Synthesis of trichlorosilanes from tetrachlorosilanes and hydridosilanes

Abstract

The present invention relates to a method for the preparation of trichlorosilane (HSiCl3) which comprises the reaction of tetrachlorosilane (SiCl4) with a hydridosilane in the presence of a catalyst. [Selected Figure] Figure 1

Description

[Background technology]

[0001] Trichlorosilane is conventionally produced by treating powder metallurgy-grade silicon with hydrogen chloride at 300°C. Si + 3HCl -> HSiCl3 + H2

[0002] Yields of 80-90% can be achieved. This is an important intermediate in the production of solar silicon, where trichlorosilane is distilled in a complex process and decomposed into silicon, tetrachlorosilane, and hydrogen chloride on heated ultra-high purity silicon rods. 2HSiCl3 -> Si + SiCl4 + 2HCl

[0003] Trichlorosilane is also produced from tetrachlorosilane. 3SiCl4+Si+2H2->4HSiCl3(+H2SiCl2+HCl) Temperature T = 500°C (thermodynamically limited yield of 20%)

[0004] In the Bayer process, SiCl4 reacts with activated carbon or transition metals and barium supported on activated carbon as accelerators at T=600-900°C, resulting in a SiCl4 / HSiCl3 conversion rate of approximately 15%.

[0005] The reaction SiCl4 + H2 -> HSiCl3 + HCl requires temperatures exceeding 1000°C, has a conversion rate of approximately 20%, and consumes approximately 1.3 kWh / kg of energy for SiCl4 conversion (http: / / www.gtsolar.com).

[0006] Non-industrial procedures are described in the following scientific literature. a) Preparation of trichlorosilane from hydrogenation of silicontetrachloride in thermal plasma: W. Qingyou, C. Hanbin, L. Yuliang, T. Xumei, H. Zhijun, S. Shuyong, Y. Yongxiang, D. Xiaoyan, In: Inorganic Materials 2010, 46 (3), 251-254. (Yield of HSiCl3 is approximately 70% (maximum), average yield is approximately 60%, energy: approximately 3.2 kWh / kg for HSiCl3). b) Gas-Dynamicand Thermal Process in the Synthesis of Trichlorosilane by Hydrogen Reductionof Silicon Tetrachloride in a High-Frequency Discharge: RA Kornev, VAShaposhnikov, AM Kuz'min in: Russian Journal of Applied Chemistry2014, 87 (9), 1246-1250. c) Mechanism of the silicide-catalyzed hydrodehalogenation of silicon tetrachloride totrichlorosilane: H. Walter, G. Roewer, K. Bohmhammel, in: J. Chem. Soc. FaradayTrans. 1996, 92 (22), 4605-4608 (conversion rate approximately 15%, T=600℃). d) Hydrodehalogenation of Chlorosilanes in the Presence of Metal Silicides: Experimental Studies of Gas and Solid Phase Composition related toThermodynamic Calculations: K. Bohmhammel, G. Roewer, H. Walter. In: J. Chem.Soc. Faraday Trans. 1995, 91 (21), 3879-3882. e) Catalytic conversion of silicontetrachloride to trichlorosilane for a poly-Si process: JY Lee, WH Lee, Y.-Ki Park, HY Kim, NY Kang, KB Yoon, WC Choi, O-Bong Yang, in: Solar Energy Materials and Solar Cells 105 (2012) 142-147 (Use of carbon-based catalyst (metal-carbon composite catalyst in a continuous flow fixed-bed reactor), T approximately 650°C, yield HSiCl 38-20%). f) Base-catalyzed Hydrogenation of Chlorosilanes by Organotin Hydrides: U. Paetzold, G. Roewer in: Organosilicon Chemistry II, N. Auner, J. Weiss (editors), VCH1996, 55-62; J. of Organomet. Chem. 1996, 508, 147-152 (SiCl4 + Bu3SnH -> HSiCl3 + SiH4 (+H2SiCl2 + H3SiCl), where R4PCl and R4NCl are suitable catalysts for obtaining explosive SiH4). However, tin hydride is highly toxic and unsuitable for industrial applications.

[0007] Patent publications related to the production of trichlorosilane include, for example, US7442824 B2, US2008 / 0112875 A1, US2013 / 0216464 A1, US2016 / 0002052 A1, and US2017 / 0369325A1. [Overview of the Initiative]

[0008] Technical problems The conversion of SiCl4 to HSiCl3 in high yield and with easy preparation is economically necessary (B. Ceccaroli, O. Lohne, Handbook of photovoltaic Science and Engineering, Solar Grade Silicon Feedstock, Edited by A. Luque and S. Hegedus 2003, 167-172). The most desirable outcome is the selective monohydrogenation of SiCl4 to produce HSiCl3. However, reduction of SiCl4 with common reducing agents, such as LiH (W. Sundermeyer DE1080077B, 1957; W. Sundermeyer, LM Litz, Chemie-Ing.-Tech. 1965, 37, 14-18; HJ Klockner, M. Eschwey, Chem.-Ing.-Tech. 1988, 60, 815-821) and LiAlH4 (Hollemann-Wiberg, Handbuch der Anorganischen Chemie, 102. Auflage, Walter de Gruyter, Berlin, New York, 2007, p. 938), results in perhydrogenated SiH4 that quantitatively lacks selectivity for HSiCl3.

[0009] In the conventional process for producing HSiCl3, silicon reacts with gaseous HCl on a large scale in a direct process in a fluidized bed reactor at 300-450°C: Si + 3HCl -> HSiCl3 (80%) + SiCl4 (20%) + H2. Since the late 1970s, large quantities of SiCl4 have been formed and recovered as follows: Si + 3SiCl4 + 2H2 -> 4HSiCl3 (T=500°C, yield 20%).

[0010] According to direct synthesis, HSiCl3 is contaminated with electronically active impurities such as boron, phosphorus, and arsenic chlorides, along with trace amounts of hydrocarbons. When HSiCl3 deposition is performed to produce silicon and HCl in the Siemens process, only one-third of the silicon is converted to polysilicon, one-third is converted to SiCl4, and one-third is not converted by decomposition, leaving reactor exhaust gases still containing HCl. The formation of HSiCl3 depends on the quality of the silicon: industrial-grade silicon requires higher temperatures but produces more SiCl4 at the same time. Pure and high-purity silicon produces less SiCl4 but significantly increases the overall cost. At higher temperatures, H2SiCl2 is formed from the disproportionation of HSiCl3 (and results in SiCl4). Thus, silicon impurities catalyze SiCl4 formation. In summary, the technical process for producing semiconductor silicon is based on CVD (chemical vapor deposition) of chlorosilane or silane. Chlorosilane-based processes share a common consequence: only about 25% of the chlorosilane used is converted to the final silicon product, while 75% is converted to the by-product tetrachlorosilane (SiCl4). Since 75% of the world's ultra-high purity silicon production is based on the Siemens process using HSiCl3 as a starting material, profitably disposing of SiCl4 is a major economic factor, as most of it is converted to fumed silica (SiO2) by hydrolysis at high temperatures, thus reducing economic benefits (H. Jacob, Prax. Naturwiss. Chem. 1988, 37, 4; K. Bohmhammel, G.Roewer, H. Walter, J. Chem. Soc. Faradaytrans. 1995, 91, 3879-3882). To date, intensive efforts to convert SiCl4 to HSiCl3 have focused on developing processes for homogeneous vapor-phase hydrogenation at 1200°C and hydrogenation in the presence of metallurgical silicon at 600°C.Numerous studies have investigated the hydrogeno-dehalogenation of chlorosilanes in the presence of metal silicates (H. Walter, G. Roewer, K. Bohmhammel, J. Chem. Soc. Faraday Trans. 1996, 92, 4605-4608), but the reaction temperature for HSiCl3 recovery was high (approximately 600°C) and the yield was low (conversion rate SiCl4 / HSiCl3 4-7 mol%). The technically preferred reaction 3SiCl4 + Si + 2H2 -> 4HSiCl3 (+H2SiCl2 + HCl) is carried out at 500°C with a thermodynamically limited yield of 20%. In the Bayer process, SiCl4 reacts with activated carbon or transition metals and Ba (barium) supported on activated carbon as accelerators at temperatures between 600°C and 900°C, with a SiCl4 / HSiCl3 conversion rate of approximately 15%. The reaction SiCl4 + H2 -> HSiCl3 + HCl requires temperatures exceeding 1000°C, has a conversion rate of approximately 20%, and consumes approximately 1.3 kWh / kg of energy for SiCl4 conversion (http: / / www.gtsolar.com).

[0011] Therefore, there is a strong demand for an economically viable, energy-efficient process that selectively prepares trichlorosilane in high yield from readily available starting materials, proceeds at low temperatures, and allows for easy separation of trichlorosilane from by-products.

[0012] Description of the Invention The inventors have found that trichlorosilane can be prepared in high yield from tetrachlorosilane and hydridosilane, and that this process is energy-efficient, proceeds at low temperatures, and allows for easy separation of trichlorosilane from by-products.

[0013] The present invention provides a method for preparing trichlorosilane (HSiCl3), which includes the reaction of tetrachlorosilane (SiCl4) with hydridosilane in the presence of a catalyst.

[0014] In a preferred embodiment of the present invention, hydridosilane is of the following formula: R n SiXm H 4-n-m (1), and R o Si2X p H 6-o-p (2) Selected from the group consisting of, Here R is an organic group, X is a halogen or alkoxy, n is 0 to 3, preferably 1 to 3, more preferably 2. m is 0 to 2, preferably 0, and n+m=0 to 3, preferably 1 to 3, more preferably 2, o is 0 to 5, preferably 1 to 5. p is 0 to 5, preferably 0, and o + p = 1 to 5.

[0015] In formulas (1) and (2) above, R is preferably selected from an aromatic or aliphatic hydrocarbon group having up to six carbon atoms, preferably from a C1 to C6 alkyl group or a C2 to C6 alkenyl group, and more preferably from a C1 to C4 alkyl group.

[0016] The organic compounds of the organyl group R may be the same or different, and preferably R includes aromatic groups such as phenyl, tolyl, and / or aliphatic hydrocarbon groups, more preferably R is an alkyl group such as methyl, ethyl, n- or iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, iso-pentyl, sec-pentyl, n-, iso- or sec-hexyl, n-, iso- or sec-heptyl, n-, iso- or sec-octyl, and even more preferably R is an n-alkyl group or R is an alkenyl group.

[0017] More preferred groups R are selected from the group of Me = methyl, Et = ethyl, Vi = vinyl, n-Pr = n-propyl, i-Pr = isopropyl, allyl, t-Bu = tert-butyl, n-Bu = n-butyl, Hex = n-hexyl, Ph = phenyl, p-Tol = para-tolyl, Bz = benzyl, Mes = mesityl, or mixtures thereof. Most preferably, R is a methyl group.

[0018] X is a halogen atom, preferably chlorine or bromine, more preferably chlorine or an alkoxy group, such as C1 to C6 alkoxy, preferably methoxy or ethoxy, etc.

[0019] Preferably, the hydridosilane is selected from the group consisting of SiH4, H3SiCl, H2SiCl2, MeSiH3, Me3SiH, Me2SiH2, Et2SiH2, MeSiHCl2, Me2SiHCl, PhSiH3, Ph2SiH2, PhMeSiH2, iPr2SiH2, Hex2SiH2, tBu2SiH2, Me2Si(OEt)H, ViSiH3, ViMeSiH2, Me2HSi-SiHMe2, MeH2Si-SiH2Me, MeH2Si-SiHMe2, Me3Si-SiHMe2, Me3Si-SiH2Me, H3Si-SiH3, HSi2Cl5, preferably Me2SiH2.

[0020] The method according to the invention is carried out in the presence of a catalyst that promotes the selective reduction of SiCl4 to HSiCl3. The catalyst is preferably - R 1 4QZ, where R 1 is independently selected from hydrogen or an organo group (such as those described for R above), more preferably an aromatic group or an aliphatic hydrocarbon group, even more preferably an n-alkyl group, and most preferably an n-butyl group, Q is phosphorus, nitrogen, arsenic, antimony, or bismuth, and Z is a halogen, - a phosphine of the formula R 1 3P, where R 1This is as defined above, preferably an organyl group (such as those described for R above), preferably PPh3 or n-Bu3P. - Formula R 1 3N amine, here R 1 This is as defined above, preferably an organyl group (such as those described for R above), preferably n-Bu3N or NPh3. - N-heterocyclic amines, preferably non-N-substituted methylimidazoles such as 2-methylimidazole and 4-methylimidazole. - Alkali metal halides such as LiCl, and - Alkaline earth metal halides It is selected from the group consisting of the following.

[0021] In a preferred embodiment of the present invention, the method for preparing trichlorosilane is: Formula R 1 This was carried out in the presence of a 4QZ catalyst, where R 1 Q is an organyl group, more preferably an aliphatic hydrocarbon group, even more preferably an n-alkyl group, and most preferably an n-butyl group, where Q is phosphorus or nitrogen, and Z is chlorine.

[0022] A preferred catalyst is, - Quaternary ammonium or phosphonium compounds, - R 1 4PCl, here R 1 is a hydrogen or organyl group, which may be the same or different, more preferably an aromatic group or an aliphatic hydrocarbon group, even more preferably an n-alkyl group, and most preferably an n-butyl group, such as n-Bu4PCl. - R 1 4NCl, here R 1 is a hydrogen or organyl group, which may be the same or different, more preferably an aromatic group or an aliphatic hydrocarbon group, even more preferably an n-alkyl group, most preferably an n-butyl group, such as Bu4NCl, - Formula R 13P phosphine, here R 1 is hydrogen or an organyl group, preferably an organyl group, and preferably the phosphine is PPh3 or n-Bu3P. - Formula R 1 3N amine, here R 1 This is as defined above, preferably an organyl group, and preferably the amine is n-Bu3N or NPh3. - N-heterocyclic amines, preferably non-N-substituted methylimidazoles such as 2-methylimidazole and 4-methylimidazole, are preferred, as is the fact that the nucleophilicity at the nitrogen atom of such N-heterocyclic amines is not reduced by inductive or mesomeri interactions, and cyclic amides in particular are generally unsuitable as redistribution catalysts. - Alkali metal halides such as NaCl, KCl, and LiCl - Alkaline earth metal halides such as MgCl2 and CaCl2, It is selected from the group consisting of the following.

[0023] Furthermore, a combination of two or more types of catalysts can be used.

[0024] The most preferred redistribution catalyst is one with the general formula R 1 4PC1 or R 1 Selected from 4NCl compounds, where R 1 R is a hydrogen or organic group. 1 They may be the same or different, preferably R 1R is an aromatic group such as R mentioned above, for example, phenyl, tolyl, and / or an aliphatic hydrocarbon group, more preferably R is an alkyl group, for example, methyl, ethyl, n-, or iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, iso-pentyl, sec-pentyl, n-, iso-, or sec-hexyl n-, iso-, or sec-heptyl, n-, iso-, or sec-octyl, even more preferably R is an n-alkyl group, and most preferably the compound of general formula R4PC1 or R4NCl is n-Bu4PC1 or n-Bu4NCl.

[0025] A more preferred catalyst is triorganophosphine PR 1 Selected from 3, R 1 R is hydrogen or an organyl group such as R mentioned above, 1 R may be the same or different, and more preferably R 1 The catalyst is an alkyl, cycloalkyl, or aryl group as described above, and most preferably the organophosphine is PPh3 or n-Bu3P. A more preferred catalyst is triorganoamine NR 1 Selected from 3, R 1 R is preferably an organyl group, more preferably an alkyl group, and most preferably the triorganoamine is n-Bu3N or NPh3. Further preferred catalysts are N-heterocyclic amines, such as non-N-substituted methylimidazoles like 2-methylimidazole and 4-methylimidazole, most preferably 2-methylimidazole.

[0026] With respect to the molar ratio of catalyst to tetrachlorosilane, it is preferably in the range of about 0.0001 mol% to about 600 mol%, more preferably about 0.01 mol% to about 20 mol%, even more preferably about 0.05 mol% to about 2 mol%, and most preferably in the range of about 0.05 mol% to about 1 mol%.

[0027] Here, the molar ratio in percent is defined as follows: [n(molar amount of catalyst) / n(molar amount of tetrachlorosilane)] x 100.

[0028] In another preferred embodiment of the present invention, formula R 1 The compound of 4PCl is, formula R 1 3P and R 1 It is formed in situ from a compound of Cl, and here R 1 is either H or the organyl group defined above.

[0029] According to the present invention, R 1 4PCl or R 1 4NCl also depends on the combination of compounds in the reaction vessel where the reaction takes place, R 1 3P or R 1 3N and R 1 It can be formed in place from Cl.

[0030] In the present invention, n-Bu4PCl and n-Bu4NCl were found to be particularly effective catalysts.

[0031] In a particularly preferred embodiment, the present invention relates to a method for preparing trichlorosilane by reacting tetrachlorosilane with dimethylsilane.

[0032] In certain preferred embodiments, the present invention relates to a method for preparing trichlorosilane, comprising the reaction of tetrachlorosilane with dimethylsilane according to reaction formula (I) or (II). Me2SiH2+2SiCl4->2HSiCl3+Me2SiCl2(I) Me2SiH2+SiCl4->HSiCl3+Me2SiHCl (II)

[0033] Therefore, the molar ratio can be appropriately selected depending on whether the formation of Me2SiCl2 or Me2SiHCl, which are intermediates in the production of silicones and functionalized silicones, is preferred. Also in this particular process, the catalyst is preferably R as defined above. 1Selected from 4QZ, here R 1 Q is an organyl group, more preferably an aliphatic hydrocarbon group, even more preferably an n-alkyl group, and most preferably an n-butyl group, Q is phosphorus or nitrogen, and Z is chlorine, and most preferably the catalyst is selected from n-Bu4PCl and n-Bu4NCl.

[0034] Another particularly preferred embodiment of the present invention relates to the process of the reaction Me3SiH + SiCl4 -> Me3SiCl + HSiCl3.

[0035] The method for preparing trichlorosilane according to the present invention can be carried out in or without a solvent. When a solvent is used, the method of the present invention is preferably carried out in the presence of one or more solvents selected from ether solvents. According to the present invention, the ether solvent can be selected from ether compounds, preferably from the group consisting of linear and cyclic aliphatic ether compounds. In the present invention, the term "ether compound" means a compound containing an ether group -O-, particularly of formula R 2 -OR 3 This refers to any organic compound of which, where R 2 and R 3 R is independently selected from the organyl groups R described above. Preferably in the present invention, R generally represents an organyl group bonded to a silicon atom via a carbon atom, and the organyl groups may be the same or different. Preferably, the organyl group is optionally substituted, more preferably unsubstituted, and is selected from the group consisting of alkyl, aryl, alkenyl, alkynyl, alkaryl, aralkyl, alalkenyl, aralkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloaralkyl, cycloaralkenyl, and cycloaralquinyl, more preferably selected from alkyl, cycloalkyl, alkenyl, and aryl, and more preferably selected from methyl, vinyl, and phenyl, and most preferably R is a methyl group (abbreviated as Me herein).

[0036] Preferably, R 2 and R 3 R is a substituted or unsubstituted linear or branched alkyl or aryl group, which may have further heteroatoms such as oxygen, nitrogen, or sulfur. In the case of cyclic ether compounds, R 2 and R 3 The ether compound can optionally consist of substituted alkylene or arylene groups, which may have further heteroatoms such as oxygen, nitrogen, or sulfur. The ether compound may be symmetric or asymmetric with respect to substituents on the ether group -O-. A mixture of one or more ether compounds and one or more non-ether compounds can also be used as a solvent. Preferably, the one or more non-ether compounds forming the mixture with the one or more ether compounds are selected from solvents with lower polarity than the ether compounds used, and particularly preferably from aliphatic or aromatic hydrocarbons. In a more preferred embodiment of the method according to the present invention, the ether compound used as a solvent is selected from the group of linear, cyclic, or complexed ether compounds. In this specification, the linear ether compound is defined as the ether group R as defined above. 2 -OR 3 A compound containing the oxygen atom of the ether group, R 2 and R 3 There is no bond between the group and the other, for example, in a symmetric ether, R 2 =R 3 These include asymmetric ethers such as Et2O, n-Bu2O, Ph2O, or diisoamyl ether (i-Pentyl2O), as well as t-BuOMe (methyl t-butyl ether, MTBE) or PhOMe (methylphenyl ether, anisole). Cyclic ether compounds used as solvents are compounds in which one or more ether groups are contained in a ring formed by a series of atoms, such as tetrahydrofuran, tetrahydropyran, or 1,4-dioxane, which may be substituted with alkyl groups, for example. Linear ether compounds may also include multiple ether groups that form di, tri, oligo, or polyether compounds, where R 2 and R 3If it is a terminal group of the compound, it constitutes an organyl group, and if it is an internal group, it constitutes an alkylene or arylene group. In this specification, a terminal group is defined as any group linked to one oxygen atom that is part of an ether group, while an internal group is defined as any group linked to two oxygen atoms that are components of an ether group. Preferred examples of such compounds, but are not limited to these, are dimethoxyethane, glycol diethers (glimes), particularly diglyme or tetraglimes. In the sense of the present invention, the term “complex ether” is understood to be an ether compound as defined above that can complex a cation, preferably a metal cation, more preferably an alkali and alkali metal cation, even more preferably an alkali metal cation, and most preferably a lithium cation. Preferred examples of such complex ethers according to the present invention are glycol diethers (glimes), particularly diglyme, triglyme, tetraglim or pentaglime, or crown ethers, but are not limited to 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, and diaza-18-crown-6. The ether solvent is preferably selected from the group consisting of linear ethers, such as diethyl ether, di-n-butyl ether, complexed ethers, such as dimethoxyethane, diethylene glycol dimethyl ether (diglym), or tetraethylene glycol dimethyl ether (tetraglyme), alkylated polyethylene glycol (alkylated PEG), and cyclic ethers, such as dioxane, preferably 1,4-dioxane, 2-methyltetrahydrofuran, tetrahydrofuran, or tetrahydropyran. In a particularly preferred embodiment of the method according to the present invention, the ether compound is a high-boiling ether compound, preferably diglym or tetraglym. According to the present invention, the term "high-boiling ether compound" is defined as an ether compound as defined above, having a boiling point at 1.01325 bar (standard atmospheric pressure) preferably at least about 70°C, more preferably at least about 85°C, even more preferably at least about 100°C, and most preferably at least about 120°C.High-boiling ethers can facilitate the separation of desired products from reaction mixtures containing the solvent and residual starting materials. The products generally have lower boiling points than the starting materials, and these boiling points are also lower than those of the high-boiling ethers mentioned above. For example, while the boiling point of each HSiCl3 compound (at standard atmospheric pressure) is 32°C, a typical high-boiling ether compound, diglym, has a boiling point of approximately 162°C. By using a higher-boiling ether compound as the solvent, higher reaction temperatures can be utilized, simplifying the separation of desired products from the reaction mixture by distillation.

[0037] The method for preparing trichlorosilane according to the present invention is preferably carried out at a temperature in the range of about -40°C to about 250°C, more preferably in the range of about 0°C to about 200°C, and even more preferably in the range of about 25°C to about 150°C.

[0038] The method for preparing trichlorosilane according to the present invention is preferably carried out at a pressure of about 0.1 to about 10 bar, and preferably the reaction is carried out at approximately atmospheric pressure (about 10¹³ millibars).

[0039] The method of the present invention is preferably carried out under inert conditions. According to the present invention, the term “inert conditions” means that the process is carried out partially or completely with the ambient air, particularly moisture and oxygen, excluded. To exclude ambient air from the reaction mixture and reaction products, a sealed reaction vessel, reduced pressure and / or an inert gas, particularly nitrogen or argon, or a combination of such means may be used.

[0040] The method of the present invention can be carried out continuously or discontinuously, such as in a batch process.

[0041] In a preferred embodiment of the method according to the present invention, the chlorosilane formed from the obtained trichlorosilane and hydridosilane is separated from the reaction mixture by distillation. The term “distillation” in the sense of the present invention relates to any process for separating components or substances from a liquid mixture by selective evaporation and condensation. Among these, distillation may result in substantially complete separation, leading to the isolation of a nearly pure component, or it may be a partial separation that increases the concentration of a selected component in the mixture. The distillation process that may constitute separation step B) may be simple distillation, fractional distillation, vacuum distillation, short-pass distillation, or other types of distillation known to those skilled in the art. The step of separating the chlorosilane formed from the trichlorosilane and hydridosilane may include one or more batch distillation steps, or it may include a continuous distillation process.

[0042] A particular preferred process of the present invention further comprises the steps of hydrogenating the obtained chlorosilane to a hydridosilane of formula (1) or (2), and recycling the hydridosilane for a reaction with tetrachlorosilane.

[0043] For example, in a specific process for the preparation of trichlorosilane, preferably involving the reaction of tetrachlorosilane with dimethylsilane according to reaction formula (I) or (II), Me2SiH2+2SiCl4->2HSiCl3+Me2SiCl2(I) Me2SiH2+SiCl4->HSiCl3+Me2SiHCl (II) The resulting Me2SiCl2 or Me2SiHCl is separated, and at least part or all of it is hydrogenated to Me2SiH2, which is then reused in the reaction with tetrachlorosilane.

[0044] Preferably, the step of hydrogenating the chlorosilane is carried out using a hydrogenating agent selected from the group consisting of metal hydrides, preferably alkali metal hydrides such as LiH, NaH, KH, alkaline earth metal hydrides such as calcium hydride, or complex metal hydrides such as LiAlH4, NaBH4, n-Bu3SnH, (i-Bu2AlH)2, or sodium bis(2-methoxyethoxy)aluminum hydride. More preferably, the hydrogenating agent is selected from LiAlH4, LiH, CaH2, or LiH formed in situ by mixing LiCl and NaH, followed by heating the mixture to a temperature in the range of about 60°C to about 200°C.

[0045] Suitable hydrogenating agents generally include metal hydrides, among which are preferably selected from binary metal hydrides such as LiH, NaH, KH, CaH2 or MgH2, complex metal hydrides such as LiAlH4 or NaBH4, and organometallic hydride reagents such as n-Bu3SnH, i-Bu2AlH or sodium bis(2-methoxyethoxy)aluminum hydride. Alternatively, the hydrogenating agent may be selected from boron-containing hydride donors, more preferably from organohydridoborane, hydridoboranate, hydridoboronate and hydridoborate, and even more preferably from the corresponding boranate, boronate and borate which are the Lewis acid portion of a frustrated Lewis acid / Lewis base pair, as well as from hydridoboranate, hydridoboronate and hydridoborate produced from H2. The use of tin hydride is generally less preferred.

[0046] The most preferred hydrogenating agent is lithium hydride.

[0047] In preferred embodiments of the method according to the present invention, the amount of hydrogenating agent, particularly a metal hydride, preferably LiH, in the hydrogenation reaction involving the chlorosilane compound is in the range of about 1 mol% to about 600 mol%, preferably about 1 to about 400 mol%, more preferably about 1 to about 200 mol%, and most preferably about 25 to about 150 mol%, based on the total molar amount of chlorine atoms present in the chlorosilane compound.

[0048] As described above, the most preferred hydrogenation source is LiH, which is converted to lithium chloride (LiCl) in this reaction. In a particular preferred embodiment of such a process using lithium hydride, the formed LiCl is separated and subjected to a purification step, optionally mixed with KCl to prepare a LiCl-KCl eutectic composition, the eutectic or molten LiCl is electrolyzed to obtain metallic Li, and LiH is produced from the Li thus prepared.

[0049] A particular advantage of this embodiment is that it makes the method of the present invention economical and efficient, especially including the conversion reaction (Di->M2H), by recycling and valuing the accumulated LiCl and converting it back to LiH. Thus, the cost of the Li metal present in both components (LiH and LiCl) is excluded from the overall cost consideration, and only the conversion cost required to convert LiCl back to LiH is considered. Furthermore, recycling proceeds along the current production routes of LiH. In fact, the hydride material is made from LiCl in two consecutive steps: a) Li metal is produced by electrolysis of LiCl in the form of a eutectic system (KCl, Downs cell / process, etc.); followed by step b) LiH is produced by hydrogenation of the Li metal at high temperature using hydrogen gas (H2) (paraphrased): [ka] (Complete stoichiometry: 2LiCl -> 2Li + Cl2 2Li + H2 -> 2LiH).

[0050] Preferably, the hydrogenation reaction is carried out in the presence of one or more solvents, preferably selected from the ether solvents described above.

[0051] Therefore, a particularly preferred embodiment of the present invention relates to a method for preparing trichlorosilane, which is, A) Formula R 1Reaction of tetrachlorosilane and dimethylsilane according to reaction formula (I) or (II) in the presence of a 4QZ catalyst: Me2SiH2+2SiCl4->2HSiCl3+Me2SiCl2(I) Me2SiH2+SiCl4->HSiCl3+Me2SiHCl (II), Here R 1 is an organyl group, more preferably an aliphatic hydrocarbon group, even more preferably an n-alkyl group, and most preferably an n-butyl group, where Q is phosphorus or nitrogen, and Z is chlorine. B) Separating HSiCl3 from Me2SiCl2 or Me2SiHCl from the reaction mixture. C) Hydrogenating Me2SiCl2 or Me2SiHCl or a portion thereof with a hydrogenating agent selected from metal hydrides, preferably LiH, to form Me2SiH2, and D) Recycle Me2SiH2 to step A), Includes.

[0052] The method of the present invention enables the preparation of trichlorosilane with high selectivity. In particular, the selectivity for the formation of HSiCl3, as defined below: Molar amount of HSiCl3 formed / Formed silane hydride (ΣH 1-4 SiCl 0-3 (Here, the total number of hydrogen atoms and chlorine atoms is 4) × 100 Preferably, the hydrogen content is at least 90%, preferably at least 95%, and even more preferably 99%. That is, according to the method of the present invention, tetrachlorosilane selectively reacts to trichlorosilane without forming higher hydrogenated products such as H2SiCl2, H3SiCl, and H4Si.

[0053] Furthermore, the conversion rate in the method of the present invention is preferably at least 90%, preferably at least 95%, and more preferably at least 99%. In the present invention, the term "conversion rate" means, for example, that the conversion rate is 100% when Me2SiH2 reacts and all hydrogen atoms are used to form HSiCl3. If other monosilanes (such as Me2SiHCl) are also formed, the conversion rate decreases accordingly. The following example is for illustrative purposes: Example 1) Me2SiH2 + 2SiCl4 -> Me2SiCl2 + 2HSiCl3 corresponds to a 100% conversion rate. Example 2) 10Me2SiH2 + 20SiCl4 -> 5Me2SiCl2 + 15HSiCl3 + 5Me2SiHCl + 5SiCl4 (residual) -> 75% conversion rate (because 75% of all hydrogen atoms were used to form HSiCl3 and 25% were used to form Me2SiHCl). Example 3) 10Me2SiH2 + 20SiCl4 -> 10Me2SiHCl + 10HSiCl3 + 10SiCl4 (residual) -> 50% conversion rate, because only half of all the hydrogen atoms used were used to form HSiCl3.

[0054] Therefore, for a conversion rate of 100%, the hydridosilane used must be completely chlorinated to form HSiCl3 and must not retain any hydrogen atoms. Thus, the conversion rate is defined by the following formula: (Number of hydrogen atoms in the formed HSiCl3) / (Total number of hydrogen atoms used in the hydridosilane used) or (Number of hydrogen atoms in the hydridosilane used that led to the formation of HSiCl3) / (Total number of hydrogen atoms in the hydridosilane used), or otherwise (monosilane R 4-n SiH n (In this case) (Molar amount of HSiCl3 formed) / [(R used) 4-n SiH n (molar amount of) * n] (In the case of disilane, the formula must be adapted accordingly). Usually, a 100% conversion rate is desirable, but by working at a lower conversion rate, it is possible to form Me2SiHCl, which can be used, for example, in the formation of functionalized polysiloxanes.

[0055] In the method for preparing trichlorosilane according to the present invention, preferably the molar ratio of hydridosilane to tetrachlorosilane (SiCl4) is in the range of about 0.05 to about 2, preferably in the range of about 0.08 to about 1.5, more preferably in the range of about 0.09 to about 1, and most preferably in the range of about 0.1 to about 0.9.

[0056] In a preferred embodiment of the present invention for the preparation of trichlorosilanes, hydridosilanes are formed in situ from chlorosilane and LiH. In a preferred embodiment of this situ process, SiCl4 reacts with LiH. In such a process, it is assumed that SiH4 (formed in situ) reduces excess SiCl4 to selectively yield HSiCl3, while monosilane formation from SiCl4 and LiH (described in W. Sundermeyer, DE1080077, 1957; W. Sundermeyer, LM Litz, Chem. Ing. Tech 1965, 37, 14-18; HJ Klockner, M. Eschwey, Chem. Ing. Tech. 1988, 60, 815-821) yields a non-selective perhydrogenated silane.

[0057] Any numerical ranges listed herein are described in the examples or elsewhere in the specification and should be understood to include all subranges within that range, and any combination of various endpoints of such ranges or subranges.

[0058] Furthermore, it should be understood that each number mentioned herein may be subject to a certain degree of inaccuracy, and therefore each number should be associated with "approximately".

[0059] Any component of the present invention described herein by any particular genus or species detailed in the Examples section thereof may, in one embodiment, be used to define each of the alternatives to any endpoint of the range described elsewhere herein with respect to that component, and thus, in one non-limiting embodiment, may also be used to replace the endpoint of such range, as described elsewhere.

[0060] Any compound, material, or substance disclosed explicitly or implicitly in the specification and / or described in a claim as belonging to a group of compounds, materials, or substances that are structurally, compositionally, and / or functionally related includes individual representatives of that group and all combinations thereof. While the above description contains many details, these details should not be construed as limitations on the scope of the invention, but merely as examples of preferred embodiments. Those skilled in the art can envision many other possible variations that fall within the scope and spirit of the invention as defined by the claims appended herein. [Brief explanation of the drawing]

[0061] [Figure 1] Figure 1 shows the formation of HSiCl3 from Me3SiH (top, registration b in Table 2) and MeSiH3 (bottom, registration a in Table 2). [Figure 2] Figure 2 shows the formation of Me2SiCl2 (top, registered as e in Table 2) and Me2SiHCl (bottom, registered as g in Table 2) by the formation of HSiCl3 from Me2SiH2. [Examples]

[0062] The present invention can be further illustrated by the following examples, without limitation.

[0063] General To obtain organohydridosilanes as starting materials, conventional reducing agents such as metal hydrides MH or MH2 (M = alkali metal, alkaline earth metal), complex metal hydrides (LiAlH4, NaBH4, i-Bu2AlH, etc.), or mixtures thereof were used to convert chlorosilanes, particularly organochlorosilanes R3SiCl, R2SiCl2, and RSiCl3 (R = alkyl, aryl, alkenyl), in particular the corresponding organomono-, di-, and trihydridosilanes R3SiH, R2SiH2, and RSiH3, in ether as a solvent (e.g., diethyl ether, di-n-butyl ether, diglyme, 1,4-dioxane, or mixtures thereof). While the use of sodium hydride is preferable and attractive due to safety and economic considerations, it only reduces chlorosilane under harsh conditions such as high temperatures of approximately 250°C (AR Gilbert, GD Cooper, RW Shade, Industrial and Engineering Chemistry 51, 5, 665-668, 1959). On the other hand, lithium hydride (in diglym as a solvent) reduces chlorosilane in high yield under moderate conditions (AN Kornev, VV Semenov, Organomet.Chem. in the USSR 4 (4), 420-422, 1991). Considering the technically easy recycling of LiH from LiCl in KCl / LiCl melts, the use of lithium hydride for chlorosilane reduction is strongly supported.

[0064] Tetrachlorosilanes, used as reaction partners for organosilanes to obtain trichlorosilanes and organochlorosilanes, are a major byproduct of Siemens processes, including the production of trichlorosilanes from silicon metal and HCl, and are widely available on the market. The reaction was carried out by dissolving and mixing the reaction partner, i.e., hydridosilane (0.1 ml), and the required stoichiometric amount of SiCl4 in an excess of approximately 20-50 mol%, in diglyme (0.2-0.3 ml) and hydrogenation catalyst (1-3 wt%) in an NMR tube. After cooling the samples with liquid nitrogen (approximately -196°C), the tubes were evacuated under vacuum (approximately 0.1 mbar) and sealed to prevent loss of low-boiling point monosilanes such as Me2SiHCl (bp 35°C), MeSiHCl2 (bp 41°C), Me2SiH2 (bp -20°C), MeSiH3 (bp -58°C), HSiCl3 (bp 32°C), H2SiCl2 (bp 8°C), H3SiCl (bp -30°C), and SiH4 (bp ​​-112°C). The boiling point of SiCl4 is 57°C. The boiling point of Me2SiCl2 is 70°C (all bp at atmospheric pressure). NMR spectra were recorded according to reaction time and temperature. To compare catalytic activity, each sample was first subjected to NMR spectroscopy ( 29 Si and 1 The reaction conditions were analyzed by 1H NMR, either at room temperature for 8 hours or at 80°C for 2 hours. If the reduction of SiCl4 was not complete, the sample was further heated to achieve this (the experimental conditions for each experiment are shown in Table 2). The molar ratio of the formed products was determined by integrating the relevant NMR signals assigned to specific products in the mixture; the conversion rate SiCl4->HSiCl3 is defined as 100% if the organosilane R3SiH, R2SiH2, or RSiH3 is completely consumed (quantitatively chlorinated); if the compound R2SiHCl is formed, the maximum conversion rate is 50%.

[0065] After optimization and completion of the hydrogenation reaction SiCl4 + SiH -> HSiCl3 + SiCl, the NMR tube was opened and the product mixture was analyzed by GC-MS. Product identification was verified in all cases for the major product.

[0066] The amount of product formed can be estimated by the molar ratio measured by NMR spectroscopy and the amount of starting material applied.

[0067] The optimal reaction conditions were evaluated from NMR experiments, and the synthesis of HSiCl3 from tetrachlorosilane was carried out on a representative preparation scale using organosilanes Me2SiH2, Me3SiH, and PhSiH3 as hydrogen transfer reagents. Even on the preparation scale, to avoid evaporation of the compound, the reduction of tetrachlorosilane was carried out at high temperature (80°C) in a sealed glass ampoule. The NMR experiments and experiments in the sealed glass ampoule were carried out with a high-boiling point solvent such as diglym to reduce the overall pressure at high temperature. Polar ether solvents were not required, and non-polar solvents (benzene) did not affect the reaction process; the reduction of tetrachlorosilane to produce HSiCl3 also works without a solvent.

[0068] The glass ampoule had a length of 150 mm, an outer diameter of 50 mm, and a wall thickness of 2 mm (internal volume of approximately 200 ml). For high-boiling point organosilanes such as PhSiH3, the reaction can be carried out in an open system. This is illustrated in the following section.

[0069] Identification of compounds The product 1 H and 29 The spectra were analyzed by Si NMR spectroscopy. The spectra were recorded using a Bruker AV-500 spectrometer equipped with a ProdigyBBO 500S1 probe. 1 The 1H NMR spectrum shows the proton resonance of the residual solvent ([D6]benzene δ HCalibration was performed against (=7.16 ppm). Product identification was further supported by GC-MS analysis and verified identification of the major product. GC-MS analysis was performed using a ThermoScientific Trace GC Ultra in combination with an ITQ900MS mass spectrometer. The stationary phase (Machery-Nagel PERMABOND silane) had a length of 50 m and an inner diameter of 0.32 mm. 1 μl of the analyte solution was injected, and 1 / 25 of it was transferred to the column at a flow rate of 1.7 ml / min carried by helium gas. The column temperature was initially maintained at 50°C for 10 minutes. The temperature was then increased to 250°C at a rate of 20°C / min and held at that temperature for a further 40 minutes. After exiting the column, the substance was ionized at 70 eV, and the cation fragments were measured in the range of 34–600 m / z (mass per charge). Prior to measurement, the product mixture was diluted with benzene.

[0070] Starting material and the reaction product formed 29 SiNMR chemical shift and coupling constant 1 J 29 Si- 1 H} and 2 J 29 Si- 1 Table 1 shows the H} values. Spectroscopic and analytical data of the starting hydridosilane and the formed product are consistent with published values. Table 2 shows the distribution of tetrachlorosilane monohydrogenation, hydrogenation catalyst used, SiCl4->HSiCl3 conversion rate, and molar product, performed in a sealed NMR tube. [Table 1] [Table 2A] [Table 2B] *General conditions: Adding an excess of SiCl4 to the stoichiometric amount is suitable for complete conversion: approximately 20-50 mol%. If the conversion rate of SiCl4->HSiCl3 is not 100%, the sample was further heated to complete reduction (+ means in addition to the reaction conditions mentioned above). 1 The conversion rate SiCl4->HSiCl3 is based on the complete chlorination of the starting organic hydridosilane by monohydrogenation of SiCl4. In all cases, SiCl4 is selectively monohydrogenated to produce HSiCl3. In the case of organic hydridochlorosilane formation (e.g., R2SiH2 + SiCl4->HSiCl3 + R2SiHCl), the maximum conversion rate SiCl4->HSiCl3 is 50%. 2 Clearly, due to the steric requirements of the hexyl group, Hex2SiH2 does not react with SiCl4 under certain conditions. 3 Clearly due to the steric requirements of the t-butyl group, tBu2SiH2 reacts with SiCl4 only at 120°C, selectively producing tBu2SiHCl (SiCl4->HSiCl3 conversion rate: 50%). 4 The excess SiCl4 is almost completely consumed by a side reaction (ethoxychlorosilane formation). Only 1% of SiCl4 remains in the reaction mixture. X = unidentified compound.

[0071] As can be concluded from Table 2, the degree of monohydrogenation that selectively produces trichlorosilane from tetrachlorosilane is mainly accounted for by two factors: firstly, the steric requirements of the organic substituent at the silicon center of the monosilane with hydrogen as the transfer agent, and secondly, the hydrogenation activity of the catalyst investigated. Methyl-substituted hydridosilanes MeSiH3, Me2SiH2, and Me3SiH (registration ag) already initiate the hydrogenation of SiCl4 at room temperature (approximately 25°C), as described for Me2SiH2 (registration dg), showing a SiCl4 / HSiCl3 conversion rate of 40% to 80%, and finally reacting quantitatively at 80°C (100%). Experiments with registration dg) clearly show that the catalytic hydrogenation activity or possibility decreases in the order n-Bu4PCl ≈ n-Bu4NCl > n-Bu3P > n-Bu3N. This allows for experimentally simple reaction control, such as synthesizing hydridochlorosilane (R2SiHCl) separately from trichlorosilane (registered eg) at room temperature, or producing fully chlorinated methylsilane (registered ac) under moderate conditions (2 hours / 80°C). A series of experiments with eg clearly demonstrate that the chlorination of hydridosilane occurs stepwise. Notably, in none of the experiments was the formation of dichlorosilane H2SiCl2 by double hydrogenation of SiCl4 detected, indicating that the hydrogenation and dechlorination of tetrachlorosilane to produce trichlorosilane is highly selective. A similar trend has been recorded for diethylsilane, Et2SiH2 (registered hl), already indicating an increased steric requirement for the ethyl group compared to the methyl substituent: even after a reaction time of 26 hours at a reaction temperature of 80°C, Et2SiHCl was formed almost quantitatively under n-Bu3N catalysis (conversion rate SiCl4 / HSiCl3 54%, registered l), while Me2SiHCl was already formed from Me2SiH2 after 2 hours / 80°C (registered g). As expected, using n-Bu4NCl or n-Bu4PCl as catalysts yielded a 100% conversion rate with the dihydridosilane completely chlorinated (registered h and i).Considering the stepwise chlorination of methylsilanes (registers a, c, d) by tetrachlorosilanes, methylchlorosilanes MeSiHCl2 and Me2SiHCl were expected to quantitatively yield trichlorosilanes and their respective methylchlorosilanes under n-Bu4PCl catalysis—experimental evidence is shown in Table 2 (registers m and n). The steric requirements of vinyl and planar phenyl substituents on silicon are relatively low, and experiments did not show steric hindrance to SiCl4 / HSiCl3 conversion: phenylsilanes (register oq) and vinylsilanes (registers v and w) were completely chlorinated by SiCl4, resulting in a SiCl4 / HSiCl3 conversion rate of 100%. The increased steric requirements of isopropyl groups on silicon were convincingly demonstrated by iPr2SiH2, which yielded a SiCl4 / HSiCl3 conversion rate of 56% (2 hours / 80°C), mainly with iPr2SiHCl as its counterpart. A long reaction time of 32 hours yielded iPr2SiCl2 quantitatively (registered as r). The same was true for tBu2SiH2, which quantitatively produced tBu2SiHCl after 12 hours by starting the reaction only at 120°C (SiCl4 / HSiCl3 conversion rate 50%, registered as t). Furthermore, Hex2SiH2 showed no hydrogenation activity at all (registered as s), completely preventing the conversion of SiCl4 / HSiCl3. The highly sensitive ethoxy substituent of Me2Si(OEt)H caused a side reaction with excess tetrachlorosilane, producing ethoxychlorosilane (EtO) as a byproduct. n SiCl 4-n (n=1-3) was produced, but the SiCl4 / HSiCl3 conversion was 20% (Registered u). Experiment Registered x showed that excess SiCl4 is not required for monohydrogenation to produce HSiCl3 (conversion rate SiCl4 / HSiCl3 97% (Registered h) vs 93%, however, increased to 100% after 4 hours / 80°C). The main factor in product formation is determined by the stoichiometry of the reaction partners.

[0072] A) Synthesis of HSiCl3 from Me2SiH2 and SiCl4 on a preparation scale a) Synthesis of Me2SiH2 by reduction of Me2SiCl2 with LiH in THF 7.22 g (0.88 mol, 97%) lithium hydride (LiH) was placed in a 250 ml three-necked flask equipped with a dropping funnel, reflux condenser, and magnetic stirrer, and suspended in 100 ml of completely dry tetrahydrofuran (THF) under an inert nitrogen atmosphere. The THF / LiH suspension was carefully weighed from oxygen / air by degassing under vacuum and refilling with gaseous nitrogen to establish inert conditions. To the vigorously stirred suspension, 56.84 g (53.6 ml, 0.44 mol) of dimethyldichlorosilane (Me2SiCl2) was slowly added to the dropping funnel. Furthermore, the reduction of Me2SiCl2 was initiated by self-heating the solution to approximately 54°C after a 5-minute induction period. Dimethylsilane (Me2SiH2, bp: -20°C) was continuously formed, evaporated, and frozen in a cooling trap (-196°C) connected to the top of the reflux condenser. After the addition of Me2SiCl2 was complete (1 hour, final temperature 50°C), the mixture was subsequently heated under reflux for another hour (oil bath temperature 75°C) and then cooled to room temperature. To completely collect Me2SiH2 in a cooling trap, the reaction flask was subjected to vacuum and the product was pumped out. The Me2SiH2 in the cooling trap was separated from THF by cold distillation in 96% yield (25.4 g, 0.42 mol). The formed LiCl was separated in 36.05 g (96% conversion from LiH to LiCl, theoretical yield after 100% conversion: 37.56 g) by removing THF and the remaining silane under vacuum at 160°C, which is consistent with the amount of Me2SiH2 formed.

[0073] b) Synthesis of HSiCl3 A glass ampoule (length: 15 cm, inner diameter: 5 cm, wall thickness: 2 mm) was evacuated and then filled with gaseous nitrogen to create an inert atmosphere. Next, 96.6 g (0.57 mol) of SiCl4, 2.15 g (0.007 mol, 2 wt%) of n-Bu4PCl, and 43 ml (39.63 g) of diglym were packed into the ampoule, frozen at -196°C (liquid N2), and evacuated under vacuum. 13.58 g (0.23 mol) of Me2SiH2 was added by cold condensation. Subsequently, the ampoule was sealed, warmed to room temperature (25°C), and then heated to 80°C for 5 hours. After completion, the reaction mixture was frozen (-196°C), and the ampoule was opened under an inert atmosphere. The volatile products were condensed in a flask connected to a distiller connected to a Vigreux column (50 cm) and a cooling trap (-196°C) capable of collecting unreacted Me2SiH2. The distillation condenser was cooled to 8°C in a cryostat, and the flask receiving the product was cooled to -10°C (HSiCl3 b.p.: 32°C) to reduce the loss of HSiCl3. Careful fractional distillation at atmospheric pressure yielded a first fraction containing 37 g of HSiCl3 in addition to 6 g of SiCl4 and 4 g of Me2SiCl2. The second fraction consisted of 22 g of HSiCl3, 15 g of SiCl4, and 22 g of Me2SiCl2. 2 g of Me2SiCl2 remained in the residue. The Me2SiH2 was completely consumed. After the second distillation step, HSiCl3 was isolated in excellent isolation yield: 57 g (0.42 mol), 93% with respect to the molar amount of Me2SiH2 reacted.

[0074] B) Synthesis of HSiCl3 from Me3SiH and SiCl4 on a preparation scale a) Synthesis of Me3SiH by reduction of Me3SiCl with LiH in a diglyme As described in the synthesis of Me2SiH2, 34.00 g (0.31 mol) of Me3SiCl was reacted with 2.50 g of LiH (0.31 mol). After the reduction of chlorosilane and collection of Me3SiH with some diglyme in a cooling trap was completed, trimethylsilane was isolated by cold distillation in 97% yield (bp 6.7°C, 22.5 g, 0.30 mol). The formed LiCl was separated in 12.94 g (97% conversion from LiH to LiCl; theoretical yield after 100% conversion: 13.26 g) by removing diglyme and the remaining silane in a vacuum at 160°C, which is consistent with the amount of Me3SiH formed.

[0075] b) Synthesis of HSiCl3 Similar to the HSiCl3 synthesis using Me2SiH2 as the hydrogenating agent, 12.34 g (0.17 mol) of Me3SiH, SiCl4 (35.1 g, 0.21 mol), 0.5 g of n-Bu4PCl (1.7 mmol, 1.0 wt%), and 20 ml of diglym were reacted in a sealed glass ampoule at 80°C for 14 hours. The product mixture before workup was 29 SiNMR analysis showed complete conversion (100%) from tetrachloro- to trichlorosilane with no residual Me3SiH. The molar ratio of Me3SiCl / HSiCl3 / SiCl4 was 45 / 43 / 12. Careful fractional distillation (50 cm Vigreux column, distillation condenser: 8°C) yielded 97% (21.78 g, 0.16 mol) of HSiCl3 relative to the molar amount of reacted Me3SiH. Boiling points: HSiCl3 32°C, Me3SiCl 57°C.

[0076] C) Synthesis of HSiCl3 from PhSiH3 and SiCl4 using an open-system preparation scale The reaction of PhSiH3 and SiCl4 for the synthesis of HSiCl3 was carried out in an open system. 72.19 g (424.9 mmol) of SiCl4, 52 ml of diglyme, and 0.54 g (1.8 mmol) of n-Bu4PCl were mixed in a two-neck Schlenk flask equipped with a reflux condenser (cooling temperature 27 °C) and a dropping funnel under an inert N2 atmosphere. The reaction mixture was heated to reflux (oil bath temperature 80 °C), and 9.50 g (87.8 mmol) of PhSiH3 was slowly added via the dropping funnel. After the addition was complete (30 min), the reaction mixture was heated to reflux for an additional 4 h (oil bath temperature 80 °C). During the heating period, HSiCl3 was continuously condensed in a cold trap (-196 °C) connected to the reflux condenser. Subsequently, the product mixture was frozen (-196 °C), the reaction system was evacuated, and when warmed to room temperature, all volatile substances condensed in the cold trap. After condensation was complete, all volatile substances in the cold trap were condensed into a glass ampule (-196 °C, 59.44 g) fitted with an NMR tube. The glass ampule was sealed under vacuum, warmed to room temperature, and 0.5 ml of the product mixture was poured into the attached NMR tube. The NMR tube was removed from the glass ampule, and the condensed reaction product (Table 3) and the remaining residue in the reaction flask were 1 examined by 29 1H and

Table 3

[0077] PhSiH3 was completely perchlorinated to obtain PhSiCl3 remaining in the reaction flask. The corresponding conversion rate of SiCl4 -> HSiCl3 / H2SiCl2 was 100%. The molar ratio of HSiCl3 / H2SiCl2 was 94 / 6.

[0078] D) Synthesis of HSiCl3 and Me2SiHCl on a preparative scale Similar to the HSiCl3 synthesis using Me2SiH2 as the hydrogenating agent in B), 6.62 g (0.11 mol) Me2SiH2, SiCl4 (38.12 g, 0.22 mol), 0.5 g n-Bu3N (3.4 mmol, 1.4 wt%), and 20 ml of diglyceride were reacted in a sealed glass ampoule fitted with an NMR tube at 80°C for 4 hours. After the sample was cooled to room temperature, 0.5 ml of the product mixture was poured into an NMR tube, the NMR tube was sealed, and the formed product was analyzed by NMR spectroscopy. 29 The SiNMR analysis results are shown in Table 4 (yield in mol%). [Table 4]

[0079] Next, the product mixture was heated at 80°C for a further 2 hours to complete the conversion from Me2SiH2 to Me2SiHCl. Then, the product mixture was frozen in liquid nitrogen (-196°C), opened, and all volatile compounds were pumped into a cooling trap (-196°C). Because the boiling points of the target products, HSiCl3 and Me2SiHCl, are very similar (32°C vs. 35°C), further separation was not possible with the available distillation apparatus and was therefore not considered. The product distribution of the collected volatile substances (35.4g) was as follows: 1 H and 29 The results were investigated by Si NMR analysis and are shown in Table 5. A small amount of SiCl4 remained in the residue. [Table 5]

[0080] The conversion rate of SiCl4 / HSiCl3 is 45%. For quantitative reactions with a conversion rate of 50%, the overall yield of product formation is 91%.

[0081] E) Synthesis of HSiCl3 from Et2SiH2 and SiCl4 under LiCl and KCl catalytic conditions 0.08 ml (0.62 mmol) of Et2SiH2, 0.17 ml of SiCl4 (1.45 mmol), 0.3 ml of diglym, and 0.05 ml of C6D6 were mixed in separate NMR tubes with a catalytic amount of lithium chloride or potassium chloride (0.10 mmol). The NMR tubes were cooled to -196°C, evacuated, and sealed. The samples were heated according to Table 6 and analyzed by NMR spectroscopy. [Table 6]

[0082] In the case of LiCl catalysis, no Et2SiH2 remained after a reaction time of 54 hours at 120°C. Et2SiHCl was selectively formed by the monochlorolysis of Et2SiH2. Therefore, the conversion rate SiCl4->HSiCl3 was 50%. Dichlorosilane was formed only in very small amounts.

[0083] Under equivalent conditions, only 3% of HSiCl3 and Et2SiHCl were formed by the substitution of LiCl for KCl, thus characterizing LiCl as a much more potent hydrogenation catalyst. However, the catalytic activity of LiCl is inferior to that of ammonium chloride and phosphonium chloride, phosphine, and amines.

[0084] F) Synthesis of HSiCl3 from methylhydridodisilane and SiCl4 F1) 0.1 ml (0.61 mmol) of Me2HSi-SiHMe2, 0.21 ml of SiCl4 (1.8 mmol), 0.3 ml of diglym, and 0.05 ml of C6D6 were mixed with a catalytic amount of phosphonium chloride (0.02 mmol) in an NMR tube. The NMR tube was cooled to -196°C, evacuated, and sealed. The sample was heated at 80°C for 4 hours and analyzed by NMR spectroscopy (Table 7). [Table 7]

[0085] This example clearly demonstrates that tetramethyldisilane is a hydrogen shuttle that selectively mono-dehalogenates tetrachlorosilane to produce pure trichlorosilane (conversion rate SiCl4 / HSiCl3: 100%). Organochlorodisilanes R n Si2Cl 6-n (n = 1 - 5, R = organic substituent) generally have much higher boiling points compared to the corresponding monosilanes. Thus, this process will significantly reduce organochlorosilane / trichlorosilane, which is a separation problem with conventional distillation procedures. Since the reaction conditions required for the mono-reduction of tetrachlorosilane are relatively smooth, hydrosilylation catalysts do not effect disilane cleavage (in the case of n = 4 - 5), and thus the recycling of methylchlorodisilane is easily preparable by conventional reduction (in the case of tetramethyldichlorosilane, even LiH is suitable for the quantitative formation of hydride-substituted disilane), making this process route very attractive for practical and industrial use.

[0086] F2a) 0.05 ml (0.4 mmol) of MeH2Si - SiH2Me, 0.4 ml of SiCl4 (3.5 mmol), 0.3 ml of diglyme, and 0.05 ml of C6D6 were mixed with a catalytic amount of phosphonium chloride (0.02 mmol) in an NMR tube. The NMR tube was cooled to -196 °C, evacuated, and sealed. The sample was left at room temperature for 15 hours and analyzed by NMR spectroscopy (Table 8). [Table 8]

[0087] As can be concluded from Table 8, which includes the product distribution in mole % including both the case of excess SiCl4 and the case of no SiCl4, HSiCl3 is already formed at room temperature at 37% (68%) in 15 hours, while dimethyltetrachlorodisilane is 2 mol% * (3 mol%) **It was formed by [formation]. Therefore, disilane cleavage under phosphonium chloride catalyst to produce MeSiCl3 and MeSiHCl2 is already detectable under smooth conditions. SiH4 is 1 mol% * (2 mol%) ** While these compounds are formed, monosilane and dichlorosilane were not formed at all. This demonstrates that dimethyldisilane reduces SiCl4 as a hydrogen transfer reagent and simultaneously cleaves disilane to produce MeSiCl3 and MeSiHCl2. From equivalent control experiments in which a genuine sample of dimethyldisilane was reacted with a catalytic amount of n-Bu4PCl from room temperature to 50°C, methylsilane MeSiH3 (with the exception of some oligosilanes) was quantitatively formed. Although this compound was not detected in the product mixture, according to registration a) in Table 2, methylsilane quantitatively reduces SiCl4 to produce HSiCl3 and MeSiCl3.

[0088] A sample equivalent to F2b) [0.05 ml (0.4 mmol) of MeH2Si-SiH2Me, 0.4 ml of SiCl4 (3.5 mmol), 0.3 ml of diglyme, 0.05 ml of C6D6, and a catalytic amount of phosphonium chloride (0.02 mmol)] was heated at 80°C for 12 hours, and the formed product was analyzed by NMR spectroscopy (Table 9). The distribution of the product is shown in mol% for cases with excess SiCl4 and without SiCl4. [Table 9]

[0089] When the sample was heated at 80°C for 12 hours, 39 mol% * (70 mol%) ** HSiCl3, 13 mol% * (twenty four%) ** MeSiCl3 and 4 mol% * (6 mol%) ** MeSiHCl2 was formed. Clearly, neither dimethyltetrachlorodisilane nor monosilane formation was detected.

[0090] 0.07 ml of methylhydride disilane mixture (disilane distribution shown in Table 10), 0.21 ml of SiCl4 (1.8 mmol), 0.3 ml of diglym, and 0.05 ml of C6D6 were mixed with a catalytic amount of phosphonium chloride (0.02 mmol) in an NMR tube. The NMR tube was cooled to -196°C, evacuated, and sealed. The sample was heated at 80°C for 4 hours and analyzed by NMR spectroscopy (Table 11). [Table 10] [Table 11]

[0091] The experiment described in F3) is the Mueller-Rochow direct process for the production of methylchlorosilane (Si + MeCl / Cu catalyst / 350℃->Me n SiCl 4-n (n=1-3)) This clearly links the Siemens process of silicon deposition. Methylchlorodisilane Me needs to be recycled into valuable monosilane under smooth reaction conditions in order to improve economic benefits and reduce environmental pollution. n Nut2Cl 6-n Considering the direct process residue consisting of (n=2-6), (i) conventional reduction pathways (e.g., using LiAlH4 to retain the disilane skeleton, or using LiH to reduce the disilane Me) n Nut2Cl 6-n (i) Simultaneous cleavage of (n<4) to the corresponding hydride-substituted monosilane, and (i) addition of excess SiCl4 to the hydride-(di)-silane mixture are suggested. Simultaneous disilane cleavage / SiCl4 reduction and methylchlorosilane formation (exemplarily shown in Table 11) yield the most valuable monosilanes, e.g., HSiCl3 other than MeSiHCl2, in excellent yields.

[0092] All experiments performed and listed in Table 2, as well as the synthesis of trichlorosilanes on a preparation scale, were carried out according to the stoichiometric requirements for defined product formation. As described above, the conversion from tetrachlorosilane to trichlorosilane occurred with excellent selectivity with respect to the monohydrogenation of SiCl4, which was mainly used in a molar excess of 20-50% to prevent high hydrogenation that would form dichlorosilane and / or monochlorosilane. The hydrogenation of SiCl4 with Et2SiH2 (Table 2, registered x) clearly demonstrates that a high molar excess of SiCl4 is not required for the formation of HSiCl3. The excess used in our experiments was due to safety requirements to prevent the mainly possible formation of explosive monosilane, SiH4, by complete hydrogenation of tetrachlorosilane. In particular, the low boiling points of H3SiCl (-30°C) and SiH4 (-112°C) could have caused the explosion of glass ampoules or, worse, NMR tubes during measurements.

[0093] G) One-step synthesis of HSiCl3 from SiCl4 under n-Bu4PCl catalytic action A quasi-stoichiometric amount of lithium hydride (LiH, 4.3 mg) was added to tetrachlorosilane (0.4 ml), diglym (0.3 ml), C6D6 (0.05 ml), and n-Bu4PCl (1 wt%) in an NMR tube under inert conditions. The reaction mixture was frozen (liquid N2, -196°C), evacuated, and the NMR tube was sealed under vacuum. After warming to room temperature, the sample was heated to 100°C for 10 hours. 29 Si NMR analysis demonstrated the selective formation of HSiCl3 (conversion rate SiCl4 / HSiCl3 = 100%). The molar ratio of SiCl4 / HSiCl3 was 85 / 15. Clearly, hydridosilane H n SiCl 4-nThe formation of (n=2-4) was not detected but was predicted. Monosilane formation from SiCl4 and LiH (W. Sundermeyer, DE1080077, 1957; W. Sundermeyer, LM Litz, Chem. Ing. Tech 1965, 37, 14-18; HJ Klockner, M. Eschwey, Chem. Ing. Tech. 1988, 60, 815-821) results in a non-selective perhydrogenated silane. Therefore, in our case, SiH4 (formed in situ) reduces excess SiCl4 to selectively yield HSiCl3.

[0094] H) Synthesis of HSiCl3 from SiCl4 using pentachlorodisilane (PCDS, HSi2Cl5) with different catalysts Tetrachlorosilane (0.2 ml), pentachlorodisilane (0.2 ml), diglym (0.2 ml), and C6D6 (0.05 ml) were mixed with different catalysts (0.02 mol) (shown in Table 12) in NMR tubes under inert conditions. The reaction mixture was frozen (liquid N2, -196°C), evacuated, and the NMR tubes were sealed under vacuum. After allowing the samples to reach room temperature, they were heated to 80°C for 10 hours. 29 The results of the Si NMR analysis are shown in Table 12. [Table 12]

[0095] In all experiments, SiCl4-monoreduction was selective, with a conversion rate of 100% SiCl4 / HSiCl3. Chlorination of PCDS produced hexachlorodisilane (Si2Cl6), which was then cleaved by the catalyst used for reduction (CJ Wilkins, J. Chem. Soc. 1953, 3409 - 3412; J. Inorg. Nucl. Chem. 1964, 26, 409-414; J. Tillmann, H.-W.Lerner, M. Wagner, DE102015105501A1, 2016) to yield tetrachlorosilane SiCl4.

[0096] I) Synthesis of HSiCl3 from SiCl4 and Et2SiH2 in the presence of nBu4PCl and benzene as a solvent A series of experiments were conducted to investigate the role of stoichiometry in the mono-reduction of tetrachlorosilanes in detail. As an example, Et2SiH2 was reacted with SiCl4 to obtain HSiCl3 and Et2SiCl2 in C6D6 as a solvent and under nBu4PCl catalysis. According to the stoichiometry required for the quantitative reaction, in experiment a) SiCl4 and Et2SiH2 were reacted in a 2:1 molar ratio, in experiment b) SiCl4 was reacted in an excess of approximately 6 mol%, and in experiment c) Et2SiH2 was used in an excess of 12 mol% for the preparation of HSiCl3. The experiments were performed in sealed NMR tubes, and NMR spectroscopy was controlled as the reaction temperature and time increased. The results obtained are shown in Table 12.

[0097] Preparation of stock solution: 1.00 ml (7.7 mmol) of Et2SiH2 was mixed with 1.80 ml (15.5 mmol) of SiCl4 and 2.8 ml of benzene as a solvent.

[0098] In the first of three competitive experiments, 0.6 ml of stock solution and a catalytic amount of nBu4PCl (5 wt%) were mixed in an NMR tube cooled to -196°C. The NMR tube was evacuated and sealed (experiment a). In the second experiment (prepared similarly to experiment a), 0.1 mmol of SiCl4 (b) was added, and in the third experiment, 0.1 mmol of Et2SiH2 was added. The three samples were heated to 80°C and analyzed by NMR spectroscopy after reaction times of 3, 6, and 30 hours, respectively (Table 13). [Table 13]

[0099] As expected, the reaction of equimolar amounts of Et2SiH2 and SiCl4 (experiment a) resulted in a final molar ratio of HSiCl3 / H2SiCl2 of 91 / 9, with 6 mol% of SiCl4 still remaining. In the case of excess SiCl4 (experiment b), the final ratio HSiCl3 / H2SiCl2 was 94 / 6, and in the case of excess hydridosilane, the HSiCl3 / H2SiCl2 ratio was the lowest at 86 / 14. The series of experiments demonstrates that increasing the molar excess of SiCl4 primarily prevents hydrogenation by a factor of two or even three, and thus experimentally increases the selectivity and conversion rate of SiCl4->HSiCl3. Clearly, performing the experiments with diglyceride as the solvent resulted in a similar trend.

[0100] J) Synthesis of HSiCl3 from SiCl4, Et2SiH2, and nBu4PCl (without solvent) 0.6 ml (5.2 mmol) of SiCl4 was mixed with 0.17 ml (1.3 mmol) of Et2SiH2 and 0.05 g (0.17 mmol) of nBu4PCl in an NMR tube. The NMR tube was cooled to -196°C, evacuated, and sealed. The sample was heated to 80°C for 5 hours and analyzed by NMR spectroscopy. The product mixture consisted of 32.8% HSiCl3, 45.9% SiCl4, 11.7% Et2SiCl2, 9.3% Et2SiHCl, and 0.3% H2SiCl2.

[0101] Further heating of the sample at 80°C (for an additional 7 hours) yielded 42.0% HSiCl3, 36.6% SiCl4, 20.8% Et2SiCl2, and 0.6% H2SiCl2.

[0102] Advantages of the present invention 1) The formed product can be separated by distillation at atmospheric pressure, taking into account its boiling point: HSiCl3b.p. 32℃, Me2SiCl2b.p. 70℃, MeSiCl3b.p. 60℃, Me3SiCl bp 57℃, Me2SiHCl bp 35℃.

[0103] 2) Me n SiCl4-n Reactants such as (n=1-3) and SiCl4 are liquids that can be easily purified by conventional distillation, and in many cases, SiCl4 is already of ultra-high purity from the Siemens process, thus the resulting HSiCl3 is of high purity. The quality of HSiCl3 in the technical process is highly dependent on particle size and impurities, so higher quality can be easily obtained from pre-washed starting materials.

[0104] 3) SiCl4 / HSiCl3 conversion has conventionally worked at high temperatures (approximately 1000°C) or with metal silicide catalysis (600°C), with conversion rates of approximately 20% and 4-7%, respectively. The proposed process is far more energy-efficient (see Table 2, reaction time of several hours at 80°C from room temperature) and is characterized by a very high SiCl4 / HSiCl3 conversion rate.

[0105] 4) "Hydrogen Shuttle" Me n SiH 4-n (n=1-3) is the Mueller-Rochow direct process (Si + MeCl (Cu catalyst, ΔT) -> Me n SiCl 4-n n=1-3; n=2: approximately 90%). This is especially true for the main product, Me2SiCl2.

[0106] 5) Me n SiCl 4-nThe hydrogenation of (n=1-3) is possible with all common reducing agents, including alkali and alkaline earth hydrides or complex metal hydrides, such as LiAlH4 or NaBH4. The most preferred is LiH, and the reduction is carried out quantitatively (AN Kornev, VV Semenov, Metalloorg.Khim. 1991, 4, 860-863). LiCl formed by chlorosilane reduction is simply recycled in LiCl / KCl molten electrolysis to produce Li metal, which reacts with hydrogen gas at high temperatures to produce LiH. To summarize the Me2SiCl2->Me2SiH2->Me2SiCl2 cycle, Me2SiH2 is a hydrogen shuttle that is not consumed but can be easily recycled. LiH (or other reducing agents) is the "actual" agent for the monohydrogenation of SiCl4->HSiCl3, which could not be carried out otherwise.

[0107] 6) The stepwise chlorination of hydridosilanes RSiH3 and R2SiH2 depends on the reaction conditions and the hydrogenation catalyst used (see Table 2), allowing for the simultaneous formation of organochlorosilanes RSiHCl2, particularly Me2SiHCl. "Triple" hydrogenation of SiCl4 to H3SiCl is not observed; explosive SiH4 is not formed (e.g., redistribution of HSiCl3 or hydrogenation of SiCl4 with tin hydride). Therefore, the reaction proceeds as described above. Me2SiH2+SiCl4->Me2SiHCl+HSiCl3 This process has high economic value. It is highly economical and can be used in the silicon industry and silicon deposition. Since most silicon consuming companies run both direct processes (Mueller Rochow and Siemens), this process can easily be included in the main product stream. Furthermore, all consumers involved have highly developed distillation equipment to pre-purify the starting materials for producing high-purity products, such as HSiCl3 and Me2SiHCl.

Claims

1. - Formula R １ ４ One or more compounds of QZ, where R １ Q is independently selected from aliphatic hydrocarbon groups, where Q is phosphorus, nitrogen, arsenic, antimony, or bismuth, and Z is a halogen. - Formula R １ ３ P is a 1-terephosphine, here R １ This is as defined above, - formula R １ ３ one or more amines of N, where R １ is as defined above, and - One or more non-N-substituted methylimidazoles, SiCl ４ to at least one Hydride orchid, Here, at least one hydridosilane is MeSiH ３ Me ３ SiH, Me ２ SiH ２ , Et ２ SiH ２ Me ２ SiHCl, PhSiH ３ Ph ２ SiH ２ iPr ２ SiH ２ ,tBu ２ SiH ２ Me ２ Si(OEt)H, ViSiH ３ , ViMeSiH ２ Me ２ HSi-SiHMe ２ MeH ２ Si-SiH ２ Me, MeH ２ Si-SiHMe ２ Me ３ Si-SiHMe ２ and Me ３ Si-SiH ２ Selected from the group consisting of Me, This includes reacting with HSiCl ３ Method of preparation.

2. The method comprises reacting tetrachlorosilane with dimethylsilane according to reaction formula (I) or (II), Me ２ SiH ２ +2SiC- ４ ->2HSiC- ３ +Me ２ SiCS ２ (I), 7e ２ ｳiｨ ２ ｳiCl ４ ->23iCl ３ +e ２ 3i223l h(99) The method according to claim 1.

3. R １ ４ This is carried out in the presence of QZ, where R １ The method according to claim 2, wherein is an aliphatic hydrocarbon group, Q is phosphorus or nitrogen, and Z is chlorine.

4. The method according to any one of claims 1 to 3, which is carried out in the presence or absence of at least one solvent.

5. The method according to any one of claims 1 to 4, which is carried out at a temperature in the range of -40°C to 250°C.

6. The method according to any one of claims 1 to 5, carried out at a pressure of 0.1 to 10 bar.

7. The method according to any one of claims 1 to 6, carried out under inert conditions.

8. MeSiH ３ Me ３ SiH, Me ２ SiH ２ , Et ２ SiH ２ Me ２ SiHCl, PhSiH ３ Ph ２ SiH ２ iPr ２ SiH ２ ,tBu ２ SiH ２ Me ２ Si(OEt)H, ViSiH ３ , ViMeSiH ２ Me ２ HSi-SiHMe ２ MeH ２ Si-SiH ２ Me, MeH ２ Si-SiHMe ２ Me ３ Si-SiHMe ２ and Me ３ Si-SiH ２ The method according to any one of claims 1 to 7, further comprising hydrogenating a reaction product of the method according to any one of claims 1 to 7 that produces a hydridosilane selected from the group consisting of Me, and recycling the produced hydridosilane for a reaction with tetrachlorosilane.

9. The method according to claim 8, wherein the hydrogenation step is carried out using at least one hydrogenating agent selected from the group consisting of metal hydrides.

10. A) Formula R according to reaction formula (I) or (II) １ ４ Reacting tetrachlorosilane with dimethylsilane in the presence of a QZ catalyst, Me ２ SiH ２ +2SiC- ４ ->2HSiC- ３ +Me ２ SiCS ２ (I) 7e ２ ｳiｨ ２ ｳiCl ４ ->23iCl ３ +e ２ 3i223l (99)、 Here R １ Q is an aliphatic hydrocarbon group, Q is phosphorus or nitrogen, and Z is chlorine. B) HSiCl ３ and Me ２ SiCl ２ or Me ２ separating SiHCl from the reaction mixture, C) Me ２ SiCl ２ Or Me ２ Hydrogenating all or part of SiHCl with at least one metal hydride to Me ２ SiH ２ To form, D) Me ２ SiH ２ To recycle it in step A), The method according to any one of claims 1 to 9, including the method described in any one of claims 1 to 9.

11. The formed HSiCl ３ Molar amount of / ΣH １－４ SiCl ０－３ The molar amount of HCl, where the total number of hydrogen and chlorine atoms is 4, is defined as HCl × 100. ３ The method according to any one of claims 1 to 10, wherein the selectivity for the formation is at least 90%.

12. SiCl of hydridosilane ４ The method according to any one of claims 1 to 11, wherein the molar ratio to is in the range of 0.05 to 2.

13. The method according to any one of claims 1 to 12, wherein the hydridosilane is formed in a reaction system from chlorosilane and LiH.

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