cas 75-54-7, Dichloromethylsilane | Articles data

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Synthesis and application of immobilized catalysts for the heterogeneously catalyzed cleavage of the Si-Si bond of chloromethyldisilanes
Lewis bases like bis(dimethylamide)phosphoryl compounds (2, 5-7), N-heterocycles (8 and 9) and N,N-dialkylamino-3-propylsilanes bearing alkoxy groups are grafted via siloxane bonds onto silica carriers. The preparation and characterisation of 5-9 are reported. The grafted bis(dimethylamide)phosphoryl compounds (2, 5-7) and N-heterocycles (8, 9) are efficient catalysts for the disproportionation of chloromethyldisilanes into chloromethyloligosilanes and chloromethylsilanes. Grafted N,N-dialkylamino-3-propylsilyl compounds heterogeneously catalyze the Si-Si bond cleavage of the disilanes with hydrogen chloride at 170°C in excellent yields. A mixture of chloromethylmonosilanes is obtained. This reaction is also performed under pressure.
Richter, Robin,Schulze, Norbert,Roewer, Gerhard,Albrecht, Jens
p. 145 - 151
(1997)
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PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS
The invention relates to a process for the stepwise synthesis of silahydrocarbons bearing up to four different organyl substituents at the silicon atom, wherein the process includes at least one step a) of producing a bifunctional hydridochlorosilane by a redistribution reaction, selective chlorination of hydridosilanes with an ether/HCI reagent, or by selective chlorination of hydridosilanes with SiCI4, at least one step b) of submitting a bifunctional hydridochloromonosilane to a hydrosilylation reaction, at least one step c) of hydrogenation of a chloromonosilane, and a step d) in which a silahydrocarbon compound is obtained in a hydrosilylation reaction.
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Page/Page column 61; 62

(2021/12/08)

Borohydride catalyzed redistribution reaction of hydrosilane and chlorosilane: A potential system for facile preparation of hydrochlorosilanes
Various borohydrides were found to catalyze the redistribution reaction of hydrosilane and chlorosilane in different solvents to produce hydrochlorosilanes efficiently and facilely. The redistribution reaction was affected by solvent and catalyst. The substrate scope was investigated in HMPA with LiBH4 as catalyst. A possible mechanism was proposed to explain the redistribution process.
Ai, Liqing,Chen, Yi,Li, Yongming,Xu, Caihong
p. 17404 - 17407
(2020/06/19)

SYNTHESIS OF ORGANO CHLOROSILANES FROM ORGANOSILANES
The invention relates to a process for the production of chlorosilanes by subjecting one or more hydndosilanes to the reaction with hydrogen chloride in the presence of at least one ether compound, and a process for the production of such hydndosilanes serving as starting materials.
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Page/Page column 36; 37; 38; 39; 40; 49; 50

(2019/04/16)

PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES
The invention relates to a process for the manufacture of organomonosilanes, in particular, bearing both hydrogen and chlorine substituents at the silicon atom by subjecting a silane substrate comprising one or more organomonosilanes, with the proviso that at least one of these silanes has at least one chlorine substituent at the silicon atom, to the reaction with one or more metal hydrides selected from the group of an alkali metal hydride and an alkaline earth metal hydride in the presence of one or more compounds (C) acting as a redistribution catalyst.
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Page/Page column 28; 29; 30; 32; 37

(2019/04/16)

PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES
The invention relates to a process for the manufacture of organomonosilanes bearing both hydrogen and chlorine substituents at the silicon atom by subjecting a silane substrate comprising one or more silanes selected from organomonosilanes, organodisilanes and organocarbodisilanes, with the proviso that at least one of these silanes has at least one chlorine substituent at the silicon atom, to a redistribution reaction in the presence of a phosphane or amine acting as a redistribution catalyst.
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Page/Page column 35; 36

(2019/04/16)

INTEGRATED PROCESS FOR THE MANUFACTURE OF METHYLCHLOROHYDRIDOMONOSILANES
The present invention relates to an integrated process for the manufacture of methylchlorohydridomonosilanes in particular, from products of the Müller-Rochow Direct Process.
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Page/Page column 35; 36; 37; 41

(2019/04/16)

Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts
The industry-scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6-n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono- and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride.
Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
supporting information
p. 13202 - 13207
(2019/10/22)

Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes
The industrial production of monosilanes MenSiCl4?n (n=1–3) through the Müller–Rochow Direct Process generates disilanes MenSi2Cl6?n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si?Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions.
Sturm, Alexander G.,Santowski, Tobias,Schweizer, Julia I.,Meyer, Lioba,Lewis, Kenrick M.,Felder, Thorsten,Auner, Norbert,Holthausen, Max C.
supporting information
p. 8499 - 8502
(2019/06/13)

CLEAVAGE OF METHYLDISILANES TO METHYLMONOSILANES
The invention relates to a process for the manufacture of methylmonosilanes comprising the step of subjecting one or more methyldisilanes to the cleavage reaction of the silicon-silicon bond, and optionally a step of separating the resulting methylmonosilanes.
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Page/Page column 25; 27; 28

(2019/04/16)

PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES FROM HYDRIDOSILANES
The invention relates to a process for the manufacture of organomonosilanes bearing both hydrogen and chlorine substituents at the silicon atom by subjecting one or more organomonosilanes to the reaction with one or more di- or carbodisilanes in the presence of one or more compounds (C) acting as a redistribution catalyst, wherein at least one of the silanes has only hydrogen and organic residues at the silicon atoms.
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Paragraph 49

(2019/04/16)

CLEAVAGE OF METHYLDISILANES, CARBODISILANES AND METHYLOLIGOSILANES WITH ALKALI-AND ALKALINE EARTH METAL SALTS
The invention relates to a process for the manufacture of methylmonosilanes comprising the step of subjecting one or more methyldisilanes, one or more methyloligosilanes, one or more carbodisilanes, or mixtures thereof to cleavage conditions resulting in the cleavage of silicon- silicon bonds or silicon-carbon bonds in carbodisilanes, and optionally a step of separating the resulting methylmonosilanes.
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Page/Page column 53; 54

(2019/04/16)

Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4?n (n=1–3) generates a disilane residue (MenSi2Cl6?n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.
Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
supporting information
p. 3809 - 3815
(2019/02/13)

Lewis Base Catalyzed Selective Chlorination of Monosilanes
A preparatively facile, highly selective synthesis of bifunctional monosilanes R2SiHCl, RSiHCl2 and RSiH2Cl is reported. By chlorination of R2SiH2 and RSiH3 with concentrated HCl/ether solutions, the stepwise introduction of Si?Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si?H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.
Sturm, Alexander G.,Schweizer, Julia I.,Meyer, Lioba,Santowski, Tobias,Auner, Norbert,Holthausen, Max C.
supporting information
p. 17796 - 17801
(2018/11/23)

Honeycomb-like CuO/ZnO hybrid nanocatalysts prepared from solid waste generated in the organosilane industry
We report the preparation of honeycomb-like CuO/ZnO (CZx/y) nanocatalysts with CuO nanospheres (NSs) adhered with ZnO nanoparticles (NPs) for the Rochow reaction. The synthesis was carried out via adsorption of Cu2+/Zn2+ ions on carbon black (CB) which acted as both the agglomeration inhibitor and the hard template, and followed by calcination in air. The low cost Cu2+/Zn2+ ions were recovered from the solid waste generated in the organosilane industry via a simple ammonia leaching treatment. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction. The as-obtained CZx/y nanohybrids had a honeycomb-like structure with large voids and openings among the CuO NSs. When re-used as a Cu-based catalyst for the Rochow reaction, the CZx/y NPs sample with an optimized ratio showed significantly improved dimethyldichlorosilane (M2) selectivity and silicon (Si) conversion as compared with the CuO/ZnO NPs prepared in the absence of CB, discrete CuO or ZnO NPs and the CuO/ZnO NPs with different compositions, mainly due to the unique honeycomb-like structure, smaller crystal size and synergistic electronic effect at the interface between Cu and ZnO in CZx/y NPs.
Li, Jing,Liu, Hezhi,Ji, Yongjun,Zhang, Yu,Wang, Guangna,Zhu, Yongxia,Zhong, Ziyi,Hu, Xiao,Su, Fabing
p. 59737 - 59748
(2016/07/06)

Controllable wet synthesis of multicomponent copper-based catalysts for Rochow reaction
This work aims to provide a facile, low-cost and scalable method for the preparation of multicomponent Cu-Cu2O-CuO catalysts, which are of high interest to the organosilane industry. A series of submicrometer-sized and Cu-based catalysts containing CuO, Cu2O and Cu, or some combination of them, were synthesized by a simple low-temperature wet chemical method using CuSO4·5H2O as the precursor and N2H4·H2O as a reducing agent. The samples were characterized by X-ray diffraction, thermogravimetric analysis, temperature-programmed reduction, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning electron microscopy techniques. It was observed that the composition of the samples could be tailored by varying the amount of reducing agent at a given reaction temperature and time. These catalysts were then tested in the Rochow reaction, using silicon powder and methyl chloride (MeCl) as reactants to produce dimethyldichlorosilane (M2), which is the most important organosilane monomer in the industry. Compared with bare CuO and Cu particles, the ternary CuO-Cu2O-Cu catalyst displayed much improved M2 selectivity and Si conversion, which can be attributed to the smaller copper particle size and the synergistic effect among the different components in the CuO-Cu2O-Cu catalyst. This catalyst preparation method is expected to yield efficient and low-cost copper catalysts for the organosilane industry.
Zhai, Yanzhao,Ji, Yongjun,Wang, Guangna,Zhu, Yongxia,Liu, Hezhi,Zhong, Ziyi,Su, Fabing
p. 73011 - 73019
(2015/09/15)

Heterojunctions generated in SnO2-CuO nanocatalysts for improved catalytic property in the Rochow reaction
We report the improved catalytic performance of SnO2-CuO hybrid nanocatalysts synthesized by rationally designing and controlling the local heterojunction structure. The SnO2 nanoparticle (NP) decorated CuO nanorods (NRs) (SnO2-CuO) with a mace-like structure and with various CuO:SnO2 ratios were prepared via depositing pre-synthesized SnO2 NPs on CuO NRs in the presence of polyvinylpyrrolidone molecules. The CuO NRs were obtained by a facile hydrothermal reaction using Cu(NO3)2·3H2O as the precursor. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction analyses. The results indicated that in the SnO2-CuO hybrid nanostructures, the heterojunctions were well generated as the SnO2 NPs were well dispersed on the CuO NRs. Their catalytic performances were then explored via the Rochow reaction, in which solid silicon (Si) reacts with gaseous methyl chloride (MeCl) to produce dimethyldichlorosilane (M2). Compared to separate CuO and SnO2 as well as their physical mixture, the SnO2-CuO hybrids exhibit significantly enhanced M2 selectivity and Si conversion because of the enhanced synergistic interaction between SnO2 and CuO due to the generated heterojunctions. This work demonstrates that the performance of heterogeneous catalysts can be improved by carefully designing and controlling their structures even when their composition remains unchanged.
Zou, Shanying,Ji, Yongjun,Wang, Guangna,Zhu, Yongxia,Liu, Hezhi,Jia, Lihua,Guo, Xiangfeng,Zhong, Ziyi,Su, Fabing
p. 63355 - 63362
(2015/08/11)

Synergistic effect in bimetallic copper-silver (CuxAg) nanoparticles enhances silicon conversion in Rochow reaction
The oleylamine thermal reduction process was employed to prepare bimetallic copper-silver (CuxAg (0 ≤ x ≤ 50)) nanoparticles, such as Cu, Cu50Ag, Cu20Ag, Cu10Ag, Cu5Ag, CuAg, CuAg2, and Ag, by using Cu(CH3COO)2 and AgNO3 as the precursors. The samples were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The CuxAg hybrid nanostructure showed good particle dispersion, and Cu and Ag metals were well mixed. The catalytic properties of these bimetallic CuxAg nanoparticles as model catalysts for the Rochow reaction were explored. Compared to monometallic Cu and Ag nanoparticles, bimetallic CuxAg nanoparticles resulted in a much higher silicon conversion, which is attributed to the synergistic electronic effect between Cu and Ag metals. For example, the Cu atom was observed to have a lower electron density in the CuxAg bimetallic nanoparticle than that in monometallic Cu nanoparticles, which enhanced the formation of methylchlorosilanes on the silicon surface with chloromethane, demonstrating the significance of the CuxAg bimetallic catalysts in catalytic reactions during organosilane synthesis. The insights gained in this study should be conducive to the design of good Cu-based catalysts for the Rochow reaction.
Zhang, Zailei,Ji, Yongjun,Li, Jing,Zhong, Ziyi,Su, Fabing
p. 54364 - 54371
(2015/06/30)

Controllably oxidized copper flakes as multicomponent copper-based catalysts for the Rochow reaction
The metallic Cu flakes prepared by milling metallic Cu powder were controllably oxidized in air at different temperatures to obtain the Cu-based catalysts containing multicomponents of Cu, Cu2O, and CuO. These catalysts are explored in the Rochow reaction using silicon powder and methyl chloride (MeCl) as reactants to produce dimethyldichlorosilane (M2), which is the most important organosilane monomer in the industry. The samples were characterized by X-ray diffraction, temperature-programmed reduction, thermogravimetric analysis, oxidimetry analysis, particle size analysis, transmission electron microscopy, and scanning electron microscopy. Compared to the metallic Cu powder and Cu flakes, the controllably oxidized Cu flakes containing Cu, Cu2O, and CuO species show much higher M2 selectivity and silicon conversion in the Rochow reaction. The enhanced catalytic performance may stem from the larger interfacial contact among the gas MeCl, solid Si particles, and solid Cu-based catalyst flakes, as well as the synergistic effect among the different Cu species. The work would be helpful to the development of novel Cu-based catalysts for organosilane synthesis.
Liu, Shaomian,Wang, Yingli,Zhu, Yongxia,Wang, Guangna,Zhang, Zailei,Che, Hongwei,Jia, Lihua,Su, Fabing
p. 7826 - 7833
(2014/02/14)

INTEGRATED PROCESS FOR CONVERSION OF STC-CONTAINING AND OCS-CONTAINING SIDESTREAMS INTO HYDROGEN-CONTAINING CHLOROSILANES
The invention relates to a process for producing a product gas mixture containing hydrogen-containing chlorosilanes within an integrated process by hydrogenating integrated process by-product silicon tetrachloride and organochlorosilane, more particularly methyltrichlorosilane, with hydrogen in a pressurized hydrogenation reactor comprising one or more reaction spaces each consisting of a reactor tube of gastight ceramic material, wherein the product gas mixture is worked up and at least a portion of at least one product of the product gas mixture is used as starting material for the hydrogenation or as starting material for some other process within the integrated process. The invention further relates to an integrated system useful for practising the integrated process.
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Page/Page column

(2014/08/07)

PROCESS FOR SELECTIVE PRODUCTION OF HALOSILANES FROM SILICON-CONTAINING TERNARY INTERMETALLIC COMPOUNDS
A process includes contacting an organohalide with a ternary intermetallic compound at a temperature of 300 °C to 700 °C to form a reaction product including a halosilane. The ternary intermetallic compound includes three metals. The first metal is Cu or Mg; the second metal is Au, Ni, or Pd; and the third metal is Si.
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Paragraph 0040

(2014/08/06)

PROCESS FOR THE PRODUCTION OF SILANE PRODUCTS FROM CALCIUM SILICIDE
A process for preparing a reaction product including a silane product includes step (i), (ii), and (iii). Step (i) is contacting an organohalide with a calcium silicide at a temperature from 300 °C to 700 °C to form the reaction product including a spent reactant and the silane product. The silane product has formula RmHnSiX(4-m-n), where each R is independently a monovalent organic group, each X is independently a halogen atom; subscript m is 0 to 4; subscript n is 0 to 2; and a quantity (m + n) is 0 to 4. Step (ii) is contacting, at a temperature from 200 °C to 1400 °C, the spent reactant with a silane of formula HaRbSiX(4-a-b), where subscript a is 0 to 4, subscript b is 0 or 1, a quantity (a + b) ≤ 4. The silane of formula HaRbSiX(4-a-b) is distinct from the silane product of formula RmHnSiX(4-m-n). When the quantity (a + b) 2; thereby forming a reactant. Step (iii) is contacting the reactant formed in step (ii) with an additional organohalide at a temperature from 300 °C to 700 °C to form an additional silane product of formula RmHnSiX(4-m-n). Steps (ii) and (iii) are performed separately and consecutively after step (i).
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Paragraph 0051

(2014/11/11)

SYNTHESIS OF ORGANOHALOSILANE MONOMERS FROM CONVENTIONALLY UNCLEAVABLE DIRECT PROCESS RESIDUE
Disclosed herein is a catalytic process for the synthesis of organohalosilane monomers from tetraorganodihalodisilanes and other compounds that are not cleaved during the conventional hydrochlorination of Direct Process Residue. The process is characterized by the use of a catalyst containing (1) one or more heterocyclic amines and/or one or more heterocyclic ammonium halides, and (2) one or more quaternary Group 15 onium compounds.
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Paragraph 0098; 0100

(2013/07/19)

Flower-like ZnO grown on urchin-like CuO microspheres for catalytic synthesis of dimethyldichlorosilane
We report the rational growth of flower-like ZnO on urchin-like CuO (f-ZnO@u-CuO) microspheres via a facile solvothermal method using copper nitrate and zinc nitrate as precursors in the presence of sodium nitrate and ethanol. A formation mechanism was proposed based on the observation of a series of reaction intermediates. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectrometer, and temperature-programmed reduction. It was found that the morphology of the samples was highly dependent on the synthesis conditions, particularly the reaction time and the ammonia amount added. As a copper-based catalyst for dimethyldichlorosilane synthesis via the Rochow reaction, f-ZnO@u-CuO microspheres show better catalytic performance than the Cu-based catalysts physically mixed with ZnO promoter, probably because of the well-developed p-n heterojunction structures at the CuO and ZnO interfaces that generate a much strong synergistic effect. The work provides a simple method to synthesize hierarchical CuO/ZnO composites and would be helpful for understanding the catalytic mechanism of the Rochow reaction.
Zhu, Yongxia,Wang, Yingli,Song, Lianying,Chen, Xin,Liu, Wuyuan,Sun, Jin,She, Xilin,Zhong, Ziyi,Su, Fabing
p. 9794 - 9802
(2013/09/02)

Catalyst for hydrodechlorination of chlorosilanes to hydrogen silanes and method for implementing hydrogen silanes using said catalyst
The invention relates to a method for producing hydrogen silanes of general formula RnCl3-nSiH by converting chlorosilanes of general formula RnCl4-nSi, where R, in both formulas simultaneously and independently of each other, is a hydrogen atom, an optionally substituted or unsubstituted hydrocarbon radical having 1 to 18 carbon atoms, and n can have the value of 1-3, and hydrogen gas in the presence of a catalytic quantity (K): zinc and/or an alloy comprising zinc on a metal oxide carrier.
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Page/Page column 2-3

(2012/06/18)

METHOD OF MAKING A TRIHALOSILANE
A method of making a trihalosilane comprising contacting an organotrihalosilane according to the formula RS1X3 (I), wherein R is C1-C10 hydrocarbyl and each X independently is halo, with hydrogen, wherein the mole ratio of the organotrihalosilane to hydrogen is from 0.009:1 to 1:2300, in the presence of a catalyst comprising a metal selected from (i) Re, (ii) a mixture comprising Re and at least one element selected from Pd, Ru, Mn, Cu, and Rh, (iii) a mixture comprising Ir and at least one element selected from Pd and Rh, (iv) Mn, (v) a mixture comprising Mn and Rh, (vi) Ag, (vii) Mg, and (viii) Rh at from 300 to 800 °C to form a trihalosilane.
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Page/Page column 24

(2012/06/30)

METHOD OF PREPARING AN ORGANOHALOSILANE
A method of preparing organohalosilanes comprising combining an organohalide having the formula RX (I), wherein R is a hydrocarbyl group having 1 to 10 carbon atoms and X is fluoro, chloro, bromo, or iodo, with a contact mass comprising at least 2% (w/w) of a palladium suicide of the formula PdxSiy (II), wherein x is an integer from 1 to 5 and y is 1 to 8, or a platinum suicide of formula PtzSi (III), wherein z is 1 or 2, in a reactor at a temperature from 250 to 700 °C to form an organohalosilane.
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Page/Page column 11

(2011/08/21)

METHOD FOR PRODUCING -HETERO-SUBSTITUTED ALKYLHALOHYDROSILANE AND USE THEREOF
Method for efficiently producing α-hetero-substituted alkylhalohydrosilane,and use thereof. A method for producing (A) a halohydrosilane compound represented by the general formula (1): H-SiR2c(CR13-bYb)aX3-a-c (1) (wherein, R1 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group; R2 represents a substituted or unsubstituted hydrocarbon group; X represents a halogen atom; Y represents a hetero substituent; a is 1 or 2; b is any one of 1, 2 and 3; c is 1 or 0), by allowing (B) a halosilane compound represented by the general formula (2) : SiR2c(CR13-bYb)aX4-a-c (2) (wherein, R1, R2, X, Y, a, b and c are as defined above) to react with (C) a hydrosilane compound. A method for producing a reactive silicon group-containing polymer using the halohydrosilane compound (A).
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Page/Page column 24; 25; 26

(2011/04/25)

PROCESS FOR PRODUCING ORGANOHALOHYDROSILANES
The invention pertains to a method of producing organohalohydrosilanes by treating a silicon metal with a halogen-containing compound, wherein the halogen-containing compound has a formula selected from RdSiX4-d (II) and RX (III), combining a catalyst and a promoter with the treated silicon metal, and contacting the combination with hydrogen gas and an organohalide. The invention also pertains to a method of producing organohalohydrosilanes by contacting an organohalide and hydrogen gas with a combination of silicon metal, a catalyst, a promoter and a hydrogen- storage material. The invention also pertains to a method of producing organohalohydrosilanes by contacting an organohalide and hydrogen gas with a combination of a silicon metal, a catalyst, a promoter and a hydrogenation catalyst. The invention also pertains to a method of producing organohalohydrosilanes by contacting an organohalide and hydrogen gas with a reaction mass residue and optionally a hydrogenation catalyst.
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Page/Page column 22-23

(2010/07/09)

Process For Preparing Methylchlorosilanes
The invention relates to a process for the direct synthesis of methylchlorosilanes by reaction of chloromethane with a contact composition comprising silicon and copper catalyst, wherein the concentration of oxygen in the chloromethane used is reduced by mixing a) chloromethane which contains oxygen, and b) chloromethane which contains a gaseous boron compound.
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Page/Page column 3

(2008/06/13)

Process For Preparing Si-H-Containing Silanes
Silanes of the general formula (1) [in-line-formulae]RaSiHbX4-b-a ??(1)[/in-line-formulae] are prepared by disproportionating at least one more highly chlorinated silane in the presence of a homogeneous catalyst in an apparatus with at least one reactive distillation column and at least one additional reactor selected from among prereactors and side reactors, where R is an alkyl, aryl, alkaryl or haloalkyl radical, X is a halogen atom, a is 0 or 1, and b is 2, 3 or 4.
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Page/Page column 3

(2009/01/24)

Process for preparing organohydrongenosilanes
Preparation of organylhydrogensilanes comprises comproportionating a mixture of organylhalosilanes in the presence of a catalyst, which contains at least one completely organically substituted ammonium or phosphonium unit. Preparation of organylhydrogensilanes comprises: comproportionating a mixture of organylhalosilanes by reaction of a organylhalosilane compound of formula (Z-R aSiCl 4-a) with organylhalosilane compound of formula (SiH bCl 4-b) to give a organylhalosilane compound of formula (Z-R aSiCl 3-a) and a organylhalosilane compound of formula (SiH b-yCl 4-b +y) in the presence of a catalyst which contains at least one completely organically substituted ammonium or phosphonium unit. R : alkyl, aryl, or alkaryl radical (optionally substituted with halo); a : 1-3; y, Z : 1-4; and b : 2-4.
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Page/Page column 3; 8

(2008/06/13)

METHOD FOR MAKING ALKYHALOSILANES
A method for making alkylhalosilanes is provided comprising reacting an alkyl halide and silicon in the presence of a copper catalyst comprising copper powder, particulate copper, copper flake, or combinations thereof and at least one co-catalyst.
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Page/Page column 6-8

(2008/06/13)

Composite copper/tin/alkali metal catalysts for the direct synthesis of alkylhalosilanes
The alkylhalosilanes are directly synthesized while diminishing the formation of coke by reacting an alkyl halide with silicon in the presence of a catalytically effective amount of (α) a copper metal or a copper-based compound catalyst and (β) a catalyst promoter intermixture therefor which comprises an effective minor amount of an additive β1 selected from the group consisting of tin, a tin-based compound and mixture thereof, optionally, an effective minor amount of an additive β2 selected from the group consisting of zinc metal, a zinc-based compound and mixture thereof, an effective minor amount of an additive β3 selected from the group consisting of cesium, potassium and rubidium, and compound and mixture thereof, and, optionally, an effective minor amount of an additive β4 selected from the group consisting of the element phosphorus, a phosphorus-based compound and mixture thereof.
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Page/Page column 4

(2008/06/13)

Process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorsilanes
The invention provides a continuous process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorosilanes which comprise liquid constituents with a boiling point of at least 70° C. at 1013 hPa and may also contain solids, with hydrogen chloride, by passing the residues at a temperature not above 200° C. and hydrogen chloride at a temperature higher than the latter into a reactor so that the resultant reaction temperature is from 400° C. to 800° C.
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Page/Page column 2

(2008/06/13)

Process for preparing organohalosilanes
Organohalosilanes are prepared by reacting metallic silicon with a halogenated hydrocarbon in the presence of a copper or copper compound catalyst and an activated aluminum, aluminum alloy or aluminum carbide promotor. The reaction is carried out at a temperature of 250-400° C. in a stirred tank reactor or a fluidized bed reactor. The inventive process shortens the time required for activation in the Rochow reaction and increases the selectivity for desirable diorganodihalosilanes. The steady state is thus prolonged and conversion of the silicon enhanced, resulting in an improved reaction performance.
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Table 1

(2008/06/13)

Bis(chloromethylsilyl)amine and bis(chloromethylsilyl)methylamine; preparation, reactivity and spectroscopic studies of their stereoisomers and conformers
The compounds NH(SiHMeCl)2 I and NMe(SiHMeCl)2 2 have been prepared by treating SiHMeCl2 with CaCl2·8NH3 and NH2Me respectively. Each was characterised by elemental analysis, mass spectrometry, NMR and IR spectroscopy. Dipole moments were also measured. The NMR spectra indicate that both compounds form 1:1 mixtures of the rac and meso diastereomers, their abundances corresponding to a statistically controlled synthetic pathway. The NMR and mass spectra also show that 1,5-dichloro-1,2,3,4,5-pentamethyltrisilazane, SiHMe[NMe(SiHMeCl)]2 3, which is formed as a side product in the synthesis of 2, also consists of two diastereomers. Variable-temperature 1H NMR spectra of NH(SiHMeCl)2 indicate participation of H(N) in hydrogen bonding. The compound is decomposed by heat and reacts with pyridine to form NH4Cl, SiHMeCl2 and polysilazanes, whereas NMe(SiHMeCl)2 shows only slight decomposition up to 80°C and does not react with pyridine. Infrared spectra in the v(SiH) region are interpreted in terms of the results of ab initio calculations of frequency, intensity and conformer abundance. The two bands near 2200 cm-1 in the spectrum of 2 have their origin in two effects: different orientations of the Si-H bonds relative to the Si-N-Si plane in several conformers and an unprecedented strong dipole-dipole coupling between the two Si-H bond stretching motions in situations where the bonds are roughly parallel. The absence of such an observed splitting for 1 is likely to be due in part to signal averaging during a free internal rotation. Significant couplings are also calculated to occur between Si-Cl bond-stretching motions, whose source must be different from that for the Si-H bond stretches.
Fleischer, Holger,McKean, Donald C.,Pulham, Colin R.,Buehl, Michael
p. 585 - 592
(2007/10/03)

Kinetics of dichlorosilylene trapping by methane and mechanism and kinetics of the methyldichlorosilane decomposition
Data relative to methane trapping of SiCl2 and a rate constant for the SiCl2 into C-H bond insertion process of k-1 = 13.4 M-1s-1 at 921 K are reported. Results on the decomposition of the trapping product, methyldichlorosilane, are also reported. This decomposition follows first-order kinetics with a rate constant of k = 1.5±0.2×10-3 s-1 at 905 K and produces methane, trichlorosilane, methyltrichlorosilane, and tetrachlorosilane. It is argued that the decomposition involves silylene intermediates, is nonchain, and is initiated primarily by the molecular methane elimination process MeSiHCl2-1→CH4+SiCl2. Free radicals and Si-C bond fission may also contribute to the decomposition but are not dominant. The kinetics of MeSiHCl2 decomposition are shown to be consistent with the kinetics of the reverse SiCl2/CH4 trapping reaction and with the overall reaction thermochemistry. Reaction modeling gives product yields, reactant conversions, and rates in reasonable agreement with the data.
Ring,O'Neal,Walker
p. 89 - 97
(2007/10/03)

Intermediacy of surface silylene in the direct synthesis of methylchlorosilanes
The reaction of silicon with methyl chloride was carried out in the presence of butadiene. The products consisted of 1,1-dichlorosila-cyclopent-3-ene, 1-methyl-1-chlorosilacyclopent-3-ene and 1-chlorosilacyclopent-3-ene besides methylchlorosilanes. Silacyclopent-3-enes accounted for 25% of the whole products. The high selectivity for silacyclopent-3-enes indicates that surface silylene is the intermediate in the reaction of silicon with methyl chloride.
Okamoto, Masaki,Onodera, Satoshi,Okano, Tomoki,Suzuki, Eiichi,Ono, Yoshio
p. 67 - 71
(2007/10/03)

Hydrogenation of Silicium-Halogen-Compounds with Trialkylstannyl Chloride/Sodium Hydride
Organotinchlorides of the general formula R3SnCl and R2SnCl2 (R = Me, n-Bu, Ph) can easily be converted into the corresponding hydrides R3SiH and R2SiH2 employing NaH in diethylene glycol dialkyl ethers.Using trialkyltinhydrides like Bu3SnH in combination with a catalyst (tertiary amines, N-heterocycles, phosphonium or ammonium salts), Si-Cl bonds in mono- and disilanes are hydrogenated.In the case of disilanes, Si-Si bond cleavage and concurrent hydrogenation can be afforded with strongly nucleophilic catalysts.Partial hydrogenation is also possible.The whole process can be run cyclically. - Keywords: Alkylstannylhydride; Hydrogenation; Organochlorsilane.
Hengge, E.,Grogger, C.,Uhlig, F.,Roewer, G.,Herzog, U.,Paetzold, U.
p. 549 - 556
(2007/10/02)

Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
Disclosed is a process for preparing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, comprising reacting (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative with (ii) a silicon halide compound or a germanium halide compound in the presence of a cyanide or a thiocyanate. The cyanide or the thiocyanate is preferably a copper salt. According to the process of the invention, a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, which is very useful for the preparation of a metallocene complex catalyst component, can be prepared in a high yield for a short period of time.
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(2008/06/13)

The role of silylenes in the direct synthesis of methylchlorosilanes
From butadiene trapping experiments in a batch flow reactor, the silylene intermediates SiMeCl and SiCl2 are shown to be formed during the Direct Synthesis.Two types of silylene intermediate are believed to be involved.Silylenoids are formed on the surface where they react with methyl chloride yielding methylchlorosilanes (SiMeCl gives Me2SiCl2, SiCl2 gives MeSiCl3) in accordance with the van den Berg mechanism.Free silylenes are released into the gas phase, where they may be trapped by butadiene, but are not directly involved in methylchlorosilane production.The addition of Me3SiH to the methyl chloride promotes radical reactions; the major product is Me3SiCl.Me3SiCl is believed to result from an efficient chain sequence proceeding mainly on the surface involving Me3Si. radicals which scavenge surface-bound chlorine.
Clarke, Michael P.,Davidson, Iain M. T.
p. 149 - 156
(2007/10/02)

Neue Wege zu Polysilanen
Disilane dervatives undergo disproportionation reactions to polysilanes.Investigated were 1,2-dimethyldisilane and 1,2-dimethyltetrachlorodisilane with catalysts like NH4Cl, AgCN, and Na-cyanamide.In case of 1,2-dimethylsilane, with more than catalytic amounts of NH4Cl, a nitrogen containing polysilane is formed.Two new compounds MeSiH(NCO)2 and Me2Si2(NCO)4 were synthesized and characterized.The last one leads to a polymer at heating.Additionally an electrochemical formation of polydimethylsilane is described.
Hengge, Edwin,Kalchauer, Wilfried
p. 793 - 802
(2007/10/02)

Direct Formation of (CH3)2HSiCl from Silicon and CH3Cl
A Cu-catalyzed reaction procedure was found for the selective formation of dimethylchlorosilane from the direct reaction of CH3Cl with solid Si.The new procedure is a two-step process.A Cu/Si sample is prepared by evaporating Cu onto clean polycrystalline Si under ultrahigh vacuum, and the Cu/Si surface is first activated by exposure to 10percent HSiCl3/CH3Cl at 598 K.After the HSiCl3/CH3Cl mixture is evacuated from the reactor, the activated Cu/Si surface is reacted in fresh CH3Cl.For low surface concentrations of Cu, the partially hydrogenated silane, (CH3)2HSiCl, is selectively produced.Trichlorosilane was also found to activate polycrystalline Si (in the absence of Cu) for production of highly chlorinated methylchlorosilanes at a much higher rate than on the Cu/Si surface but with poor selectivity to (CH3)2HSiCl.All reactions are carried out at atmospheric pressure in a reactor that is attached to an ultrahigh-vacuum chamber.This allows surface analysis by Auger electron spectroscopy, which detected SiClx on reacted surfaces.These SiClx sites, which appear necessary for methylchlorosilane formation, are apparently formed during activation by HSiCl3.
Magrini, Kimberly A.,Falconer, John L.,Koel, Bruce E.
p. 5563 - 5568
(2007/10/02)

Reduktive Oligomerisierung von 1,2-Di-tert-butyl-1,1,2,2-tetrachlordisilan: Das Tetracyclo2,7.03,6>octasilan- und das Tricyclo2,5>hexasilan-System
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Kabe, Yoshio,Kuroda, Mutsumi,Honda, Yoshihiro,Yamashita, Osamu,Kawase, Takeshi,Masamune, Satoru
p. 1793 - 1795
(2007/10/02)

Hetero-?-Systems, 8. Silaethene
By means of a combination of vacuum flash pyrolysis and matrix isolation silaethene (1a) and its simply substituted derivatives 1b-f can be prepared starting with precursors 9a-f of the silabicyclooctadiene type.Silaolefins 1a-f are stable in argon at 10 K and can be identified by their characteristic IR and UV spectra.
Maier, Guenther,Mihm, Gerhard,Reisenauer, Hans Peter
p. 2351 - 2368
(2007/10/02)

THERMOCHEMISTRY OF SILICON-CONTAINING COMPOUNDS PART 1.-SILICON-HALOGEN COMPOUNDS, AN EVALUATION
Literature data on the heats of formation of silicon-halogen compounds have been collected and reviewed.The coverage includes all tetravalent monosilicon compounds containing Si-H-X, where X is a single halogen, as well as the subhalides SiXn, where n = 1,2 or 3.The data are critically evaluated from the standpoints of bond addivity and general chemical reactivity of the species involved as well as by detailed consideration of individual studies.Earlier compilations or reviews are discussed.A set of recommended values (with uncertainties) is proposed.For the divalent species, SiX2, a self-consistent set of lone-pair stabilisation energies is obtained.
Walsh, Robin
p. 2233 - 2248
(2007/10/02)

Hydroalkenyloxysilanes
The invention provides a novel class of organosilicon compounds which are hydrogenalkenyloxysilanes represented by the general formula STR1 in which R1 is a monovalent hydrocarbon group having from 1 to 8 carbon atoms, R2, R3 and R4 are each a hydrogen atom or a monovalent hydrocarbon group having from 1 to 8 carbon atoms and n is a number of zero, 1 or 2. The silane compounds are readily obtained by the dehydrochlorination reaction between a corresponding hydrogen-containing chlorosilane compound and an α, β-unsaturated aldehyde compound or a ketone compound in the presence of an acid acceptor. The compounds are useful as a modifying agent in the silicone technology and also serve as a curing agent.
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(2008/06/13)

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Partial reduction of MeSiCl3 and Me2SiCl2 using CaH2 or (TiH2)n at high temperature (300°C) leads to MeSiHCl2 and Me2SiHCl, respectively, in good yields but in low proportion. In the presence of AlCl3 as catalyst the reaction affords Me2SiCl2 and Me3SiCl, in yields higher than those previously observed in the absence of a reducing agent. These redistribution reactions involve MeSiHCl2 and Me2SiHCl as intermediates. Consequently Me2SiHCl with or without Me2SiCl2 and Alcl3 deposited on carbon black as catalyst can undergo disproportionation to give Me3SiCl.
Simon, Gerard,Lefort, Marcel,Birot, Marc,Dunogues, Jacques,Duffaut, Norbert,Calas, Raymond
p. 279 - 286
(2007/10/02)

Stabilization of light-sensitive polymers
4-Siloxy-derivatives of sterically hindered piperidines are good light-stabilizers for organic polymers, especially for polyolefins. The stabilizers are added in an amount of from 0.01 to 5% by weight, preferably 0.02 to 1% by weight based on the polymer. The new compounds are obtainable by O-silylation of the corresponding 4-hydroxypiperidines.
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(2008/06/13)