- 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 54; 58
(2021/12/08)
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- A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
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Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.
- Naganawa, Yuki,Nakajima, Yumiko,Sakamoto, Kei
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supporting information
p. 601 - 606
(2021/01/13)
-
- Method for preparing methylchlorosilanes
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The present invention relates to a method for producing methylchlorosilane by a direct synthesis method and, more specifically, to a method for preparing dimethyldichlorosilane with an improved output of methylchlorosilane (M2) and trimethylchlorosilane (M3). According to the present invention, the method for preparing methylchlorosilane comprises the step of reacting a contact composition including metal silicon, aluminum, a catalyst and a cocatalyst with methyl chloride, wherein the contact composition includes 0.1 to 0.2 parts by weight based on 100 parts by weight of metal silicon.(AA) MCS+ECM+Unreacted MC(BB) ECM+Unreacted MC(CC) FBR(MCS Reactor)(DD) ECM(By-product)(EE) Unreacted MCCOPYRIGHT KIPO 2021
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Paragraph 0040-0056
(2020/10/29)
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- DISILANE-, CARBODISILANE-AND OLIGOSILANE CLEAVAGE WITH CLEAVAGE COMPOUND ACTING AS CATALYST AND HYDROGENATION SOURCE
-
The invention relates to a process for the manufacture of monosilanes of formula (I): MexSiHyClz (I), comprising: the step of subjecting a silane substrate (methyldisilanes, methyloligosilanes, or carbodisilanes) to a cleavage reaction of the silicon-silicon bond(s) or the silicon- carbon bonds in silane substrates the reaction involving a cleavage compound selected from a quaternary Group 15 onium compound R4 QX, a heterocyclic amine, a heterocyclic ammonium halide, or a mixture of R3P and RX. The starting material disilanes to be cleaved has the formula (II): MemSi2HnClo (II) The starting material oligosilanes to be cleaved have the general formula (III): MepSiqHrCIs (II I), The starting material carbodisilanes to be cleaved have the general formula (IV): (MeaSiHbCle)-CH2-(MecSiHdClf) (IV)
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Page/Page column 48; 50
(2019/04/16)
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- Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts
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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)
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- Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane
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Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.
- Fan, Xuanzi,Xiao, Pin,Jiao, Zeqing,Yang, Tingting,Dai, Xiaojuan,Xu, Wengang,Tan, Jin Da,Cui, Ganglong,Su, Hongmei,Fang, Weihai,Wu, Jie
-
supporting information
p. 12580 - 12584
(2019/08/16)
-
- PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES FROM HYDRIDOSILANES
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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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Page/Page column 44; 45
(2019/04/16)
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- Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
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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)
-
- Technique and device for synthesizing methyl chlorosilane
-
The invention provides a technique and device for synthesizing methyl chlorosilane. The method comprises the following steps: a sand bath temperature control device is started to increase the temperature in a stirred bed reactor to the preset temperature; the weighed silicon powder and catalyst are uniformly mixed and pressed into the stirred bed under the action of nitrogen through a charging device on the upper part of the stirred bed reactor, and a magnetic stirring device is started; methyl chloride in a methyl chloride storage tank is vaporized by a methyl chloride vaporizer and enters the sand bath temperature control device through a fluidized bed inlet flowmeter to control the methyl chloride inlet reaction flow rate; and the reaction product is condensed by the product condenser and collected from the lower part of a product collector, and the uncondensed gas enters a tail gas buffer tank to be collected, is absorbed by an NaOH solution tank and discharged to the outside. The reaction temperature, reaction pressure, methyl chloride quality, silicon powder quality, catalyst quality and other reaction conditions in the methyl chlorosilane production process have favorable evaluation effects, thereby greatly lowering the industrial plant adjustment risks and enhancing the production efficiency.
- -
-
Paragraph 0014; 0015; 0016
(2017/07/01)
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- B(C6F5)3-Catalyzed Selective Chlorination of Hydrosilanes
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The chlorination of Si?H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl2, and CCl4. The catalytic chlorination of silanes often involves the use of expensive transition-metal catalysts. By a new simple, selective, and highly efficient catalytic metal-free method for the chlorination of Si?H bonds, mono-, di-, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O?B(C6F5)3 and HCl with the release of H2 as a by-product. The hydrides in di- and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O?B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.
- Chulsky, Karina,Dobrovetsky, Roman
-
supporting information
p. 4744 - 4748
(2017/04/11)
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- Porous (CuO)xZnO hollow spheres as efficient Rochow reaction catalysts
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Nowadays, how to achieve both high dimethyldichlorosilane selectivity and silicon conversion in the Rochow reaction still remains a major challenge in the organosilane industry, in which silicon and chloromethane are converted into methylchlorosilanes on Cu-based catalysts mixed with ZnO promoter. Therefore, this calls for the development of outstanding catalysts with both high activity and selectivity for the Rochow reaction and also for a deep fundamental understanding of the catalytic mechanism. In this work, we designed and synthesized a series of copper oxide-zinc oxide catalysts ((CuO)xZnO (0 ≤ x ≤ 49)) with a distinct porous hollow spherical structure for the reaction. These porous hollow spherical catalysts composed of CuO and ZnO nanoparticles were prepared through co-adsorption of Cu2+ and Zn2+ in the interior and outer surfaces of the hydrothermally synthesized carbonaceous spheres, followed by a new hydrothermal treatment and calcination in air. The catalytic properties of the (CuO)xZnO hollow spheres for dimethyldichlorosilane synthesis via the Rochow reaction was investigated, and a deeper understanding of the catalytic mechanism was obtained. As compared to pure CuO hollow spheres, the prepared (CuO)19ZnO hollow spheres exhibited much higher dimethyldichlorosilane selectivity and silicon conversion, which are clearly related to the synergistic electronic effect between Cu and ZnO and to the distinct catalyst structures which allow intimate contact of the reactant molecules with the active component and the efficient transport of the molecules. This work opens a new way for the fabrication of efficient and integrated Cu-based catalysts for the Rochow reaction.
- Zhang, Zailei,Ji, Yongjun,Li, Jing,Zhu, Yongxia,Zhong, Ziyi,Su, Fabing
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p. 2808 - 2819
(2016/05/19)
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- Preparation method of dimethyl dichlorosilane
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The invention relates to a preparation method of dimethyl dichlorosilane.The preparation method includes: adding carbon nano tube, grapheme, tetradecyl dimethyl hydroxypropyl phosphobetaine, Oktakis(tetramethyl ammonium)-T8-silisesquioxane, methanol, 1-propyl sulfonic acid-3-methyl imidazole trifluoromethane sulfonate and aluminum trichloride into a reaction kettle, heating to reaction temperature, filtering and drying after reaction is finished to obtain a composite catalyst; adding methyl trichlorosilane, trimethyl chlorosilane and the composite catalyst obtained into a high-pressure reaction kettle, heating to reaction temperature, and cooling to normal temperature after reaction is finished to obtain dimethyl dichlorosilane.
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-
Paragraph 0020; 0021
(2016/12/01)
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- Silanes and silicones with distinct hydrophilic and oleophobic substitution
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The invention relates to silicon compounds having formula (I): [in-line-formulae](RfCH2CH2)2-n[R(OCH2CHR′)mOR″]nSiX2??(I).[/in-line-formulae] In formula (I), Rf is a linear or branched perfluorinated hydrocarbon having 4 or more carbon atoms, R is a methyl or ethyl group, R′ is H or CH3, m is an integer of 1 to about 24, R″ is a hydrocarbon bridge having 1 to about 11 carbon atoms, n is an integer from 0 to 2, and X is H, Cl or an alkoxy group. The inventive materials may be used to produce siloxanes or silicones by hydrolytic condensation and have utility in surface modification.
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Page/Page column 3
(2016/06/28)
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- METHOD OF PRODUCING ORGANOHALOSILANES
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A method for producing an organohalosilanes comprising reacting an organic compound comprising a halogen-substituted or unsubstituted alkane, a halogen-substituted or unsubstituted alkene, or an aromatic compound and at least one hydridohalosilane of formula RnSiHmX4-m-n, wherein each R is independently C-1 -C-1 4 hydrocarbyl or C-1 -C-1 4 hologen-substituted hydrocarbyl, X is fluoro, chloro, bromo, or iodo, n is 0, 1, or 2, m is 1, 2 or 3, and m+n=1, 2 or 3, in the presence of a heterogeneous catalyst comprising an oxide of one or more of the elements Sc, Y, Ti, Zr, Hf, B, Al, Ga, In, C, Si, Ge, Sn, or Pb, at a temperature greater than 100 °C, and at a pressure of at least 690 kPa, to produce a crude reaction product comprising the organohalosilane.
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Paragraph 0084
(2016/09/22)
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- Honeycomb-like CuO/ZnO hybrid nanocatalysts prepared from solid waste generated in the organosilane industry
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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
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p. 59737 - 59748
(2016/07/06)
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- Reaction of chloro(ethyl)silanes with chloro(phenyl)silanes in the presence of aluminum chloride. Synthesis of chloro(ethyl)(phenyl)silanes
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Abstract Substituent exchange at the silicon atom between chloro(phenyl)silanes (PhSiCl3, MePhSiCl2, Ph2SiCl2) and chloro(ethyl)silanes (EtSiCl3, Et2SiCl2, Et3SiCl, Et4Si) in the presence of aluminum chloride has been studied. The examined compounds, except for PhSiCl3 and Et4Si, react fairly readily to give chloro(ethyl)-(phenyl)silanes in up to 48-52% yield. A probable mechanism has been proposed.
- Lakhtin,Eremeeva,Gordeev,Ushakov,Bykovchenko,Kirilin,Chernyshev
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p. 595 - 599
(2015/05/13)
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- METHOD FOR PREPARING A HALOSILANE
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A method for preparing a reaction product includes: steps (1) and (2). Step (1) is contacting, at a temperature from 200°C to 1400 °C, a first ingredient including a silane of formula HaRbSiX(4-a-b), where subscript a is an integer from 0 to 4, subscript b is 0 or 1, a quantity (a + b) 4, each R is independently a monovalent organic group, and each X is independently a halogen atom, with the proviso that when the quantity (a + b) 4, then the ingredient further includes H2; with a spinel catalyst including copper; thereby forming a reactant. Step (2) is contacting the reactant with a second ingredient including an organohalide at a temperature from 100°C to 600 °C; thereby forming the reaction product and a spent reactant. The reaction product is distinct from the silane used in step (1). The method may be used to prepare diorganodihalosilanes from silicon tetrahalides.
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Paragraph 0086
(2015/06/03)
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- Heterojunctions generated in SnO2-CuO nanocatalysts for improved catalytic property in the Rochow reaction
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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
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p. 63355 - 63362
(2015/08/11)
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- Synergistic effect in bimetallic copper-silver (CuxAg) nanoparticles enhances silicon conversion in Rochow reaction
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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
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p. 54364 - 54371
(2015/06/30)
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- Amorphous silicon: New insights into an old material
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Amorphous silicon is synthesized by treating the tetrahalosilanes SiX4 (X=Cl, F) with molten sodium in high boiling polar and non-polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine-containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO-H versus the Me-OH bond either yields H- and/or methyl-substituted methoxy functional silanes. Moreover, compounds, such as MenSi(OMe)4-n (n=0-3) are simply accessible in more than 75% yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes MenSi(OMe)4-n in excellent (n=0:100%) to acceptable yields (n=1:51%; n=2:27%); the yield of HSi(OMe)3 is about 85%. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon-based products. Amorphous silicon is easily synthesized from tetrahalosilanes SiX4 (X=Cl, F) and molten sodium in different solvents. Reactivity studies prove the resulting materials as versatile tools for the formation of technical important silanes, such as the silicon chloro-, alkoxy-, and methylalkoxy-substituted derivatives (see figure; bl=black, br=brown).
- Spomer, Natalie,Holl, Sven,Zherlitsyna, Larissa,Maysamy, Fariba,Frost, Andreas,Auner, Norbert
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supporting information
p. 5600 - 5616
(2015/03/30)
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- METHOD FOR PRODUCING ALKYL CHLOROSILANES BY WAY OF REARRANGEMENT REACTIONS
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Alkyl chlorosilanes from the manufacture of dialkyldichlorosilanes are rearranged in continuous fashion to dialkyldichlorosilane by a rearrangement reaction in a moving bed reactor employing a solid alumina catalyst containing aluminum chloride, spent catalyst being continuously removed from the reactor.
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Paragraph 0048
(2015/12/30)
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- Controllable wet synthesis of multicomponent copper-based catalysts for Rochow reaction
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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
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p. 73011 - 73019
(2015/09/15)
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- METHOD OF PREPARING AN ORGANOHALOSILANE BY REACTING HYDROGEN, HALOSILANE AND ORGANOHALIDE IN A TWO STEP PROCESS ON A COPPER CATALYST
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The application relates to a method for preparing organohalosilanes in a two-step process: Steps (i) contacting a copper catalyst with hydrogen gas and halogenated silanes forming a silicon-containing copper catalyst; and Step (ii) contacting said silicon-containing copper catalyst with an organohalide to form the organohalosilane.
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Paragraph 0065-0069
(2014/03/22)
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- PROCESS FOR THE PRODUCTION OF SILANE PRODUCTS FROM CALCIUM SILICIDE
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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 0052
(2014/11/11)
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- PROCESS FOR SELECTIVE PRODUCTION OF HALOSILANES FROM SILICON-CONTAINING TERNARY INTERMETALLIC COMPOUNDS
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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)
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- METHOD FOR PREPARING AN ORGANO-FUNCTIONAL SILANE
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A process includes reacting an organometallic cuprate and a silicon precursor in the presence of a solvent. The process produces a reaction product including an organo-functional silane.
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Paragraph 0026
(2014/05/24)
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- METHOD FOR PREPARING A HALOSILANE
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A method for preparing a reaction product includes separate and consecutive step (1) and step (2), where: step (1) is contacting, at a temperature from 200 °C to 1400 °C, an ingredient including 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, each R is independently a monovalent organic group, and each X is independently a halogen atom, with the proviso that when the quantity (a + b) 2; with a copper catalyst; thereby forming a reactant; and step (2) is contacting the reactant with an organohalide at a temperature from 100 °C to 600 °C; thereby forming the reaction product and a spent reactant. The reaction product is distinct from the silane used in step (1), and the reaction product includes a halosilane of formula R2S1X2, where each R is independently a monovalent organic group, and each X is independently a halogen atom.
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-
Paragraph 0060; 0061
(2014/10/03)
-
- 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
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p. 7826 - 7833
(2014/02/14)
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- Alternative methods for the synthesis of organosilicon compounds
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A method of forming chloro-substituted silanes from the reaction of an alkoxy-or acetoxy-substituted silane with a chlorinating agent in the optional presence of a catalyst is provided. For instance, chloro-substituted silanes, including but not limited to silicon tetrachloride, are formed by reacting a chlorinating agent, such as thionyl chloride, with an alkoxysilane having the formula (R'O)4-xSiRx, where R and R' are independently selected alkyl groups comprising one or more carbon atoms and x is 0, 1, 2, or 3. The catalyst may be dimethylformamide, (chloromethylene)dimethyliminium chloride, or triethylamine, among others. The chloro-substituted silane formed in the reaction along with several by-products has the formula (R'O)4-x-ySiRxCly; where x is 0, 1, 2, or 3 and y is 1, 2, 3, or 4. One of the by-products of the reaction is an alkyl chloride.
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-
Paragraph 0034; 0035; 0062-0064
(2013/09/26)
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- ALTERNATIVE METHODS FOR THE SYNTHESIS OF ORGANOSILICON COMPOUND
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A method of forming chloro-substituted silanes from the reaction of an alkoxysilane with a chlorinating agent in the optional presence of a catalyst is provided. More specifically, chloro-substituted silanes, including but not limited to silicon tetrachloride, are formed by reacting a chlorinating agent, such as thionyl chloride, with an alkylalkoxysilane having the formula (R'0)4-xSiRx, where R and R' are independently selected alkyl groups comprising one or more carbon atoms and x is 0, 1, 2, or 3. The catalyst may be dimethylformamide, (chloromethylene)dimethyliminium chloride, or triethylamine, among others. The chloro- substituted silane formed in the reaction along with several by-products has the formula (RO)4-x-ySiRxCly; where x is 0, 1, 2, or 3 and y is 1, 2, 3, or 4. One of the by-products of the reaction is an alkyl chloride.
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Paragraph 0062-0064
(2013/09/26)
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- Flower-like ZnO grown on urchin-like CuO microspheres for catalytic synthesis of dimethyldichlorosilane
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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
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p. 9794 - 9802
(2013/09/02)
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- A METHOD FOR PREPARING A DIORGANODIHALOSILANE
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A method of preparing a diorganodihalosilane, the method comprising the following separate and consecutive steps: (a) treating a metal catalyst comprising a metal selected from the groups consisting of i) gold, ii) gold and copper, iii) gold, copper and magnesium, iv) copper, rhodium and gold, v) copper, rhodium, and rhenium, vi) rhenium and palladium, vii) copper, and viii) copper and magnesium with a mixture comprising hydrogen gas and an organotrihalosilane at a temperature from 500 to 1400 °C to form a silicon-containing metal intermediate; and (b) reacting the silicon-containing metal intermediate with an organohalide according to the formula RX, wherein R is C1-C10 hydrocarbyl and X is halo, at a temperature from 100 to 600 °C to form a diorganodihalosilane and a depleted silicon-containing metal intermediate.
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Paragraph 0062
(2013/06/05)
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- SYNTHESIS OF ORGANOHALOSILANE MONOMERS FROM CONVENTIONALLY UNCLEAVABLE DIRECT PROCESS RESIDUE
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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 00149
(2013/07/19)
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- METHOD OF PREPARING A DIORGANODIHALOSILANE
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A method of preparing a diorganodihalosilane, the method comprising the following separate and consecutive steps: (i) treating a preformed metal silicide with a mixture comprising hydrogen gas and a silicon tetrahalide at a temperature from 300 to 1400 °C to form a treated metal silicide, wherein the preformed metal silicide comprises a metal selected from at least one of Ni, Pd, or Pt; and (ii) reacting the treated metal silicide with an organohalide according to the formula RX at a temperature from 250 to 700 °C to form a diorganodihalosilane, wherein R is C1 -C10 hydrocarbyl and X is halo.
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Page/Page column 11
(2012/08/08)
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- Mechanistic insights into the hydrosilylation of allyl compounds - Evidence for different coexisting reaction pathways
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The hydrosilylation of allyl compounds is often accompanied by the formation of high amounts of byproducts. The formation processes have not been fully understood so far. In this work, the allyl hydrosilylation mechanism is investigated in detail and experimental and theoretical evidence for multiple, coexisting reaction pathways is provided. Based on earlier reports and the observations during an extensive catalytic study, different pathways, leading to the observed byproducts, were identified and proven by labeling experiments and DFT calculations. Oxidative addition of the silane and the insertion of the allyl compound into the Pt-H bond turned out to be the crucial, selectivity-determining steps within the catalytic cycle. Based on these findings, it should be possible to systematically influence these steps and pave the way to a rational and straightforward design of more selective catalysts.
- Gigler, Peter,Drees, Markus,Riener, Korbinian,Bechlars, Bettina,Herrmann, Wolfgang A.,Kuehn, Fritz E.
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- Catalytic disproportionation of methyltrichlorosilane by AL-MCM-41 to prepare dichlorodimethylsilane
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Al-MCM-41 samples with various Si/Al ratios were prepared and then used to disproportionate methyltrichlorosilane (MTS) to produce dichlorodimethylsilane (DMCS). The catalysts were characterized by FT-IR, X-ray powder diffraction (XRD), 27Al magic angle spinning nuclear magnetic resonance ( 27Al MAS NMR), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and N2 absorption-desorption. It reveals that all samples show the hexagonal structure of MCM-41 and exhibit large BET surface areas (over 842m2g1). FT-IR spectra of pyridine adsorption demonstrates that Al-MCM-41 samples have Lewis (L) and Brnsted (B) acidic sites, and the B acidic sites are stable in the temperature ranging from 423 to 623K. The effects of aluminum content and temperature on the disproportionation reaction were also investigated. The results show that the Al-MCM-41 with the Si/Al ratio of 15:1 exhibits an excellent activity with 100% conversion of MTS and 47% selectivity of DMCS at 623K under atmospheric pressure. Taylor and Francis Group, LLC.
- Fu, Qiong,Zhang, Ning,Zhang, Jun,Hong, Sanguo
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experimental part
p. 1183 - 1194
(2012/10/18)
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- METHOD OF MAKING A DIORGANODIHALOSILANE
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A method of making a diorganodihalosilane contacting an organotrihalosilane according to the formula RSiX3 (I) with hydrogen in the presence of a metal catalyst comprising at least two metals and at a temperature from 300 to 800 °C to form a diorganodihalosilane, wherein R is C1 -C10 Q hydrocarbyl, X is halo, and two of the at least two metals are chosen from at least one of (i) copper and palladium, (ii) copper and gold, (iii) indium and iridium or (iv) iridium and rhenium.
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Page/Page column 10-11
(2012/06/30)
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- From CO2 to polysiloxanes: Di(carbamoyloxy)silanes Me 2Si[(OCO)NRR′]2 as precursors for PDMS
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Double insertion of carbon dioxide into the Si-N bonds of diaminosilanes of the type Me2Si(NRR′)2 gives di(carbamoyloxy)silanes Me2Si[(OCO)NRR′]2. The reactions proceed exothermically and quantitatively in most cases. A comprehensive analysis of the CO2-insertion products including single-crystal X-ray structure analyses was carried out. Quantum chemical calculations indicate an activation energy of about 124 kJ/mol for both the first and the second insertion and support the exothermal nature of the reaction. Investigation of the thermal decomposition of the di(carbamoyloxy)silanes Me2Si[(OCO)NRR′] 2 reveals the formation of oligo- and polysiloxanes. Depending on the thermolysis parameters, isocyanates, amines, and/or ureas are formed in addition to the siloxanes. Various methods were applied to study the decomposition process and to identify and quantify the products, including thermal analyses, mass spectrometry, and FTIR and NMR (solution and solid-state) spectroscopy. The overall reaction scheme provides a novel route to polysiloxanes which uses carbon dioxide as an oxygen source.
- Kraushaar, Konstantin,Wiltzsch, Conny,Wagler, Joerg,Boehme, Uwe,Schwarzer, Anke,Roewer, Gerhard,Kroke, Edwin
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scheme or table
p. 4779 - 4785
(2012/10/07)
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- METHOD OF PREPARING AN ORGANOHALOSILANE
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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)
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- METHOD OF MAKING ORGANOHALOSILANES
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The invention pertains to a process for the preparation of organohalosilanes. The process comprises contacting a first finely-divided silicon comprising from 0.08 to 0.25 % (w/w) of aluminum with an organohalide in a reactor at a temperature of from 250 to 350 °C in the presence of a Direct Process catalyst comprising copper, and a promotor; and introducing a second finely-divided silicon into the reactor comprising from 0.001 to 0.10 % (w/w) of aluminum into the reactor as needed in an amount sufficient to maintain an aluminum concentration of from 0.08 to 0.2 % (w/w), based on a weight of unreacted silicon and aluminum.
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Page/Page column 12-13
(2011/05/05)
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- A METHOD FOR PREPARING A DIORGANODIHALOSILANE
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A method of preparing a diorganodihalosilane comprising the separate and consecutive steps of (i) contacting a copper catalyst with a mixture comprising hydrogen gas and a silicon tetrahalide at a temperature of from 500 to 1400 °C to form a silicon-containing copper catalyst comprising at least 0.1% (w/w) of silicon, wherein the copper catalyst is selected from copper and a mixture comprising copper and at least one element selected from gold, magnesium, calcium, cesium, tin, and sulfur; and (ii) contacting the silicon-containing copper catalyst with an organohalide at a temperature of from 100 to 600 °C to form at least one diorganodihalosilane.
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Page/Page column 14-15
(2011/12/14)
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- Synthesis of dimethyldichlorosilane by catalytic disproportionation of methyltrichlorosilane over a H2SO4 activated chinese bentonite
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Disproportionation of methyltrichlorosilane (MTS) to produce dimethyldichlorosilane (DMCS) was firstly carried out over a bentonite from Zhejiang province (China) after H2SO4 activation. The results demonstrated that the bentonite activated with 30 wt% H 2SO4 solution exhibited an excellent activity with 92% conversion of MTS and 41% yield of DMCS at 673 K under atmospheric pressure. The catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray powder diffraction (XRD) and N2 absorption-desorption. The acidic sites of these bentonites were studied by in situ FTIR spectra of pyridine adsorption. It revealed that the coexistence of Lewis (L) and Bronsted (B) acidic sites facilitated the formation of DMCS and reaction temperature played important roles in the disproportionation reaction. Copyright Taylor & Francis Group, LLC.
- Ao, Zhiyong,Zhang, Ning,Jian, Lijuan,Fu, Qiong,Zhang, Fang,Chen, Chao
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experimental part
p. 2135 - 2144
(2011/12/01)
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- PROCESS FOR THE DIRECT SYNTHESIS OF ALKYLHALOSILANES
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Process for preparing alkylhalosilanes are provided. The process involve reacting an alkyl halide with a solid body formed of silicon and a catalytic system.
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Page/Page column 4-5
(2010/07/04)
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- Formation of silicon-carbon bonds by photochemical irradiation of (η5-C5H5)Fe(CO)2SiR3 and (η5-C5H5)Fe(CO)2Me to Obtain R3SiMe
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Photochemical irradiation of an equimolar mixture of (η5 -C5H5)Fe(CO)2SiR3, FpSiR 3, and FpMe leads to the efficient formation of the silicon-carbon-coupled product R3SiMe, R3 = Me 3, Me2Ph, MePh2, Ph3, ClMe 2, Cl2Me, Cl3, Me2Ar (Ar = C 6H4-p-X, X = F, OMe, CF3, NMe2). Similar chemistry occurs with related germyl and stannyl complexes at slower rates, Si > Ge Sn. Substitution of an aryl hydrogen to form FpSiMe2C6H4-p-X has little effect on the rate of the reaction, whereas progressive substitution of methyl groups on silicon by Cl slows the process. Also, changing FpMe to FpCH2SiMe3 dramatically slows the reaction as does the use of (η5-C 5Me5)Fe(CO)2 derivatives. A mechanism involving the initial formation of the 16e intermediate (η5-C 5H5)Fe(CO)Me followed by oxidative addition of the Fe-Si bond accounts for the experimental results obtained.
- Fortier, Skye,Zhang, Yongqiang,Sharma, Hemant K.,Pannell, Keith H.
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experimental part
p. 1041 - 1044
(2010/04/25)
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- IMPROVEMENTS IN THE PREPARATION OF ORGANOHALOSILANES AND HALOSILANES
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A semi-continuous process for producing organohalosilanes or halosilanes in a fluidised bed reactor, from silicon-containing contact mass, comprising removing silicon-containing contact mass that has been used in said reactor by: (i) elutriation in an unreacted organohalide or hydrogen halide stream and/or an organohalosilane or halosilane product stream and (ii) direct removal using gravitational or pressure differential methods and returning removed silicon-containing contact mass to the fluidised bed reactor and/or fresh silicon-containing contact mass. When used for producing organohalosilanes (e.g. alkylhalosilanes) the silicon-containing contact mass may contain catalysts and promoters in addition to silicon.
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Page/Page column 19-21
(2009/12/28)
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- Process For Preparing Methylchlorosilanes
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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)
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- Direct Method for Synthesising Alkylhalogenosilanes
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Process for the preparation of alkylhalosilanes by reaction of an alkyl halide, preferably CH3Cl, with a solid body, referred to as contact body, formed of silicon and of a catalytic system comprising (α) a copper catalyst and (β) a group of promoting additives comprising: an additive β1 chosen from metallic zinc, a zinc-based compound and a mixture of these entities, an additive β2 chosen from tin, a tin-based compound and a mixture of these entities, optionally an additive β3 chosen from cesium, potassium, rubidium, a compound derived from these metals and a mixture of these entities, said direct synthesis process being characterized by the following points, taken in combination: the copper catalyst (α) is in the form of metallic copper. of a copper halide or of a mixture of these entities, the contact body additionally includes a supplementary promoting additive β4 chosen from a derivative of an acid of phosphorus and a mixture of these entities.
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Page/Page column 3; 4
(2008/06/13)
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- PRODUCTION OF ORGANOSILANES IN THE PRESENCE OF IRIDIUM-CATALYSTS AND COCATALYSTS
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The invention relates to a method for producing silanes of general formula (I) R6R5CH-R4CH-SiR1R2R3 (I), wherein silanes of general formula (II) HsiR1R2R3 (II) are reacted with alcenes and/or allcynes of general formula (III) R6R5C=CHR4 (III), in the presence of iridium compounds as catalysts and in the presence of cocatalysts according to claim 1. The amount of cocatalysts is between 0.5 wt.- % to 5.0 wt.- %, in relation to the total weight of the used components of general formulae (II) and (III). According to the invention, R1, R2, R3, R4, R5, R6 and R have the meaning cited in claim 1.
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Page/Page column 15-16
(2008/06/13)
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- Process for preparing methylchlorosilanes
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A process for the direct synthesis of methylchlorosilanes by reaction of chloromethane with a contact composition comprising silicon, copper catalyst and from 10 to 90 ppm of strontium leads to increased selectivity and higher production rate.
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Page/Page column 2-3
(2008/06/13)
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- Process for preparing methylchlorosilanes
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The invention relates to a process for the direct synthesis of methylchlorosilanes by reaction of chloromethane with a contact composition comprising silicon, copper catalyst and a total proportion of sodium and potassium of from 10 to 400 ppm.
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Page/Page column 2-3
(2008/06/13)
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