KR940011185B1 - Method of preparing heterocylic compound containing silicone - Google Patents

Abstract

The silicon-contg. heterocyclic compound of formula (I) is produced by reacting an organic chloride cpd. of formula (II) having two chloromethyl gps. with a silicon in the presence of 5-15 wt.% copper as a catalyst, 0.1-2.0 wt.% cadmium, lead, zinc, silver, manganese, magnesium or chromium as a promotor at 240-370 deg.C in the fluidized or stirred tank reactor. In the formulas, R is -CH2-CH2-, (a) or (b). The compound 9I) is used as a starting material in the manufacture of silicon polymers.

Description

Method for preparing heterocyclic compounds including silicon

The present invention relates to a method for preparing heterocyclic compounds of silicon by the direct method. In more detail, a novel method for preparing heterocyclic compounds containing silicon such as general formula (I) by directly reacting an organic chloride having two chloromethyl groups as in general formula (II) with metal silicon under a copper catalyst The heterocyclic compounds are an important starting material for the production of silicone polymers because they can be ring-opened polymerized using a catalyst.

C1-CH ₂ -R-CH ₂ -C1

General formula (Ⅰ) General formula (II)

In formulas (I) and (II), R is —CH ₂ —CH ₂ —, ortho , Is displayed.

The production of methylchlorosilanes in which metal silicon and organohalogen compounds are reacted in the presence of a copper catalyst is introduced in US Pat. No. 2,380,995 and is based on this technology in today's silicon industry.

In this reaction, not only dimethyl diclosilane, but also products such as methyl trichlorosilane, trimethylchlorosilane and tetrachlorosilane are obtained. Besides these, a small amount of high boiling point material is obtained, and the composition of the product is a complicated reaction depending on the reaction conditions. Therefore, in order to effectively obtain the main product dimethyldichlorosilane, the reaction conditions, for example, the purity of the starting material, the type and amount of the catalyst used, the promoter, the reaction temperature, the reaction pressure, the type of reactor used.

It is known that the reaction does not proceed well when the catalyst is not used in the direct reaction between the metal silicon and the organic chloride, and copper is known as the best catalyst. In some cases, metals such as zinc, aluminum and cadmium are used as promoters. The promoter shortens the reaction start time and increases the selectivity of the production of dimethyldiclosilane in the product line (E.G. Rochow, J. Am. Chem. Soc., 67, 963 (1945)). Increasing the amount of copper catalyst increases the reaction but tends to increase the chlorine content of the products. Therefore, in the reaction between silicon and methyl chloride, about 10% of copper is used as a catalyst for the weight of silicon.

The copper used as catalyst forms silicon bonds of metallic silicon with Cu ₃ Si on η, and it has been reported that the Cu ₃ Si reacts with organic chlorides (VS Fikhtengolts and AL Klebanskii, J. Gen. Chem. USSR, 27 2535 (1957), a physical method of heating copper and silicon to 800 ° C-1,100 ° C under inert gas by forming Cu ₃ Si

(P. Trambouze, and B. Imelik, J. Chim. Phys., 51, 505 (1954)) and chemical methods of reacting cuprous chloride with silicon (RJH, Voorhoeve. And JC Vlugter, J. Catalysis, 4, 129 (1965).

n Si + CuC1 SiC1 ₄ + Cu ₃ Si + Cu + (n-2) Si

The reaction between silicon and chloromethyl occurs at high temperatures above 300 ° C and is exothermic, so if the heat of reaction cannot be effectively removed, the reactants become entangled and form a partial superheat (AL Klebamskii and VS Fikhten-golts, J.Gen. Chem. USSR). 27, 2693 (1957). If the reaction temperature is higher than the proper temperature, the amount of the desired dimethyldichlorosilane is reduced, many side reactions occur, and the starting material chloromethyl or products are decomposed to deposit carbon on the silicon surface. This leads to a sharp drop in the activity of silicon (J.C. Vlugter, and R.J.H.Voorhoeve, Conf.Accad.Lincei, Alta Tech. Chim. 1961 p81 (1962)). Therefore, it is very important to control the reaction temperature when synthesizing methylchlorosilane by direct method.

The type of reactor used in the direct method is a fixed type, stirred type, or fluidized type reaction tank. Agitated reactors are easier to control temperature than fixed reactors and are more responsive because solid particles collide with each other to renew the surface. Copper used as a catalyst is about three times higher than the density of the reactant silicon, making it very difficult to mix the two metals effectively. In order to solve this difficulty, a method of using a helical stirrer to spread the underlying solids up and reacting the organic chlorides in a gaseous state from the bottom has been introduced (J.E.Sellers and J.L.Davis, US Patent No. 2,448,921). However, this process requires the reaction of highly corrosive organic chlorides at high temperatures, making it difficult to obtain a corrosion-resistant stirrer and not suitable for mass production and continuous processes. In order to compensate for these drawbacks, a fluidized bed reactor was developed in which chloromethyl was blown under the reactor to react with fluidizing silicon and copper catalysts (BABluestrin, US Patent No. 2,887,502). The board is used for the manufacture of articles.

In 1958, 1,4-dichlorobutane was passed through a metal silicon layer under a copper catalyst at a reaction temperature of 250 ° C-380 ° C by Soviet chemical Nikkisin and his collaborators, yielding 1,1-dichloro- in 30% yield. 1-Syclocyclopentane was reported to be synthesized (GI Nikishin. DA Petrov, and SI Sadykh-Zade, Khim.i Prakt.Premeneie Kremneorg, Soedinenil. Trudy Konf., Leingrad. 1958. No. 1. 68-74. CA., 54, 1959e (1959))

In 1972, Soviet chemist Mironov and his co-workers also passed a gaseous bis (chloromethyl dimethylsilyl) disiloxane through metal silicon under copper catalyst at between 390 ° C and 360 ° C, and hexagonal 4,4-dichloro It was reported that -2,2,6,6, -tetramethylperhydro-1-oxy-2,4,6-trisiloxycyclohexane was synthesized (VFMironov, TKGar, AA Buyakov, Zh. Obshch.Khim). , 42, 1361 (1972), CA., 77, 114484f).

On the other hand, the present inventors use copper as a catalyst for a mixed gas of an organic colo compound having a chloro group at both ends of the molecule and hydrogen chloride or alkyl chloride which decomposes during the reaction to generate hydrogen chloride, and a metal such as cadmium, lead, zinc, silver, and manganese. It was found that bissilyl alkanes (bis (silyl) alkanes) can be prepared by directly reacting with metal silicon as a promoter. It was found that the use of cocatalysts together with the copper catalysts in this manufacturing process yielded significantly better yields than the copper catalysts alone. In the direct reaction between metal silicon and organic salts, the selection of catalyst and promoter is very important. As a promoter, metal such as cadmium, calcium, magnesium, chromium, lead, zinc, silver and manganese can be used. I found the best. It was also found that good control of the reaction temperature yields the desired product in good yield. If the reaction temperature is too high, the organic chloro compound decomposes and deposits carbon on the surface of the metal, thereby decreasing the reactivity. Therefore, choose a reactor that can control the reaction temperature well. A fluidized bed reactor was suitable for this purpose and a reaction vessel with a spiral stirrer was able to obtain better results than a controlled reactor without agitation.

In the present invention, the organic chloride having two chloromethyl groups as in general formula (II) is directly reacted with metal silicon to produce heterocyclic compounds containing silicon as general formula (I). As a catalyst, copper, but cadmium, calcium, magnesium, chromium, lead, zinc, silver, manganese, and other metals as a catalyst to react with it was found that the yield of the heterocyclic compounds containing silicon significantly improved. These heterocyclic compounds are the main starting materials for the production of silicone polymers because they can be ring-opened polymerized using a catalyst.

C1-CH ₂ -R-CH ₂ -C1

General formula (Ⅰ) General formula (II)

In formulas (I) and (II), R is -CH ₂ -CH _2- , ortho , It includes.

When explaining the present invention in more detail in the fluidized bed reaction tank or stirred reactor, metal silicon such as cadmium, or lead, zinc, silver, manganese, or the like, as a promoter, in a metal catalyst of 5% -15% under a copper catalyst of 5% -15%. The heterocyclic compounds containing silicon as in formula (1) were reacted directly with organic chloride having chloro group at both ends of the molecule as in formula (II) at the reaction temperature of 250 ℃ -370 ℃. Can be synthesized.

The catalyst may be copper or a copper compound capable of producing copper under reaction conditions. The amount of copper used is from 1% to 20%, but preferably 5% -10%. In addition to the copper catalyst, the use of a promoter can speed up the reaction or increase the selectivity for a particular product. Examples of suitable promoters for this reaction include, but are not limited to: At least one of metals such as calcium, zinc, lead, cadmium, manganese, magnesium, silver, and chromium or a metal compound thereof may be selected to use 0.01-5% of the total reaction solid. Of these promoters, cadmium was the best for improving the reactivity and selectivity of silicon.

Any type of reactor may be used, but a fluidized bed reactor or a stirred reactor equipped with a spiral stirrer is effective for the reaction. The reaction tank used in the present invention is preferably a stirred or fluidized bed reaction tank and can be reacted batchwise or continuously. Industrial silicon is used as the industrial silicon, the purity of 95% or more can be used, but preferably 98% or more. Suitable for the reaction The size of the silicon powder is suitable for the powder from 1 to 200 microns, but the selection of the suitable silicon powder size and distribution may vary depending on the size and shape of the reactor. Powders from 20 to 200 microns are suitable when using a fluidized bed reactor. The reaction temperature may be from 220 ° C to 350 ° C, but preferably 250 ° C to 320 ° C. The reason is that the reaction did not proceed smoothly below 220 ° C, while above 350 ° C, the yield of the target compound was reduced and a large amount of byproducts were produced. The reaction pressure can be used from normal pressure to 5 atmospheres. The higher the pressure, the faster the reaction speed. The organic chloro-compound of general formula (II), which is a reaction starting material, has a relatively high boiling point and is well-flowed using nitrogen together. This nitrogen helps to bring high boiling products out of the reactor. The use of 5-50% spherical fine powder acidic clay on the amount of silicon used to aid fluidization results in better fluidization and better reactivity and selectivity of silicon. Spiral stirrer is mixed with silicon and copper under the stirrer without using the fluidized bed reactor, and the silane with the reactant chloromethyl group is reacted by blowing it up in the gaseous state under the reactor to obtain a similar effect to that of the fluidized bed reactor. Can be. Also in this case, it is preferable to use nitrogen mixed with the vaporized silane. This reaction is economical because it is possible to use fine powder that can not be used when using a fluidized bed reactor.

The following examples will further illustrate the present invention but are not limited thereto.

Example 1

Preparation of Si / Cu Contact Mixtures (Ⅰ)

360 g of metal silicon (100-325 mesh) and 62.3 g of cuprous chloride (CuCl) were added to the reactor, and the temperature of the reactor was increased to 350 ° C. and dried for about 2 hours while flowing dried nitrogen. The temperature of the reactor after drying was 370. When raised to ℃, tetrachlorosilane is generated as the reaction product, resulting in a highly active Si / Cu contact mixture. The mixture was held at this temperature for about 3 hours to generate a contact mixture and then the reaction product, tetrachloride silane, was received. When cadmium, tin, and zinc were used as cocatalysts other than the main catalyst, after the formation of the contact mixture was completed, the upper part of the reaction tank was opened, and the required amount of cocatalyst was added, stirred, and mixed well.

Example 2

Preparation of Si / Cu Contact Mixtures (II)

360g of metal silicon (100-325mesh) and 40g of copper catalyst were put in a reactor and dried under the same conditions as in Example 1. After drying, the temperature of the reactor was increased to 350 ° C, and methyl chloride (CH ₃ Cl) was blown through the preheating tube at the bottom of the reactor. Some water was initially formed, and after about 40-70 minutes, dimethyldi was used as their reaction product. Closilane and methyltrichlorosilane begin to form and are collected in the receiving flask. They started producing Si / Cu contact mixtures, and after reacting with methyl chloride for about 2 hours, the supply of methyl chloride was stopped and the flask received the reaction product. When a promoter was required for the reaction, it was added and reacted in the same manner as in Example 1.

Si / Cu contact mixtures having different mixing ratios of the catalysts were prepared and used, and their composition is shown in Table 1 below.

TABLE 1

Composition of Si / Cu Contact Reactions Used in the Invention

Example 3

Reaction of 1,4-dichlorobutane with metal silicon

The following example is a typical example of Experiment No. 2. After preparing the contact mixture I-3 in Example 2 and adjusting the temperature of the reactor to 280 ° C, the syringe pump was filled with 1,4-dichlorobutane and 1,4-dichlorobutane was charged at a rate of 46.4 g / hr. Dropping in the preheating tube was introduced into the reactor to react with the metal silicon. At this time, the reaction product was used with nitrogen dried at a rate of 240ml / min to easily come out of the reaction tank. Under these reaction conditions, 1,4-dichlorobutane was 139.2 g and the reaction product was 127.6 g. The composition of the reaction product was analyzed by gas chromatograph (5% SE-54, 0.9m × 1/8 ”OD, SS. TCD) and fractional distillation to analyze the structure of each component using nuclear magnetic resonance spectroscopy. Analysis of the reaction product 1,1-dichloro-1-silylcyclopentane (Formula I) (NMR, δ (CDC1 ₃ ; 1.78 (m, 4H, -CH _2- ), 1.16 (m, 4H, -CH ₂₎ 86.1g (67.5%) were obtained, and as other by-products, 1,1,6,6-tetrachloro-1,6-disilihexane (Compound 1) (NMR, δ) was obtained. (CDCl ₃ ); 5.54 (t, 2H, Si-H), 1.66 (m, 4H, -CH ₂ ), 1.25 (m, 2H, -CH _2- ) are 7.9 g (3.6%), 1, 1, 1, 6, 6-pentachloro-1,6-disilihexane (Compound 2) (NMR, δ (CDCl ₃ ); 5.54 (t, 1H, Si-H), 1.69 (m, 4H, -CH _2- ), 1.45 (m, 2H, -CH ₂ ), 1.26 (m, 2H, -CH ₂ )) are 10.2 g (8.0%) and 1,1,1,6,6-hexachloro-1,6-di 5.5 g (4.3%) of silylhexane (Compound 3) (NMR, δ (CDC1 ₃ ); 1.70 (m, 4H, -CH _2- ), 1.46 (m, 2H, -CH _2- ) In addition to these compounds, the remainder is trichlorosilane And tetrachlorosilane.

Table 2 below shows the change in product composition according to the reaction temperature as a result obtained by the reaction of 1,4-dichlorobutane and metal silicon in the same reaction conditions except for the reaction temperature.

General Formula (I) Compound 1 Compound 2 Compound 3

TABLE 2

Changes in Product Composition with Reaction Temperature in the Reaction of 1,4-Dichlorobutane with Metal Silicon

Example 4

Reaction of 1,4-dichlorobutane with metal silicon

The contact mixtures of Table 2 prepared in Example 1 were prepared, and the composition of the reaction product obtained by reacting in the same state except that run number 2 of Example 3 and the type of the contact mixture were different from each other was listed in Table 3.

TABLE 3

Changes in Reaction Product Composition According to Catalyst Composition in the Reaction of 1,4-Dichlorobutane with Metal Silicon

Example 5

Reaction of α, α'-dichloro-O-xylene with metal silicon

After preparing the contact mixture 1-3 in Example 2 to adjust the temperature of the reaction tank to 280 ° C, 421.8 g of a mixture of 262.3 g of toluene and 159.5 g of α, α'-dichloro-O-xylene as a solvent was prepared and a syringe. The solution was placed in a lamp and dropped into the preheating tube at the bottom of the reactor at a rate of 40 ml / min to enter the reactor. At this time, nitrogen was flowed together at a rate of 240ml / min to easily take out the reaction product produced. The reaction solution used for the reaction for 2 hours was 77.5 g and the amount of reaction product produced was 71.2 g. These reaction products were analyzed in the same manner as in Example 3. As a result, 57.4 g (80.6%) was toluene as a solvent, and among the remaining 13.8 g, 3,4-benzo-1,1-dichloro-1-silylcyclopentane (I) (NMR, δ (CDC1 ₃ ); 7.30-7.18 ( m, 4H, benzo), 2.64 (s, 4H, -CH _2- )) contained 10.8 g (77.8%) and 3,4-benzo-1-chloro-1-silylcyclopentane (compound) 4) and 2-trichlorosilylmethyltoluene (Compound 5) and the like were obtained in 7.3% and 2.4%, respectively. Table 4 below shows the change of reaction product composition with the change of reaction temperature in the reaction of metal silicon with α, α'-dichloro-O-xylene.

Formula (I) Compound 4 Compound 5

TABLE 4

Changes in Reaction Product Composition with Reaction Temperature in the Reaction of α, α'-Dichloro-O-Xylene with Metal Silicon

Example 6

Reaction of 2,4- (bischloromethyl) 2-4-dimethyl-2,4-disiloxane with metal silicon

Contact mixture I-3 prepared in Example 2 was prepared and the reaction temperature was 320 ° C. under the same reaction conditions as in Example 3. 2,4- (bischloromethyl) -2,4-dimethyl-2,4 for 4 hours. 154.4 g of disiloxane was reacted to obtain 166.9 g of the reaction product. The reaction product was fractionated and identified as a result of 4,4-dichloro-2,2,6,6-tetramethyl-1-oxo-2,4,6-trisilylcyclohexane (I) (NMR, α (CDCl ₃ 0.67 (s, 4H, -CH ₃ ), 0.24 (s, 12H, -CH ₃ )) 95.3 g (57.1%) were obtained and the remaining compounds were unidentified.

General formula (Ⅰ)

(Wherein Me represents a methyl group)

Claims (9)

Metallic silicon and organic compounds having two chloromethyl groups at both ends of the same molecule as in general formula (II) are used as the catalyst and copper is reacted directly at the reaction temperature of 240-370 ° C to include silicon as in general formula (I). To prepare the heterocyclic compounds. C1-CH ₂ -R-CH ₂ -C1 General formula (Ⅰ) General formula (II) In formulas (I) and (II), R is -CH ₂ -CH _2- , ortho , Indicates. The method of claim 1 wherein a fluidized bed reactor is used. The method of claim 1 wherein a reactor with a spiral stirrer is used. The method of claim 1, wherein the inert gas nitrogen or argon is blown together with the reactants to facilitate fluidization and to easily remove the reaction product from the reactor. The method of claim 1 wherein the reactants and the inert gas are blown from below and the product drawn off. The method of claim 1 wherein the reactant and the inert gas are reacted under an input of from 1 atmosphere to 5 atmospheres. The method according to claim 1, wherein in order to improve flowability, 1-50% of spherical fine powder acidic clay is added and reacted. The method according to claim 1, wherein the copper compound which produces copper under metal copper or reaction conditions is reacted using 1-20% by weight of catalyst as a catalyst. 9. The method of claim 8, wherein at least one of metals such as calcium, zinc, lead, cadmium, manganese, magnesium, silver, and chromium, or a metal compound thereof is selected as a cocatalyst to the copper catalyst, to obtain 0.01-5% of the total reaction solid. How to use.