JPH0131A - Method for producing chlorine-containing metal alkoxide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a chlorine-containing metal alkoxide solution, and more specifically to a highly concentrated chlorine-containing metal alkoxide solution having a stable composition over a long period of time. Concerning the manufacturing method.

[Prior Art] Conventionally, when producing alkoxides of metals that have higher ionization energy than alkali metals and alkaline earth metals, metal chlorides have been used as starting materials. If the chlorine in this metal chloride is not completely replaced by an alkoxide group and some parts remain, it becomes a chlorine-containing metal alkoxide, but until recently this substance was used as a catalyst.
It did not have any uses that attracted much attention, and the manufacturing method itself had not been studied much. Conventional manufacturing methods, including the method for manufacturing fully substituted metal alkoxides for chlorine, which has been studied extensively, can be roughly divided into four types.

The first method is a method of mixing and heating a metal chloride and alcohol, and is represented by formula (1).

MCI,L +xRO)I →MCI,-z(OR)
z +xHC1=il) In this reaction formula, a metal is represented, ROH represents an alcohol, and n is a positive integer corresponding to the valence of the metal, while X is a positive number less than or equal to n. In this reaction, the substitution of alcohol for chlorine does not progress very much, so the chlorine content ratio cannot be controlled, and there are problems such as smoke generation due to the generation of hydrochloric acid. The manufacturing method has not yet been determined.

The second method is to simply mix a completely substituted metal alkoxide and a chloride of the same metal.As can be seen from equation (2), in this case, by changing the mixing ratio of the two raw materials, The chlorine content can be changed freely.

(n-x)MCI, +xMOR-nMclm-z(OR
)t +++ (2) However, in this method, the tta reaction is difficult to proceed and a solution with a uniform composition cannot be obtained. There is a problem in that it is expensive because it requires a complicated process of mixing.

The third method is to blow ammonia into an alcohol solution of a metal chloride, which is normally used to produce fully substituted alkoxides, and the reaction proceeds according to the chemical reaction formula shown in equation (3). Chlorine in the metal chloride reacts with ammonia to form ammonium chloride, while the metal is coordinated with the solvent alcohol.

MCI, %+XROH+ XNH3→MCI, -,
(OR)7+ Ni14 CL... (3) However, with this method, it is difficult to completely absorb the ammonia gas blown into the solution, and the degree of substitution of chlorine groups cannot be easily quantified.
As the alkoxide precipitates, the solution becomes viscous and stirring is significantly inhibited, which tends to cause problems such as local overheating, bumping, and blockage of the N13 pipe.To avoid this problem, the concentration of alkoxide must be significantly reduced. There were many problems, including the fact that ammonia tends to remain in the liquid, making it easy for the liquid to be hydrolyzed.

The fourth method is a method of producing a chlorine-containing metal alkoxide by an exchange reaction with a metal chloride using metallic sodium, and the chemical reaction formula is as shown in the following formula (4).

MCI, +xNaOR-+MCI,-, 7OR), +
xNaC1 --- (4) In this method, metal chlorides cannot be handled as they are and the reaction is violent, so conventionally they are used in a diluted solution dissolved in alcohol, and sodium alkoxide is also used dissolved in alcohol. Therefore, there was a problem that metal alkoxide containing high concentration of chlorine could not be produced.

(Refer to Japanese Unexamined Patent Publication No. 61-21919) [Problems to be Solved by the Invention] When attempting to produce a chlorine-containing metal alkoxide, it is important that the chlorine content ratio can be easily controlled. The first method and the third method have this problem and are difficult to consider in terms of actual production capacity, and the second method has the problem that a product with a uniform composition cannot be obtained.

Another important point is the issue of concentration.

Normally, when the obtained solution is used as a coating film for various purposes, it is necessary to mix the solution with various solvents to adjust the viscosity and the amount of evaporation of the solvent. For this reason, the stock solution itself needs to be highly concentrated, and a highly concentrated solution is very advantageous in terms of transportation costs. However, in the conventional method, a method of directly producing a highly concentrated source was not used, and when a highly concentrated source was required, concentration was performed, but concentration is usually performed by vacuum distillation etc. In this case, it is easy to absorb moisture in the air, and hydrolysis is accelerated due to the addition of superheating, especially Te, Zr, Fe
There was a problem in that even a trace amount of water tends to cause gelation.

[Means for Solving the Problems] The present invention has been made in view of the conventional problems, and as a result of intensive studies on a method for directly producing high-concentration chlorine-containing metal alkoxides, By using solid or liquid metal chlorides, which were considered to be stable and difficult to handle, and directly reacting them with alkali metal alkoxides obtained by reacting alcohol with alkali metals, it is possible to create highly concentrated and long-term stable compositions. It has been found that it is possible to produce chlorine-containing metal alkoxides that retain That is, in the present invention, 1 gram equivalent of metal chloride (MCI) is directly reacted with an alkali metal at a ratio of not more than n gram equivalent, and 0
．． MCI--X(O
This is a method for producing a chlorine-containing metal alkoxide having the composition R).

The metal chloride used in the present invention is T1Cl4, GeC14,5nC14, AsC13 as a liquid.
, 5bC16, 5iC14, TeCl a, and as solids TaC16, ZrC14, 5nC12, FeC
13, NbC16, 5bC13, and CuC12, but all of these are used as anhydrous salts that do not contain water, and dehydrated alcohol must be used for alcohol, and when dissolved in alcohol, it is necessary to avoid exposure to atmospheric moisture. The atmosphere must be replaced with dry gas and sealed to prevent contact. Furthermore, the alkali metal alkoxide obtained by the reaction of an alkali metal and an alcohol needs to be sufficiently cooled before reacting with a chloride. When a metal chloride is a liquid in a reaction with a chloride, the liquid gold member chloride is slowly dropped into the cooled solution of alkali metal alkoxide using an isobaric funnel, etc. The zero dropping rate is a method that can be used to monitor the reaction. It is necessary to change the temperature while watching it so that the liquid temperature does not rise. In addition, if the metal chloride is solid, after completely replacing the air in the container with nitrogen, etc., add the solid metal chloride first, then add the sufficiently cooled alkali metal alkoxide while stirring the solid. The alcohol used in the present invention is one having an alkyl group having 1 to 1 carbon atoms, or a polyhydric alcohol.

According to the production method of the present invention, a solution having a concentration of 0.8 mol/7 or more can be produced, and the chlorine content ratio of this metal alkoxide can be arbitrarily adjusted by adjusting the ratio of alkali metal alkoxide to metal chloride. That is, the reaction involves an alkali metal alkoxide and a metal chloride (M
The exchange reaction of CI,) with chlorine produces alkali metal chloride, and the substituted proportion of alkoxide coordinates to the metal. The content of chlorine can be controlled arbitrarily by setting it to an arbitrary ratio equal to or less than n grams. The alkali metals used are Na, Li,
etc. The highly concentrated chlorine-containing metal alkoxide obtained by the above method is very stable, and the conventional fully substituted alkoxide [M(OR), N] has a pot life of several days in an atmospheric exposure test. However, it is known that the product of the present invention is stable for several months, and since this solution is highly concentrated, transportation costs are very low, and it can be used depending on the purpose of actual use. It is possible to select the viscosity, concentration solvent, etc. using each diluting solvent.

Examples of diluting solvents include hydrocarbons such as hexane, peptane, and cyclohexane, aromatics such as benzene and toluene, alcohols such as methanol and ethanol, polyhydric alcohols such as ethylene glycol, and ethyl acetate and diethyl acetate such as ethylene acetate and butylene acetate. Examples include ketones, ketones such as acetone, TFIF, and chloroform.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Add ioo of n-butanol to a No. 21 Mitsuro flask.

ml, cooled sufficiently, and added 69 g of sodium in several portions. The reaction proceeds while generating hydrogen,
A sodium butoxide solution with a concentration of 3.0 mol/l is produced. This solution was sufficiently cooled f&(5 to 10
°C), 189.7 g of TiC14 stock solution is added using a roller pump. At this time, a large amount of heat is generated, so while cooling the liquid, change the charging speed while monitoring the temperature of the liquid.
The reaction was completed in about 1 to 2 hours, and Ti(OnBu) 3
A yellow solution with a C1 composition and a concentration of 0.95 sol/1 was obtained. No change was observed in this solution even when it was left in the atmosphere for more than one month.

Example 2 1000 m of n-proper tool was added to a 21-meter Mitsuro flask.
Take 110ml of sodium and add 110ml of sodium while cooling thoroughly.
Add 4 grams in several doses. The reaction proceeds while generating hydrogen, 4.8 mol/l! A sodium butoxide solution with a concentration of is produced. - Take 4349.5 g of ZrCl in a separate container (No. 21 Mitsuro flask), quickly weigh it into a container purged with nitrogen to prevent the powder from absorbing moisture in the air, and slowly stir the powder. , slowly add the cooled sodium butoxide solution. The surroundings of the container are sufficiently cooled, and the addition rate is changed while monitoring the amount of heat generated so as not to raise the liquid temperature too much.The reaction is completed in about 2 to 3 hours.

The composition, color tone, and concentration of the product are shown in Table 1. No change was observed in this solution even when it was left in the air for more than one month.

Examples 3 to 13° The same apparatus as in Example 1 was used in the case of a liquid, and the same as in Example 2 was used in the case of a solid, and the same operations were carried out. Types and amounts of metal chlorides, alcohols, and alkali metals used,
The composition, concentration, color tone, and stability of the produced solutions are shown in Table 1. Regarding stability, those that did not change in the atmosphere for one month were designated as O, and those that slightly formed a precipitate at the bottom were designated as Δ.

Table 1 Comparative Example 1 1000 l of n-butanol was added to 3! The mixture was placed in a Mitsuro flask and cooled sufficiently. After purging the inside of the flask with nitrogen gas, 4284.6 g of T1Cl was gradually added dropwise to it.
A yellow solution was obtained.

This solution was blown with NH at a rate of 500-1/inch.
3 gases were blown in. After 1 hour of blowing, a large amount of NH and CI was produced, and the slurry became viscous and difficult to stir, so benzene was added to 800 mj! I continued blowing, but it became viscous again, so I continued blowing for another 800m! In addition, I continued to blow. Since the reaction was completed in 3 hours, hot-colored transparent Ti (OBua) was obtained after two separate reactions.

The concentration was 0.52 mol/7+.

This solution gelled in about 2 days when exposed to the atmosphere.

Comparative Example 2 1800 liters of n-butanol was placed in a No. 21 Mitsulo flask and cooled sufficiently. 7 g of TiC14189 was gradually added to this to obtain a 1.16 mol/1 solution. This is called liquid A.

1 part n-butanol in a separate container (21 Mitsuro flasks)
A total of 200 liters was taken, and 69 g of Na was added while cooling sufficiently to obtain 2.5 mol/1 Na0Bu. This is called liquid B.

After the reaction in which the above solution A is gradually added to solution B using a roller pump, the generated NaCl is separated by P and the composition is Ti (OBu).
A solution of 3C1 with a concentration of 0.49 mol/l was obtained.

The obtained solution was vacuum distilled and concentrated to a concentration of 1.2 mol/1, which gelled in 4 days.

[Effects] The chlorine-containing metal alkoxide produced in the present invention can be used for various purposes. For example, when a film is formed using this as a raw material, it improves optical properties, electromagnetic properties, dielectric properties, oxidation protective film, and abrasion resistance. Applications include functional membranes with properties such as membranes, doping agents and sintering aids for ceramic powders that utilize the production of ultrafine powders through hydrolysis, fibers, porous bodies, and porous materials using the sol-gel method. A shaped glass body etc. can be made. Furthermore, in order to accommodate these various uses and functions, chlorine-containing metal alkoxides can be used not only alone, but also in combination of two or more types to provide better properties.

Claims (1)

[Claims] MCI having a concentration of 0.8 mol/l or more by directly reacting an alkali metal alkoxide with 1 gram equivalent of metal chloride (MCI_n) at a ratio of n gram equivalent or less
A method for producing a chlorine-containing metal alkoxide having the composition _n_-_x(OR)_x.