stirring. After 1 hour and 4 hours at 60°C, each sample was analyzed. 1 The reaction was monitored using 1H NMR spectroscopy. The starting materials, amounts used, and results are shown in Table 2 below.

[0055] [Table 2]

[0056] The conversion rates in Table 2 are: 1 This refers to the amount of organosilicon compounds formed by isomerization and hydrosilylation reactions (conversion to the desired product) after 1 hour and 4 hours, respectively, as measured by 1H NMR spectroscopy.

[0057] Referring to the data in Table 2 above, Comparative Examples 1, 4, and 5, and Examples 3, 5-14, used the same olefin compound (2-octene) and silyl hydride compound (MD'M), respectively. These results demonstrate that not all iridium complexes (Comparative Examples 4 and 5) can be combined with the Karrstedt catalyst to provide improved reaction rates or yields (yields exceeding 20% ​​after 4 hours) under the tested conditions. Examples 5-14 show that the use of the Karrstedt catalyst in combination with Ir(I) complexes containing COD or COE Ir(I) fragments provides synergistic results with various pair ligands such as Cl, acac, or OMe.

[0058] Furthermore, Comparative Example 2 showed that when a Pt catalyst was used but an Ir catalyst was not, the yields at 1, 4, and 24 hours were low under the tested conditions. Comparative Example 1 showed that when an Ir catalyst was used but a Pt catalyst was not, the yields at 1, 4, and 24 hours were low under the tested conditions. Comparative Example 3 showed that when an insufficient amount of Ir catalyst was used in combination with a Pt catalyst, the yield remained low. Examples 1-6 used the same olefin component (2-octene), silyl hydride compound (MD'M), and catalyst (Karstedt catalyst and [Ir(COD)Cl]2) as Comparative Examples 1-3, but showed a significant improvement in yield compared to Comparative Examples 1-3 when the amounts of each catalyst were as described herein. These examples demonstrate that the combination of C-1) platinum hydrosilylation catalyst and C-2) iridium(I) complex in the amounts described herein produces an unexpected synergistic effect of improved yield.

[0059] In Examples 15-19, the catalyst system of the present invention was used to test various internal olefin compounds and silyl hydride compounds. Comparative Examples 6 and 7 used the same silyl hydride compounds and olefin components as in Example 15, and the results showed that the combination of platinum hydrosilylation catalyst (Karstedt catalyst) and Ir complex [Ir(COD)Cl]2) in the amounts specified herein resulted in improved yield and increased reaction rate in Example 15. Example 15, containing 10 ppm of each catalyst, achieved a yield of 52% after only 1 hour, compared to Comparative Example 7, which only reached a 16% yield after 1 hour and showed no increase in yield after 4 hours. Comparative Example 8 used the same silyl hydride compounds and olefin components as in Example 16, but Example 16 showed improved yield when 10 ppm of Karstedt catalyst and 100 ppm of [Ir(COD)Cl]2 were included. Comparative Example 9 and Example 17 used MD'M and 23DM2B, respectively, and in Example 17, the conversion rate was improved when 100 ppm of [Ir(COD)Cl]2 was included. Comparative Example 10 and Example 19 also used MD'M and 23DM2B, respectively, and in Example 19, the conversion rate was improved when 100 ppm of [Ir(COD)Cl]2 was included. These examples demonstrate that the combination of starting materials C-1) and C-2) in the amounts described herein is effective for the isomerization and hydrosilylation reactions of various olefin and silyl hydride compounds. Furthermore, the reactions in the examples proceeded faster than in the comparative examples using the same A) olefin compound and B) silyl hydride compound. [Industrial applicability]

[0060] The examples and comparative examples shown above demonstrate that the combination of the platinum hydrosilylation catalyst and iridium(I) complex used in the amounts specified herein yields unexpected benefits for the hydrosilylation of various internal olefins and silylhydride compounds, including improved raw material efficiency, increased yield, and / or increased reaction rate. While not bound by theory, this process also shows improved recyclability and circularity by reducing the amount of waste generated compared to processes involving only the hydrosilylation of terminal olefin compounds.

[0061] Definitions and Use of Terms All quantities, ratios, and percentages herein are based on weight unless otherwise specified. The articles “a,” “an,” and “the” each refer to one or more unless specifically indicated by the context of the specification. The singular form includes the plural form unless otherwise stated. The “Summary of the Invention” and the “Abstract” are incorporated herein by reference. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in sections §2111.03 I, II, and III of the “Manual of Patent Examining Procedure Ninth Edition,” Revision 08.2017, Last Revised January 2018. Any feature or aspect of the Invention may be used in combination with any other feature or aspect listed herein. Abbreviations used herein have their definitions in Table 3.

[0062] [Table 3]

Claims

1. A process for preparing organosilicon compounds, １） A) Olefin component, A-1) Internal olefin compounds that are linear or branched, have at least four carbon atoms per molecule, and have at least one internal double bond per molecule, and Optionally, A-2) a terminal olefin compound that is linear or branched, has at least four carbon atoms per molecule, and has at least one terminal double bond per molecule, comprising an olefin component, B) A silyl hydride compound having at least one silicon-bonded hydrogen atom per molecule, C) A catalyst composition, At least 0.5 ppm of C-1) platinum hydrosilylation catalyst, and Iridium(I) complex having at least one ligand containing one or more olefin moieties that are at least 25 ppm C-2) linked or separated. A catalyst composition containing and a starting material containing are combined, A process comprising generating isomerization and hydrosilylation reaction products containing the organosilicon compound.

2. A-1) The internal olefin compound is of formula A-1-1): 【Chemistry 1】 (where R ２ has the empirical formula -C ｐ H （２ｐ＋１） (where the subscript p ≥ 1), R ４ has the empirical formula -C ｑ H （２ｑ＋１） (where the subscript q ≥ 1), R ８ has the empirical formula -C ｒ H （２ｒ＋１） (where the subscript r ≥ 0), R １０ has the empirical formula -C ｓ H （２ｓ＋１） (where the subscript s ≥ 0), and the quantity (p + q + r + s) is 2 to 14), the process according to claim 1, comprising an internal olefin hydrocarbon.

3. The process according to claim 2, wherein the internal olefin hydrocarbon is selected from the group consisting of 2-octene, 4-octene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene.

4. A-2) The process according to claim 3, wherein the terminal olefin compound is present and 1-octene is included.

5. A-1) The internal olefin component is of formula: 【Chemistry 2】 (In the formula, R ２ This is empirical formula -C ｐ H （２ｐ＋１） (wherein the formula, the subscript p ≥ 1) and R ４ This is empirical formula -C ｑ H （２ｑ＋１） (wherein the formula, the subscript q ≥ 1) and R ８ This is empirical formula -C ｒ H （２ｒ＋１） (In the formula, the subscript r ≥ 0) and R １０ This is empirical formula -C ｓ H （２ｓ＋１） The process according to claim 1, comprising an alkenyl ether having (wherein the formula, the subscript s ≥ 0) and a quantity (p + q + r + s) between 2 and 14.

6. The process according to claim 6, wherein the alkenyl ether comprises ethyl-1-propenyl ether.

7. The process according to claim 1, wherein the silyl hydride compound is selected from the group consisting of B-1) silanes having at least one silicon-bonded hydrogen atom per molecule, and B-2) organohydrogensiloxanes.

8. B-1) The silane is of formula H ｘ SiR １ ｙ X ｚ (In the formula, each R １ The process according to claim 7, wherein is independently selected from the group consisting of aliphatic saturated monovalent hydrocarbon groups and aliphatic saturated monovalent halogenated hydrocarbon groups, each X is an independently selected hydrolyzable substituent, the subscript x is an integer having a value of 1 to 3, the subscript y is an integer having a value of 0 to 3, and the subscript z = 4 - x - y).

9. B-2) The polyorganohydrogensiloxane is of formula: (R １ ２ HSiO １／２ ) ｈ (R １ ３ SiO １／２ ) ｉ (R １ ２ SiO ２／２ ) ｊ (R １ HSiO ２／２ ) ｋ (In the formula, each R １ The process according to claim 7, wherein is independently selected from the group consisting of non-aliphatic unsaturated monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and the subscripts h, i, j, and k represent the average number of each unit per molecule and have values ​​such that 0 ≤ h ≤ 2, 0 ≤ i ≤ 2, (h + i) = 2, 0 ≤ j < 2000, 0 < k < 2000, 0 < (j + k) < 2000, and 2 ≤ (h + k) ≤ 2000.

10. C-1) The process according to any one of claims 1 to 9, wherein the platinum hydrosilylation catalyst is selected from the group consisting of Karstedt catalyst, Spieer catalyst, and platinum on a support.

11. C-2) The iridium(I) ligand complex is of the formula [Ir(R ５ ) ｂ (R ６ ) ｃ ] ｄ (In the formula, the subscript b is either 1 or 2, and each R ５ The ligand is independently selected from the group consisting of 1,5-cyclooctadiene ligand, cyclooctene ligand, 2,5-norbornadiene ligand, and ethylene ligand, and the subscript c is 0, 1, or 2, R ６ The process according to any one of claims 1 to 10, wherein is a ligand that can be activated from the complex at a temperature below the boiling point of the silyl hydride compound, and the subscript d is 1 or 2.

12. C-2) The iridium(I) ligand complex is chloro-1,5-cyclooctadiene iridium(I) dimer, 1,5-cyclooctadiene (acetylacetonate) iridium(I), bis(1,5-cyclooctadiene) iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl] borate, di-μ-methoxobis(1,5-cyclooctadiene) diiridium(I), chlorobis(cyclooctene) iridium(I) dimer, 1,5-cyclooctadiene (hexafluoroacetylacetonate) iridium(I), bis(acetonitrile)(1,5-cyclooctadiene) iridium(I) tetrafluoroborate, bis(pyridine)(1,5-cyclooctadiene) iridium(I) hexafluorophosphate, 【Transformation 3】 The process according to claim 11, selected from the group consisting of and mixtures thereof.

13. 2) Purify the isomerization and hydrosilylation reaction product containing the organosilicon compound, thereby recovering the organosilicon compound and unreacted olefin components. Optionally, 3) Repeat the above process and recycle the unreacted olefin component in step 1), The process according to claim 1, further comprising:

14. A catalyst composition suitable for isomerization and hydrosilylation reactions, At least 0.5 ppm of C-1) platinum hydrosilylation catalyst, and Iridium(I) complex having at least one ligand containing one or more olefin moieties that are at least 25 ppm C-2) linked or separated. A catalyst composition comprising the following.

15. C-1) The platinum hydrosilylation reaction catalyst is present in an amount of 0.5 to 500 ppm, C-2) The catalyst composition according to claim 14, wherein the iridium(I) complex has at least one ligand selected from the group consisting of 1,5-cyclooctadiene, cyclooctene, 2,5-norbornadiene, and ethylene, and the iridium(I) complex is present in an amount of 25 ppm to 500 ppm.

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