- Direct Synthesis of Trimethoxysilane from Methanol and Hydrogen-Treated Silicon Using Copper(II) Chloride as a Catalyst
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When silicon, on which copper(II) chloride was supported, was pretreated under a hydrogen stream at 533 K and brought in contact with methanol at 533 K, trimethoxysilane was formed with an 89percent selectivity and a complete silicon conversion in 5.5 h.Pits were formed on the silicon surface, and grew with increasing silicon conversion.
- Suzuki, Eiichi,Kamata, Takatsugu,Ono, Yoshio
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- The direct synthesis of organic derivatives of silicon using nonhalogenated organic compounds
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Some trialkoxysilanes, (RO)3SiH (R = CH3, C2H5, n-C3H7, i-C4H9), and tetraalkoxysilanes were prepared directly by the reactions of the appropriate primary alcohol with a silicon-copper contact mixture. Similar attempts with secondary and tertiary alcohols, ethers, and secondary amines gave no silicon-containing products.
- Newton,Rochow
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- A Kinetic Study on the Copper-catalyzed Reaction of Silicon with Methanol into Trimethoxysilane
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The reaction of methanol with silicon was carried out in a fixed-bed reactor at 463-533 K.In order to determine the kinetics of the reaction per reaction site on the silicon surface, a pressure- (or temperature-) transition method was employed.The reaction order with respect to methanol was 1.0 and 1.4 for the Si-CuCl mixture preheated at 513 and 723 K, respectively, indicating that the rate-determining step is not the diffusion of silicon or copper species to the reaction site, but the chemical process involving methanol.Kinetics also indicate that the nature of the reaction sites changes with the preheating conditions of the mixture.
- Suzuki, Eiichi,Okamoto, Masaki,Ono, Yoshio
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- Hydrosilylation of ethylene
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Hydrosilylation of ethylene with trialkoxysilanes in the presence of Pt(0) complexes as catalysts affords ethyltrialkoxysilanes in almost quantitative yields. No impurities of vinyltrialkoxysilanes were detected. Experiments and ab initio calculations showed that the Pt(0) catalysts are considerably more active in ethylene hydrosilylation than Pt(II) catalysts. Pleiades Publishing, Inc., 2006.
- Chernyshev,Belyakova,Knyazev,Turkel'taub,Parshina,Serova,Storozhenko
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Read Online
- Direct reaction between silicon and methanol over Cu-based catalysts: Investigation of active species and regeneration of CuCl catalyst
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When a CuCl/Si mixture was pretreated at 200-240 °C in a N2 atmosphere, trimethoxysilane was predominantly formed in the direct reaction of silicon with methanol. When the pretreatment temperatures were raised to 260-340 °C, tetramethoxysilane was favorably formed. The CuxSiyClz species catalyzed the reaction between silicon and methanol to trimethoxysilane. Chlorination of the spent CuCl/Si mixture promoted the reaction between silicon and methanol to form both trimethoxysilane and tetramethoxysilane due to the recovery of the CuCl phase and the exposure of the metallic Cu0 phase. When Cu2O, CuO, and Cu0 were used as the catalysts, tetramethoxysilane was formed as the main product.
- Wang, Aili,Zhang, Mingming,Yin, Hengbo,Liu, Shuxin,Liu, Mengke,Hu, Tongjie
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p. 19317 - 19325
(2018/05/31)
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- A three-methoxy silane synthesis method (by machine translation)
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The invention provides a three-methoxy silane synthesis method, comprises the following steps: step 1, using wet chemical reduction method for preparing nanometer copper, step 2, by a grinding method and the microwave pre-treatment to prepare silica flour - nanometer copper catalyst mixture, step 3, using fixed bed reactor for preparing tri-methoxy silane. The present invention has the characteristic of the fixed bed reactor the production capacity is large, the operation is simple, and is suitable for industrial production. (by machine translation)
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Paragraph 0026-0029; 0046; 0047
(2017/08/27)
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- New vinyl alkoxy silane preparation process
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The present invention discloses a new vinyl alkoxy silane preparation process, which is characterized in that hydrogen chloride produced during a preparation process is adopted as a reactant to synthesize an initial raw material trichlorosilane, the hydrogen chloride is recycled, and the byproduct bis(trialkoxy)silyl ethane is adopted as a reaction solvent during a hydrogen silicon addition process, such that the byproduct emission is reduced, the new impurity introduction is avoided, and the product purity is improved. According to the present invention, the new process has characteristics of stable production, simple preparation process, and mild reaction conditions, and the yield of the product vinyl alkoxy silane is high, and the product purity is more than 99%.
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Paragraph 0037; 0038
(2016/10/08)
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- Method for synthesizing trimethoxy silane through fixed bed reaction
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The invention relates to the technical field of trimethoxy silane synthesis, and especially relates to a method for synthesizing trimethoxy silane through a fixed bed reaction. The trimethoxy silane is obtained through a direct reaction of silicon powder and methanol under the action of a copper system catalyst. The method comprises the following steps: preprocessing the silicon powder raw material and the catalyst, mixing and grinding cuprous chloride, surface silica removed silicon powder and copper oxide, screening the obtained ground mixture, carrying out microwave treatment, tabletting the treated silicon powder-catalyst mixture, and sieving the tabletted mixture to obtain a silicon powder-catalyst mixture; and placing the silicon powder-catalyst mixture in a fixed bed reactor, and carrying out a gas phase catalysis reaction on the silicon powder-catalyst mixture and methanol. The method has the advantages of large productivity of the fixed bed reactor, simplicity in operation, and good catalysis activity and stability of the catalyst in the reaction process.
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Paragraph 0018-0020; 0023-0024; 0027-0028; 0031-0032
(2017/08/25)
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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 OF PRODUCING A HYDROLYZABLE SILICON-CONTAINING COMPOUND
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The present invention provides a safe, inexpensive, and high yield means of producing a hydrolyzable silicon-containing compound, e.g., an organooxysilane and the like. A compound (A) represented by the general formula R1-O-R2 wherein R1 represents a C4-30, substituted or unsubstituted, tertiary alkyl group or aralkyl group and R2 represents a C1-30, substituted or unsubstituted, monovalent hydrocarbyl group or acyl group, is reacted in the presence of a Lewis acid catalyst with a halosilane (B) represented by the general formula R3mSiX4-m wherein R3 represents the hydrogen atom or a C1-30 substituted or unsubstituted monovalent hydrocarbyl group, X is independently bromine or chlorine, and m represents an integer from 0 to 3.
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Page/Page column 16-17; 20
(2012/07/14)
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- Nonhydrolytic synthesis of branched alkoxysiloxane oligomers Si[OSiH(OR)2]4 (R = Me, Et)
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Beyond silanol: A branched siloxane oligomer bearing terminal dialkoxysilyl groups was nonhydrolytically synthesized by direct alkoxysilylation of a tetraalkoxysilane with a chlorodialkoxysilane in the presence of the Lewis acid BiCl3 (see scheme). The reaction proceeds without the formation of intermediate silanol groups, and provides a selective route for siloxane-based oligomers. (Chemical equation presented)
- Wakabayashi, Ryutaro,Kawahara, Kazufumi,Kuroda, Kazuyuki
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supporting information; experimental part
p. 5273 - 5277
(2010/10/21)
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- Process for preparation of alkoxysilanes
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Alkoxysilanes are prepared by a process which uses microwave or RF energy. Thus, silicon metal and a copper catalyst are exposed to microwave radiation in the presence of an appropriate hydroxy compound, such as, an alcohol, and a catalyst, to yield the corresponding trialkoxysilane. The desired alkoxysilanes are prepared with high selectivity and at lower temperatures and shorter times than traditional approaches allow.
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Page/Page column 5-6
(2008/12/05)
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- Process for the direct synthesis of trialkoxysilane
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The Direct Synthesis of trialkoxysilane is carried out by conducting the Direct Synthesis reaction of silicon and alcohol, optionally in solvent, in the presence of a catalytically effective amount of Direct Synthesis catalyst and an effective catalyst-promoting amount of Direct Synthesis catalyst promoter, said promoter being an organic or inorganic compound possessing at least one phosphorus-oxygen bond.
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Page/Page column 16
(2008/06/13)
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- Process for the direct synthesis of trialkoxysilane
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This invention discloses a process to improve reaction stability in the Direct Synthesis of trialkoxysilanes. The process is particularly effective in the Direct Synthesis of triethoxysilane and its higher alkyl cognates providing improved triethoxysilane yields.
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Page/Page column 12
(2008/06/13)
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- METHOD FOR PRODUCING ORGANOSILANES
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The invention relates to a method for producing organosilanes by reacting amorphous silicon with appropriate alcohols while forming Si-C compounds. In order to produce organosilanes RnSi (OR) 4-n, X-ray amorphous silicon, which can be produced, for example, by reducing silicon tetrahalides with metals in an inert apolar solvent, are reacted with alcohols while heating.
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Page/Page column 8-10
(2008/06/13)
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- Removal of dissolved silicates from alcohol-silicon direct synthesis solvents
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Dissolved silanes, silicones and silicates from solvents used in the slurry phase Direct Synthesis of alkoxysilanes are removed by adding a carboxylic acid such as formic acid to generate filterable precipitates and reusable solvent. The solvents are thereby remediated and made suitable for reuse in Direct Synthesis processes. Foaming is reduced with the remediated solvent and silicon conversion rates are higher. The precipitates are easily filtered and retain negligible quantities of solvent.
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- Direct synthesis of methyldimethoxysilane from metallic silicon and methanol using copper(I) chloride catalyst
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When the reaction of metallic silicon with methanol in the presence of a small amount of thiophene was carried out at 653 K, methyldimethoxysilane was formed together with trimethoxysilane and tetramethoxysilane, the selectivity for methyldimethoxysilane being 22%. Further adding a small amount of trioxane, trimer of formaldehyde, to the reaction system improved the selectivity for methyldimethoxysilane. This indicates that formaldehyde formed by the dehydrogenation of methanol takes part in methyldimethoxysilane formation. The reaction of silicon with ethanol also gave a 14% selectivity of ethyldiethoxysilane with a 43% silicon conversion.
- Okamoto, Masaki,Abe, Hidenori,Kusama, Yukari,Suzuki, Eiichi,Ono, Yoshio
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- Direct synthesis of ethylmethoxysilanes by the liquid-phase reaction of silicon, methanol and ethylene
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The liquid-phase reactions of silicon, methanol and ethylene in an autoclave gave ethylmethoxysilanes (HSi(C2H5)(OCH3)2 and Si(C2H5)(OCH3)3) besides HSi(OCH3)3 and Si(OCH3)4.The reaction conditions for obtaining a high selectivity for the ethylmethoxysilanes were examined.With the use of a high pressure of ethylene and a small amount of methanol in toluene as a solvent at 433 K, ethylmethoxysilanes were obtained in 26percent selectivity at silicon conversion of 59percent.The direct reaction of silicon with ethanol and ethylene gave HSi(C2H5)(OC2H5)2 and Si(C2H5)(OC2H5)3.Keywords: Silylene; Alkene; Silane; Methanol; Liquid-phase reaction; Silicon
- Okamoto, Masaki,Watanabe, Naoto,Suzuki, Eiichi,Ono, Yoshio
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p. C12 - C16
(2007/10/02)
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- 1,3-disilacyclobutanes and the method for producing thereof
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The present invention relates to a process for preparing 1,3-disilacyclotutanes by pyrolyzing alkoxytrisilaalkaness at a temperature of from 400° C. to 800° C. at the atmospheric pressure or under the vacuum. This is a new synthetic route of 1,3-disilacyclobutanes which employs readily available starting materials without using alkaline metals or magnesium, affords very good yields, produces very clean product mixtures separable by distillation, and tolerates functionality on silicon.
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- Direct Formation of Organosilicon Compounds from Silicon, Methanol and Alkenes
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The reaction of metallic silicon with methanol in the presence of an allyl alkyl ether affords an organosilicon compound, the reaction giving a unique method of synthesizing organosilicon compounds without using organic halides.
- Okamoto, Masaki,Suzuki, Eiichi,Ono, Yoshio
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p. 507 - 508
(2007/10/02)
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- Destructable fluorinated alkoxysilane surfactants and repellent coatings derived therefrom
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The present invention provides liquid, destructible fluorinated nonionic surfactants that are water-soluble or dispersible, that are useful as stabilizers for emulsions, and that on curing as a layer on a substrate can provide the substrate with an oil- and water-repellent coating that is free of surfactant, the destructible surfactant comprising a fluorocarbylalkoxysilane having at least one polyfluorinated aliphatic group that is both hydrophobic and oleophobic and at least one, preferably two, polyoxyalkylene or other hydrophilic groups which can be cleaved from the hydrophobe by hydrolysis. More particularly, a fluorocarbylalkoxysilane comprises at least one polyfluorinated aliphatic group and at least one polyoxyalkylene group or other hydrophilic group, said fluorocarbylalkoxysilane being destructible by hydrolysis. The invention further provides an aqueous composition for providing a substrate with an oil and water repellent coating comprising the fluorocarbylalkoxysilane of the invention as well as a process for providing a substrate with an oil and water repellent coating.
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- Reaction of Methanol Vapor with Silicon into Trimethoxysilane with High Selectivity
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Trimethoxysilane was obtained with a 98percent selectivity and at an 82percent silicon conversion in 5 h of reaction time, when methanol (99 kPa) was fed at 543 K into a fixed-bed reactor containing silicon powder preheated with copper(I) chloride at 623 K for 3 h.
- Suzuki, Eiichi,Ono, Yoshio
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- Azasilatrane methanolysis pathways: Stereolectronic influences
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Trigonal-bipyramidal azasilatranes of the type ZSi(NHCH2CH2)3N (Z = H, Me, OEt) solvolyze in MeOH to give N(CH2CH2NH2)3 (tren) and ZSi(OMe)3. Whereas intermediates in this reaction are not detected, ZSi[N-(SiR3)CH2CH2]3N species afford detectable intermediates of the type ZSi[N(SiR3)CH2CH2]n(NHCH 2CH2)3-nN(n = 1, 2) before complete conversion to tren and ZSi(OMe)3 occurs. In cases where steric encumbrances weaken the Si-Nax bond in these molecules, monocyclic intermediates are detected. In contrast, methanolysis of HSi[N-(BMe2)CH2CH2]3N gives N(CH2CH2NHBMe2)3 (and HSi-(OMe)3), which in the presence of CD3OD gives (CD3O)nSi(OMe)4-n and the novel adduct N-[CH2CH2NHD·B(OCD3)Me2] 3. The possible steric and electronic influences of the equatorial substituents on the solvolysis pathways are discussed.
- Gudat, Dietrich,Verkade, John G.
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p. 2172 - 2175
(2008/10/08)
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- Process for producing epoxyorganoalkoxysilanes
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There is disclosed a process for producing certain epoxyorganoalkoxysilanes through the rhodium catalyzed hydrosilation of ethylenically unsaturated epoxides and alkoxysilanes in the presence of nitrogenous impurities.
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- Novel n-silyl substituted 1-sila-2-azacyclopentanes
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This invention relates to a novel class of N-silyl substituted 1-sila-2-azacyclopentane compounds. In a preferred embodiment of the instant invention, the novel compound 1,1-dimethoxy-2-(trimethoxysilyl)-1-sila-2-azacyclopentane is disclosed.
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- Method of pretreatment of inorganics with N-Silyl substituted 1-Sila-2-Azacyclopentanes
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This invention relates to a method of pretreatment of inorganics, such as fiberglass, with members of a class of N-silyl substituted 1-sila-2-azacyclopentane compounds and to a process for making composite materials therefrom. In a preferred embodiment of the instant invention, the pretreatment of fiberglass with 1,1-dimethoxy--2-(trimethoxysilyl)-1-sila-2-azacyclo-pentane is disclosed.
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- Process for recovering trimethoxysilane from a trimethoxysilane and methanol mixture
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An extractive distillation process for recovering trimethoxysilane from a trimethoxysilane-methanol mixture is provided using as the extractive solvent tetramethoxysilane.
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