KR860000661B1 - Process for preparing catalysts for disproportionating chlorosilane - Google Patents

Abstract

Catalyst for disproportionation reaction of chlorosilane is prepared from silicon compd. substituted with ammonium salt (I) by bonding to inorganic compd. e.g., silica or zeolite or by mixing with (II) having formula R4(CH2)nSiX'3, hydrolysis, and polymerization; where n = 1 - 4; R = C1-4 alkyl; R1, R2 = C1-8 alkyl or aryl; R3 = C1-20 alkyl or alkyl having dimethyl amino gp.; X = Cl, Br, or I; R4 = C1-6 alkyl or aryl, -H, -SH, -CN, -NR52, or -O-CO-C (CH3)=CH2; R5 = C1-4 alkyl; X1 = Cl, Br, I, or OR6 gp.; and R6 = C1-4 alkyl.

Description

Process for preparing disproportionation reaction catalyst of chlorinated silane

The present invention relates to tertiary amines and quaternary alkylammonium salts in inorganic substances by co-hydrolysis of organotrialkoxysilanes combined with tertiary amines or quaternary alkylammonium salts with other organotrialkoxy silanes or halosilanes or by reacting on silica or zeolite This is a process for preparing new and advanced disproportionation reaction catalysts of combined silane chloride.

Synthesis of chloride silanes having a bond of silicon and hydrogen can be obtained by reacting metal silicon with hydrogen chloride using copper as a catalyst. Since this reaction is exothermic, industrially, the reaction heat is removed by using a fluidized bed reactor. If the reaction temperature is not controlled, the by-products increase, and thus economical efficiency is lost. However, even if the reaction conditions are well controlled, the expected dichlorosilane is obtained in a very small amount, and the main product is obtained by about 80% with trichlorosilane, followed by about 15 tetrachlorosilanes. Therefore, this chloride silane or silane is obtained by disproportionation from trichlorosilane. A catalyst is essential for such disproportionation reactions. Conventionally, Lewis acid such as aluminum trichloride and boron trichloride may be used as a catalyst (CE Erickson, US Patent 2627451, 2735861) nitrile or amine compound, triphenylphosphine, Organic compounds such as dimethylformamide or the like (DL Dalley, US Patent 2732282), carbon powders and alkali metal salts have also been used (M, Kinger, US Patent 3627501).

A catalyst such as aluminum trichloride or boron trichloride has the advantage of being easily separated from the product after the reaction, but the reaction temperature requires a high temperature of about 200 ° C. The boiling point of the trichlorosilane is 32 ° C., and the dichlorochloride is 80 ℃, the silane is -112 ℃, if the reaction temperature is high, the pressure of the reactor should also be high, so it is difficult to operate the process, and if using the carbon or alkali metal salt, the reaction temperature should be raised to 300-350 ℃, practically little, When organic substances such as nitrile or amine compounds are used as catalysts, the reaction temperature is 100-150 ° C., but the reaction takes place at a relatively low temperature. However, the reaction time must be long. After the reaction, the catalyst is dissolved in the product to separate the catalyst from the product. It has to go through cumbersome distillation process.

Solid catalysts, which are easy to separate from such products, require high reaction temperatures, and low-temperature organic catalysts are difficult to disadvantage because the catalyst is dissolved in the product after the reaction, thus taking advantage of these two types of catalysts. As a catalyst to compensate for the shortcomings, a method of converting trichlorosilane using an organic ion exchange resin substituted with a quaternary alkylammonium salt has been developed. (J. Bakay, US Pat. No. 3928542), ion exchange resins do not dissolve in chloride silanes and are easy to separate, and the reaction occurs at a temperature below 100 ° C., and the reaction time is short within 30 minutes. Ion-exchange resins used for this purpose include Amberyst A-21 and A-26 of Tom End Haas, Inc. of the United States, and Amberite IRA-400 and the like, and are known as the most convenient and convenient catalysts among known catalysts.

However, such a catalyst has a low specific gravity, so that it is cumbersome to be filled with a support so as not to be swept away from the reactants in a continuous process. There are disadvantages. It is believed that this is due to the structural characteristics in which the quaternary alkylammonium salt is bound to the ion exchange resin which is an organic polymer.

Therefore, in order to use such an ion exchange resin as a catalyst, it is necessary to solve the problem of low specific gravity of resin and the problem of increasing the stability of the catalyst.

Inorganic materials such as silica and zeolites have some reactive hydroxyl group bonds, and thus can be bonded to organosilicon compounds reactive with this functional group (FR Hartley & PN Vezey, Avd. In Organometal Chem. V15, 189 (1978) ). Coupling an organosilicon compound to a functional group on the surface of such an inorganic material is widely used when surface-treating inorganic fillers used in the plastics industry.

The inventors of the present general formula (1) is treated with a silicon compound substituted with a quaternary ammonium salt, and when inorganic matters such as silica or zeolite are reacted with the hydroxyl group of the inorganic compound and the organosilicon compound as described below, the inorganic material in which the quaternary ammonium salt is chemically bonded The inorganic material thus prepared was found to be effective as a catalyst in the disproportionation of chlorochloride.

And wherein n is an integer of 1-4, R is an alkyl group of C ^₁ -4, R ₁ and R ² are the same or different is hydrogen or an alkyl group of C ₁ -8, or an aryl group, R ³ is C ₁ -20 Is an alkyl group having an alkyl group or a dimethylamino group, and X is a halogen element of chlorine, bromine or iodine.

The catalyst of the present invention prepared as described above has a specific gravity greater than that of a quaternary ammonium-bonded catalyst in a known organic resin, so it is not easily swept when the reactants pass through in a continuous process, and thus the active quaternary ammonium salt is an inorganic material. Since it is bound to the surface of the reaction, it is easy to contact with the reactants, and thus has high reactivity.

In addition, the organosilicon compound substituted with the ammonium salt of the general formula (1) can be used as a catalyst by making a solid silicone resin without treating inorganic substances. That is, when the compound capable of forming the silicone resin of the general formula (11) and the compound of the general formula (1) are mixed in an appropriate amount to be hydrolyzed and polymerized, the solid silicone resin in which the quaternary ammonium salt is bound by the following reaction It is a structure similar to the form in which the compound of formula (1) is bonded to the surface of silica, and is used as a catalyst for disproportionation reaction of silane chloride.

R ⁴ (CH ₂ ) _n SiX ₃ ¹ (11)

기이며, (R⁵는 C₁-4의 알킬기임) X¹은 염소, 브롬, 요오드, 또는 OR⁶기이다. (R⁶는 C₁-4의 알킬기임).In general formula (11), R ⁴ is a C _1-6 alkyl or aryl group, -H, -SH, -CN, -NR ⁵ ₂ ,

And (R ⁵ is an alkyl group of C _1-4 ) X ¹ is a chlorine, bromine, iodine, or OR ⁶ group. (R ⁶ is an alkyl group of C _1-4 ).

The method of preparing the catalyst of the present invention will be described in more detail. The compound of formula (I) is dissolved in methanol at a concentration of 40-70%, silica is added to the solution, and the diluted hydrochloric acid solution is gradually added. To hydrolysis. The compound of general formula (II) which has some tertiary amine group can also be mixed and hydrolyzed here. When these compounds are hydrolyzed and polymerized, they can chemically bond with silica and even polymerize themselves. The solid catalyst is filtered out of the aqueous solution and the water is removed. Since the quaternary ammonium salt decomposes at high temperature, it is distilled off using a solvent such as alcohol or benzene that boils with water, and blows off the solvent under reduced pressure while maintaining the temperature below 150 ° C.

In the process of bonding the quaternary ammonium salt to the zeolite, first, the zeolite 13 × is treated with an ammonium chloride solution to exchange sodium ions in the zeolite with ammonium ions, and the zeolite in which the ammonium ions are exchanged is heated to a temperature of 300-400 ° C. Blows off ammonia (DW Breck, "Zeolite Molecular Sieves" Wiley, New York 1974).

The zeolite thus treated is treated with a solution in which the compound of the general formula (1) is dissolved in methanol at 70%, and methanol, which is a solvent, is distilled off. Zeolites with the compound of formula (1) are treated with dibutyltindilaurate (5%) in a solution of toluene at a concentration of 5% and the toluene is distilled off. The remaining solid is removed by volatiles in vacuo while heating to about 100 ° C. to complete the reaction. In the preparation of a solid silicone resin in which a quaternary ammonium salt is bound, the compound of formula (1) is dissolved in methanol, mixed with 1-10 times an organotrialkoxy silane (formula (11)), and then weakly acidic water is used. Made by addition and hydrolysis. After hydrolysis, a gel-like solid is obtained, which is dried and separated from the aqueous solution, washed several times with anhydrous alcohol, and dried in a vacuum dryer to obtain a solid in the form of a lump. In this step, when an appropriate amount of dimethylaminopropyltriethoxy silane is mixed and hydrolyzed, an inorganic substance having both a quaternary ammonium salt and a tertiary amine can be obtained.

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

Example 1

Into a round-bottomed flask with three liters of one-liter spout equipped with a stirrer, a dropping funnel, and a condenser, 200 grams of silica gel in the shape of a piece were added. 200 grams (0.16 Moles) of decyldimethyl ammonium solution was added. 300 milliliters of water, which had dropped a few drops of hydrochloric acid solution to light acidity, was poured into the dropping funnel, and the water was slowly added while the stirrer was operated violently, and after stirring for an additional hour to complete the reaction, the replacement subsided. The solid is dried and washed twice with 200 ml of anhydrous ethanol, and 200 ml of benzene is added and distilled to remove water, ethanol and benzene contained in the solid. Traces of the remaining solvent were dried by heating to 90 ° C. under reduced pressure. The catalyst thus produced was 256 grams.

Example 2

A catalyst was prepared in the same manner as in Example 1 using 100 grams (0.16 Moles) of 3- (trimethoxy silyl) propyltrimethyl ammonium salt 40% methanol solution.

Example 3

The catalyst was prepared by adding 0.01 Moles of dimethyl aminopropyltrimethoxy silane under the same conditions as in Example 1.

Example 4

As in Example 1, 94 grams (0.5 Moles) of cyanopropyltrimethoxysilane was added to a round-bottomed flask equipped with three 1 liter spouts equipped with a stirrer, dropping funnel, and condenser, and 40% in methanol. Dissolve 63 grams (0.05 Moles) of 3- (trimethoxysilyl) propyloctadecyldimethylammonium chloride solution dissolved in 300 ml of water, and put it in a dropping funnel to operate the stirrer and slowly open the cock in the dropping funnel for 1 hour. To the reaction mixture was added dropwise, and 100 ml of 1 N HCl solution was added to the reaction and the mixture was stirred for 30 minutes. The resulting solid was carbonized to give a solid lumpy solid. The solid was washed twice with anhydrous alcohol and dried for 2 hours in a vacuum dryer to prepare a catalyst.

Example 5

A catalyst was prepared in the same manner as in Example 4 using 3- (trimethoxy silyl) propyl allyldimethyl ammonium chloride in place of the 3- (trimethoxy silyl) propyloctadecylammonium chloride solution.

Example 6

The catalyst was prepared by adding 0.01 Moles of dimethyl aminopropyltrimethoxysilane under the same conditions as in Example 4.

Example 7

To 100 grams of zeolite (13 ×), 29 grams of ammonium chloride was added to a solution of 120 milliliters of water. The mixture was left to heat at 80 ° C. for 2 hours, filtered, and replaced again with an ammonium salt. The zeolite was filtered, dried roughly and heated to 300-400 ° C. for 2 hours. The zeolite thus treated is wetted with 30 grams of a 70% metal solution of 3- (trimethoxysilyl) tropyladecyldimethylammonium chloride, followed by distillation of the metalol and when the zeolite dries, 2 grams of dibutyltin dirorate is 40 It was dissolved in gram of toluene and treated with zeolite. Toluene was distilled off and heated to 100 ° C. to extract volatiles in vacuum to complete the reaction to prepare a catalyst.

Claims (3)

A method for producing a disproportionation catalyst for chlorochloride, characterized in that the quaternary ammonium salt of formula (1) is substituted with a silicon compound substituted with an inorganic material such as silica or zeolite.

N is an integer from 1 to 4 in the general formula (1), R is an alkyl group of C ₁ -4, and R ² and R ¹ are the same or different alkyl group of C ₁ -8, or an aryl group, R ³ is C ₁ An alkyl group having a -20 alkyl group or a dimethylamino group, and X is a halogen element of chlorine, bromine or iodine. A method for producing a catalyst for disproportionation reaction of chloride silane, in which a compound of the formula (1) is mixed in a ratio of 0.01-5 moles to 1 mole of the compound of formula (11) to hydrolyze and polymerize. R ⁴ (CH ₂ ) _n SiX ¹ ₃ (11) In formula (11), n is an integer of 1-4, R ⁴ is a C _1-6 alkyl or aryl group or -H, -SH, -CN, -NR ⁵ ₂ ,

(R ⁵ is an alkyl group of C _1-4 ) and X ¹ is a chlorine, bromine, iodine or OR ⁶ group. (R ⁶ is an alkyl group of C _1-4 ). When bonding the compound of the formula (1) to an inorganic material such as silica or zeolite, disproportionation of the chloride silane which adds 0.01-10 mol of the compound of the formula (11) to 1 mole of the compound of the formula (1) Method for preparing a reaction catalyst.