SU116640A1 - Method for producing alkyl (aryl) chlorosilanes - Google Patents

Description

The preparation of alkyl (aryl) chlorosilanes by the addition of hydrides to unsaturated compounds in the presence of catalysts is known. At present, this process is carried out in sealed glass ampoules or in periodically operating autoclaves at 20-250 °, while obtaining significant quantities of adducts is difficult. This occurs, firstly, because the performance of periodically operating equipment is small and, secondly, increasing the dimensions of autoclaves is unsafe — due to the strong exothermic reaction, working with large loads often leads to explosions, which is a serious obstacle to the use of this reaction. . The obvious value of the reaction of the addition of hydridsilanes (CisSiH, CHsSiHCb and C2H5SiIiCl2) to ethylene, propylene, acetylene and other non-cedar compounds, which allows one to easily obtain valuable monomers, makes it possible to develop a simple, efficient and quite safe way of performing it.

A method for carrying out this reaction is proposed, which makes it possible to increase the productivity of the apparatus and ensure the safety of the process. Its distinguishing feature is that the process is carried out in a continuous reactor filled with a nozzle with a developed surface, in the presence or absence of an inert solvent. In this case, the initial hydridsilane flows in the form of a film over the packing, and the addition reaction takes place during the passage of liquid through the reactor. In this case, the reagents can be two liquids or a liquid and a gas entering through the fluid-free channels inside the nozzle. Thus, only small amounts of reagents are simultaneously involved in the reaction, thereby eliminating the danger of an explosion. In the event that the BC explosion nevertheless occurred in accordance with No. 116640-2

outside the local overheating, due to: p-1O1-o violation of the technological mode, it is in the presence of minimal k; The quality of the reagents would be localized only in a small section of the reactor. The nozzle that is filled with the last one can be chemically inert (for example, Ragzig compounds) or catalytically active (for example, pieces of silica gel that are coated with platinum).

An installation diagram for carrying out the proposed method for the addition of hydridsilanes to olefins is shown in the drawing. Silane from Merinka 1, in which it is under nitrogen pressure, is fed to mixer 2. Reactor gas is also supplied there (if the unsaturated compound taken for the reaction is gaseous; when working with hard olefims, they are mixed with silane in a mercury) . The flow rate of the fluid into the mixer is regulated by means of the metering valve 3. Gas is supplied to the mixer from the cylinder (wet gases are preliminarily passed through the dehumidification vessel) to the required pressure, which is kept at about a constant level. From the mixer, the reagents enter reactor 4, which is a thick-walled cylinder filled with a nozzle. The reaction products pass through cooler 5 and are collected; sepa fi, from where they are released as they accumulate.

The reaction with; the compounds can be carried out in the presence of a catalnase (for example, chlorophosphoric acid), radionuclide in a liquid reagent, or on a solid contact filling the reactor (Pt on supports).

In order to direct the reaction to the desired route, it is sometimes advisable to use a solution of a silane in a suitable inert solvent (nanrnmer, polucheplie methyl. Or ethylvinyl dichlo) silanes).

The capacity of the plant is limited by the rate of fluid flow through the reactor and the cooling efficiency of the latter. On the basis of the preparation of methylethyldichlorosilane from methyldichlorosilane and ethylene, it was shown that the removal of catalyzate from 1 liter of e) of the reactor mHet exceeds 4. The indicated performance is not a limiting one.

Example I. A 500X27 mm reactor, filled with 3X2X1 mm Raschig's porcelain rings, is passed at 120-130 ° with 161 g of methyldichlorosnlan containing 0.3 ml of a 0.1 m solution of HaPtCle bNoO in isopropyl alcohol for 30 minutes. At the same time, ethylene is fed into the reactor at a pressure of 30 atm. During the process, the reactor is intensively cooled with water. This gives 172 g of catalysate, during the distillation of 100 ml of which the fractions are separated:

The third fraction is pure methylethyldichlorosilane -

20:; 0

d 1.0614; According to 1.4195.

Soderlsanne h.lora in%: found-49.1, calculated - 49.6. Lnt data-t. kip 100 ° (747 liO, / 1.0630, p 1.4197.

Approx. 2. At 40–50 ° C, 130 g of ethyldichlorosilane containing 0.3 ml of a 0.1 m solution of H2PO1b 6H2O in isopropyl alcohol is passed through a 300X20 m reactor filled with Raschig's porcelain rings at a rate of 60 g / h. At the same time, ethylene is fed to the reactor under a pressure of 34 atm. After distillation of 148 g of catalysate, 139 g (89% of the theoretical yield) of pure diethyldichlorosilane (m.p., 127-128.5 °) are obtained.

Example 3. 123 g of methyldichloroilane containing 0.3 ml of a 0.1 m solution of H2PtCle bNaO are passed through the same reactor at 160-220 at a speed of 82 g / h. At the same time, propylene under pressure of 9 atm is obtained in the reactor. 142 g of catalysate containing 76% methyl propyl dichlorosilane (bp. 124-125 °) and 22% of the original methyldichloroilane are obtained. The yield of the first is 73% for the reacted (60% for the taken) methyldichlorosilane.

Example 4. 60 g of methyldichloroilane containing 1.2 ml of a 0.1 m solution of HaPtCla are passed through the same reactor at 20-60 ° at a speed of 30 g / hour. At the same time, acetylene is fed to the reactor under a pressure of 16 atm. During the distillation of 53 g of catalyzate, 44 g of bis (methyldichlorosilyl) ethane (m.p. 212.5-214 °, m.il. 31.5-33 °) and 6.6, unreacted methyldichlorosnlan are obtained.

Example 5. A solution of 50 g of methyldichloroilane in 75 g of chloroform containing 2.5 ml of a 0.1 m solution of HgP1C1b is passed through the same reactor at 50 °. 6H2O, its rate is 25 g of silane per hour. At the same time, acetylene at a pressure of 16 atm is fed into the reactor. After distilling off the chloroform, a product containing 32.2 g (71.5%) of metlvinyl dichlorosilane (bp 92-93.5 °) and 9 g of () bis (methyldichlorosilyl) ethane is obtained. The output of the first - 52% of the theoretical.

Example 6. 140 g of trichlorosilane containing 0.3 ml of a 0.1 m solution of H2PtCi6 is passed through the reactor at a rate of 170 g / h. bNAO in isopropyl alcohol. Before adding to trichlorosilane, the catalyst is shifted from 10 ml of ethyldichloroilane. At the same time, ethylene is fed to the reactor. 160 g of catalyzate are obtained, the following are isolated by distillation:

trichlorosilane - 10 g, t. Kip. ZG;

ethyltrichlorosilane - 132 g, t. Kip. 96-97;

Diethyldichlorosilane - 3.5 g, t. Kip. 125-127.

Ethyltrichlorosilane yield 85% for the reacted (78% for the taken) trichlorosilane.

PRI me R 7. In the lower part of the reactor load porcelain rings Raschiga, and in the upper part - a mixture And g of silica gel with 11 g of 0.5% Ft on silica gel. 77 g of ethyldichloroilane are passed through the reactor at a rate of 300 g / hour at 100-170 and at the same time ethylene is supplied. Obtain 77 g of catalyzate containing 95% diethyldichloroilane with so Kip. 128 ° at 730.5 mm. Exit 88% of the theoretical.

Example 8. In the same reactor load 10 g 0, Pt on the silcadel and at 90-150 ° pass 115 g of methyldichloroilane at a speed of 230 g / hour. At the same time, ethylene is fed under a pressure of 30 atm. Get the catalyzate containing 95% methylphenylsilane.

Example 9. In the same reactor load 11 g of 0.5% Pt on silica gel in a mixture with 11 g of pure silica gel and passed at 100-200 65 -: methyldichlorosilane at a speed of 110 g / hour. The ethylene pressure was 32 atm. After the distillation of 59 g of catalyzate, 48.3 g (61% of the theoretical yield) of methylethyldichlorosilane (m.p. 100-100.5 at 730.5 mm) and 6 2 unreacted methyldichloroilane are obtained.

The method of obtaining alknl (aryl) chlorosilanes g. By the addition of t; li; hydridsilanes to unsaturated compounds in the next known

- 3 - - “NO 116640

Subject invention

cata.Hizachors. under dosing at 20-250 °, characterized in that, in order to increase equipment performance and ensure explosion-proof working conditions, the process is carried out in a continuously operating reactor, filled with a nozzle with a developed surface, both B absence and presence inert solvent.

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