JPH08804B2 - Method for producing isocyanates - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an isocyanate or a carbamic acid ester or a thiocarbamic acid ester (hereinafter collectively referred to as carbamic acid esters) in the presence of a catalyst by thermal decomposition in the gas phase. The present invention relates to a method for obtaining a thioisocyanate (hereinafter, these are collectively referred to as isocyanates) in high yield. Isocyanates are highly reactive and useful compounds widely used as raw materials for urethanes, pharmaceuticals, agricultural chemicals and the like.

[0002]

BACKGROUND OF THE INVENTION Isocyanates are industrially produced by reacting amines with phosgene, but this method uses highly toxic phosgene and produces a large amount of hydrogen chloride that corrodes equipment. Since it has serious problems such as the above, a method for producing isocyanates without using phosgene is strongly desired.

As one of them, a number of methods by thermal decomposition of carbamic acid esters have been proposed. They are a method carried out in a liquid phase in the presence of a catalyst and a method carried out in a high temperature gas phase in the presence of a catalyst. It is roughly divided into.

As an example of the liquid phase reaction, a method using a basic catalyst such as an alkaline earth metal and its inorganic compound (JP-A-54-88201), a heavy metal catalyst or a heavy metal compound catalyst in an inert solvent is used. Method (JP-A-51-197)
21), Ib, IIb, IIIa, IVa, IVb in an inert solvent,
Method using at least one metal compound catalyst selected from the group consisting of Vb and VIII (JP-A-56-16616)
0), a method of using zinc chloride as a catalyst (JP-A-57-21).
356), a method of using a compound of Tl, Sn, Sb, and Zr as a catalyst (JP-A-58-128354), and a simple substance of Mn, Mo, W, or Zn in a high-boiling solvent or a metal compound under reduced pressure. A method (JP-A-2-134355) and the like are disclosed. However, all of these methods use a catalyst that is homogeneously dissolved in the reaction solution, which requires a large amount of energy to separate the catalyst from the decomposition products and also allows the incorporation of catalyst components into the products. In addition, the catalyst is difficult to recover and reuse, and must be disposed of as waste.

As an effective method for solving these problems, a method using a solid catalyst insoluble in the reaction solution under the reaction conditions has been proposed. For example, a method in which surface-rich metal zinc, aluminum, titanium, iron, chromium, cobalt, and nickel are used as catalysts (JP-A-56-65857), copper group, zinc group, aluminum group, carbon group other than carbon, and A method of using a titanium group simple substance, an oxide or a sulfide as a catalyst (JP-A-57-158747), and a method of using a carbon group other than carbon, a titanium group, a vanadium group, a chromium group of carbides and nitrides as a catalyst. (JP-A-57-158748),
Method using a boron-containing catalyst (JP-A-57-15874)
8) etc. are disclosed. However, since these methods have low catalyst activity and use a relatively large amount of solvent, the productivity of the isocyanate is low for industrial implementation, and further, the cost for separating and recovering the solvent is high. It costs.

On the other hand, as an example of the gas phase reaction, a method of carrying out a gas phase thermal decomposition reaction at 400 ° C. to 600 ° C. in the presence of a Lewis acid catalyst (JP-A-46-17773) is disclosed. The method has the drawbacks that a large amount of polymer is by-produced, the catalyst is thermally decomposed to have a short life, the reactor is corroded, and the yield of the target product is low. Further, a method of carrying out under reduced pressure in a gas phase in the presence of a heat-resistant gas-permeable filler composed of steel, brass, copper, zinc, aluminum, titanium, chromium, cobalt, nickel, carbon and quartz (JP-A-59-59). 20535
2 and Japanese Patent Laid-Open No. 59-205353), this method has a low yield of the desired product and is also useful under reduced pressure.
Since it is carried out at a high temperature of 0 ° C., the equipment cost is high.

As described above, there is an example in which a solid acid or a solid base is used as a catalyst for a gas phase thermal decomposition reaction of carbamic acid esters into isocyanates.
All of them have low yields and a large amount of by-products of polymers or urea compounds, and industrially usable gas phase reaction catalysts have not yet been obtained.

[0008]

DISCLOSURE OF THE INVENTION In the present invention, when a carbamic acid ester is pyrolyzed to produce an isocyanate, a low yield of the objective isocyanate as described above, separation and recovery of a catalyst and a solvent are obtained. To solve problems such as difficulty in production, increase in cost, and by-product of polymer, and easy separation of product and catalyst, high space-time yield, high selectivity and stable isocyanate for a long time. It provides a method of obtaining a class.

[0009]

Means for Solving the Problems The inventors of the present invention have earnestly studied a method of thermally decomposing carbamic acid esters to produce isocyanates, and as a result, have found that an oxide sintered body is used as a catalyst for a gas phase thermal decomposition reaction. As a result, it was found that the objective isocyanates can be obtained in high yield and stably for a long time, and the present invention has been completed. The carbamic acid ester used in the present invention is a compound having a -NHCOO- group or a -NHCOS- group, and is a halogen group which is inactive to a saturated or unsaturated aliphatic group, aromatic group, or isocyanate group. , Nitro group, cyano group,
It may have a substituent such as an alkoxy group or an acyl group, but it must have a vapor pressure capable of being substantially used for a gas phase reaction under normal pressure or reduced pressure.

Examples of such carbamic acid esters include methylcarbamic acid, ethylcarbamic acid,
Propylcarbamic acid, butylcarbamic acid, pentylcarbamic acid, hexylcarbamic acid, etc., alkylcarbamic acid esters such as methyl ester, ethyl ester, propyl ester, butyl ester, hydroxyethyl ester, phenyl ester, etc., cyclopentylcarbamic acid, cyclohexylcarbamine Aliphatic carbamic acid esters such as acids such as methyl ester, ethyl ester, propyl ester, butyl ester, hydroxyethyl ester, phenyl ester, ethylene dicarbamic acid, propylene dicarbamic acid, butylene dicarbamic acid, pentamethylene diester Carbamic acid, hexamethylene dicarbamic acid, etc., dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihydroxyethyl Alkylene dicarbamic acid diesters such as stell and diphenyl ester, 1,4-cyclohexyl dicarbamic acid, isophorone dicarbamic acid and the like, dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihydroxyethyl ester, diphenyl ester, etc. Alicyclic dicarbamic acid diesters, phenylcarbamic acid, tolylcarbamic acid, etc. methyl ester, ethyl ester, propyl ester, butyl ester, hydroxyethyl ester,
Aromatic carbamic acid esters such as phenyl ester,
Phenyl ester, diethyl ester, dipropyl ester, dibutyl ester, such as phenylenedicarbamic acid, 2,4- or 2,6-tolylenedicarbamic acid,
Examples thereof include aromatic dicarbamic acid diesters such as dihydroxyethyl ester and diphenyl ester, and thiolcarbamic acid esters thereof, but the present invention is not limited thereto.

The catalyst used in the present invention is an oxide sintered body. In general, oxide particles are bonded to each other by heating at a high temperature to form larger particles. This phenomenon is called sintering. In sintering, a physical change causes volume contraction due to a decrease in interparticle voids, and a chemical change causes a decrease in strength and amount of acid-base points of an oxide. Therefore, the oxide-sintered body has a weak acid-base strength, a small amount of acid and base points, and a specific surface area of several m ^2.
The substance is considered to be inactive as a catalyst because of the following, and its use as a catalyst has not been considered at all. Therefore,
There is no case where the carbamic acid ester was used for the gas-phase thermal decomposition reaction of isocyanates.

Among oxide sintered bodies, in the periodic table
Oxide sintered body of at least one element selected from the group IIIa element, the group IVa element and the group Va element, or the oxide sintered body containing an alkali metal element and / or an alkaline earth metal element in these elements The association shows excellent performance.
Examples of IIIa, IVa, and Va group elements include B, Al, and G.
Examples thereof include a, Tl, Si, Sn, Pb, P, Sb and Bi, but the catalyst according to the present invention is not limited thereto.

These are used in the form of either a single oxide or a complex oxide. In the present invention, oxide sinters also include sintered bodies of various oxo acid salts (phosphate, borate, aluminate, silicate, etc.).

The method for preparing the catalyst is not particularly limited, and any commonly used method can be applied. Raw materials for the catalyst are oxides, oxide sols, hydroxides, halides,
Salts (carbonate, sulfate, nitrate, organic acid salt, ammonium salt, etc.), oxo acid salts (phosphate, borate, aluminate, silicate, etc.) and metals are used.

As an example of the method for preparing the catalyst of the present invention, various catalyst raw materials are dissolved or suspended in water, heated and concentrated under stirring, molded and dried and sintered to obtain a catalyst, or various catalyst raw materials are submerged in water. After dissolving or suspending and adjusting the pH to make hydroxide, filtration, washing with water, molding, drying,
A method in which a catalyst is obtained through sintering, and further, a method in which oxides or hydroxides of various elements are mixed as powders with an appropriate molding aid (for example, water, alcohol, etc.), molded, dried, and sintered. Etc. The sintering temperature depends on the constituent elements of the oxide and is usually 800 ° C to 2000 ° C.

In carrying out the present invention, the reactor may be either a fixed bed flow type or a fluidized bed type. The reaction can be carried out at normal pressure or under reduced pressure using an inert gas such as nitrogen, helium or argon as a diluent, or under reduced pressure without using an inert gas for dilution. The depressurization reaction varies depending on the kind of the raw material carbamate, and is usually 1 mmHg to 5 mm.
It is in the range of 00 mmHg. The space velocity is 500 / hr to 20000 / hr, preferably 1000 / hr to 10000 / hr when a diluent is used, and 10 / hr to 1000 / hr when a reduced pressure reaction without a diluent is used.
It is preferably 50 / hr to 500 / hr. The reaction temperature is usually 250 ° C. to 450 ° C., though it depends on the kind of raw material.

[0017]

The details of the cause of the high performance of the catalyst according to the present invention are unknown, but in the gas phase thermal decomposition reaction of carbamic acid esters carried out at a relatively high temperature, the catalytic active site (acid site and base It is considered that if the strength of point is too strong, the decomposition reaction into other than the desired isocyanates and the polymerization of the raw material or the produced isocyanates are likely to occur.
The catalyst according to the present invention is an oxide sintered at a very high temperature, its active site strength is weak and nearly neutral, and its specific surface area is very small, less than a few m ^2. With respect to the thermal decomposition reaction, weak acid points and basic points act in cooperation to exert sufficient activity, and there are no unnecessary high-strength active points, and since the specific surface area is small, The desorption of the product from the catalyst becomes rapid,
It is considered that such high performance is exhibited.

[0018]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The conversion of carbamate, the selectivity of isocyanate, and the single-flow yield of isocyanate in the examples are defined as follows.

Carbamate conversion rate (mol%) =
(Mole number of reacted carbamic acid ester) / (Mole number of supplied carbamic acid ester) × 100 Selectivity of isocyanate (mol%) = (Mole number of produced isocyanate) / (Mole of reacted carbamic acid ester) Number) × 100 Single-flow yield of isocyanate (mol%) = (mol number of produced isocyanate) / (mol number of fed carbamate) × 100 Example 1. Alumina sol (A
15 g (containing 20% by weight of 1 ₂ O ₃ ) was added and kneaded, followed by drying in air at 120 ° C. for 6 hours and sintering at 1400 ° C. for 2 hours to obtain a catalyst.

5 m of this catalyst crushed to 9-16 mesh
1 was filled in a stainless steel reaction tube having an inner diameter of 10 mm, and
After dipping in a molten salt bath at 0 ° C., a raw material gas containing 10% by volume of methyl ethylcarbamate and 90% by volume of nitrogen was passed through the reaction tube at a space velocity of 2000 / hr (STP) to carry out a reaction. The reaction products are collected separately by infrared absorption spectrum,
It was identified by nuclear magnetic resonance spectrum, weight spectrum, etc., and was collected in dioxane and quantified by gas chromatography. Table 1 shows the reaction conditions, and Table 2 shows the reaction results.

Example 2. Aluminum nitrate (9 hydrate)
37.5 g and 0.43 g of sodium nitrate were dissolved in 100 g of water, and then ammonia water was added to adjust the pH to 8, and the mixture was concentrated to dryness in a 90 ° C water bath. The obtained solid is dried in air at 120 ° C for 6 hours, and further at 230 ° C for 12 hours.
It was dried at high temperature for an hour. Then bake at 1000 ° C for 2 hours,
After sintering at 1400 ° C. for 2 hours, a catalyst having a composition of Al ₂₀ Na ₁ was obtained.

Using 5 ml of the catalyst crushed to 9 to 16 mesh, the thermal decomposition reaction of ethyl carbamic acid phenyl ester was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 and Table 2
The results shown in are obtained.

Example 3. After adding 10 g of water to 20.0 g of silicon oxide and 1.9 g of magnesium hydroxide and kneading, drying in air at 120 ° C. for 6 hours, firing at 1000 ° C. for 2 hours, and sintering at 1400 ° C. for 2 hours to remove oxygen. A catalyst having a composition of Si ₁₀ Mg _{1 in an} atomic ratio other than that obtained was obtained.

The thermal decomposition reaction of ethyl ethylcarbamic acid hydroxyethyl ester was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 using 5 ml of the catalyst crushed to 9 to 16 mesh, and the results shown in Table 2 were obtained. .

Example 4. 10 kg of water was added to 26.9 g of tin oxide and 0.74 g of calcium hydroxide and kneaded, followed by drying in air at 120 ° C. for 6 hours and firing at 1000 ° C. for 2 hours.
Sintered at 1400 ℃ for 2 hours, Sn in atomic ratio excluding oxygen
A catalyst having a composition of ₂₀ Ca ₁ was obtained.

Using 5 ml of the catalyst crushed to 9 to 16 mesh, the thermal decomposition reaction of cyclohexylcarbamic acid ethyl ester was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Example 5. 33.1 g of lead nitrate and 1.1 g of strontium nitrate were dissolved in 150 g of water, then ammonia water was added to adjust the pH to 8, and the mixture was concentrated to dryness in a 90 ° C water bath. The obtained solid is dried in air at 120 ° C. for 6 hours, at 230 ° C. for 12 hours at high temperature, and at 1000 ° C. for 2 hours.
Time calcination and sintering at 1400 ° C. for 2 hours gave a catalyst having a composition of Pb ₂₀ Sr ₁ in terms of atomic ratio excluding oxygen.

2.5 m of catalyst crushed to 9-16 mesh
Using 1, the thermal decomposition reaction of cyclohexylcarbamic acid hydroxyethyl ester was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 to obtain the results shown in Table 2.

Example 6. To 29.2 g of antimony oxide,
A solution of 0.56 g of potassium hydroxide in 10 g of water was added and kneaded, followed by drying in air at 120 ° C. for 6 hours and at 1000 ° C. for 2 hours.
Time calcination and sintering at 1400 ° C. for 2 hours gave a catalyst having a composition of Sb ₂₀ K ₁ in terms of atomic ratio excluding oxygen.

2.5 m of catalyst crushed to 9-16 mesh
The thermal decomposition reaction of phenylcarbamic acid methyl ester was carried out using 1 under the reaction conditions shown in Table 1 in the same manner as in Example 1 to obtain the results shown in Table 2.

Example 7. After 3.5 g of boron oxide and 11.5 g of 85% phosphoric acid were heated and mixed, 30 g of silicon oxide and 10 g of water were added and kneaded, and the mixture was dried in air at 120 ° C. for 6 hours, calcined at 1000 ° C. for 2 hours, and 1200 ° C. After sintering for 2 hours, a catalyst having a composition of B ₁ P ₁ Si ₅ in terms of atomic ratio excluding oxygen was obtained.

The thermal decomposition reaction of carbamic acid methyl ester of isocyanatoethyl methacrylate was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 1 using 5 ml of the catalyst crushed to 9 to 16 mesh, and the results shown in Table 2 were obtained. Obtained.

Example 8. After kneading 30 g of aluminum phosphate and 20 g of water, drying in air at 120 ° C. for 2 hours, 10
Firing at 00 ° C. for 2 hours and sintering at 1400 ° C. for 2 hours gave a catalyst having a composition of Al ₁ P ₁ in terms of atomic ratio excluding oxygen.

The thermal decomposition reaction of carbamic acid hydroxyethyl ester of isocyanatoethyl methacrylate was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1 using 5 ml of the catalyst crushed to 9 to 16 mesh to obtain the results shown in Table 2. Got

Example 9. After kneading 30 g of tricalcium phosphate and 20 g of water, drying in air at 120 ° C. for 2 hours, 10
The catalyst was fired at 00 ° C. for 2 hours and sintered at 1400 ° C. for 2 hours to obtain a catalyst having a composition of P ₂ Ca _{3 in} terms of atomic ratio excluding oxygen.

Using 5 ml of a catalyst crushed to 9 to 16 mesh, a reaction pressure of 10 mmHg, a reaction temperature of 350 ° C., a space velocity of 200 / hr (STP), and a concentration of 100% by volume of isophorone dicarbamic acid dimethyl ester were supplied. A thermal decomposition reaction was performed. The reaction product was collected by cooling, dissolved in dioxane, and quantified by gas chromatography. Table 1 shows the reaction conditions, and Table 2 shows the reaction results.

Example 10. A solution of cesium nitrate (7.8 g) and diammonium phosphate (5.3 g) in water (30 g) was added to silicon oxide (12 g) and kneaded.
Time drying, high temperature drying at 230 ° C. for 12 hours, firing at 1000 ° C. for 2 hours, and sintering at 1400 ° C. for 2 hours to obtain a catalyst having a composition of Si ₅ P ₁ Cs _{1 in} terms of atomic ratio excluding oxygen.

Using 5 ml of the catalyst crushed to 9 to 16 mesh, the thermal decomposition reaction of 2,4-toluylenedicarbamic acid dimethyl ester was carried out under the reaction conditions shown in Table 1 in the same manner as in Example 9 and shown in Table 2. I got the result.

[0040]

[Table 1]

[0041]

[Table 2]

Comparative Example 1. The calcination temperature of the catalyst of Example 4 was set to 5
Catalyst preparation and reaction were performed in exactly the same manner as in Example 4 except that the temperature was set to 00 ° C. and sintering was not performed. As a result, the conversion rate of cyclohexylcarbamic acid ethyl ester was 90.
Although it was as high as mol%, there were many solid products (urea compounds) as by-products, and the selectivity and yield of the target cyclohexyl isocyanate were extremely low, 33 mol% and 30 mol%, respectively. In this reaction, continuous reaction was impossible due to clogging of the side tube of the reaction tube with solid matter.

[0043]

INDUSTRIAL APPLICABILITY When the catalyst according to the present invention is used in the gas phase thermal decomposition reaction of carbamic acid esters to isocyanates, the isocyanates are continuously produced in a high space-time yield with high selectivity. it can. Moreover, since this continuous reaction does not accompany by-products of the polymer, it can be continued stably for a long time. Furthermore,
Since the carbamic acid ester is converted into the isocyanate only by passing through the catalyst layer, there is no need to separate and recover the catalyst, and no catalyst-containing waste liquid is generated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location // B01J 21/04 21/10 X 23/04 X 23/14 X 27/18 X 27/182 X C07B 61/00 300

Claims (2)

[Claims] 1. A group IIIa element in the periodic table, IV
At least one selected from Group a elements and Group Va elements
A method for producing isocyanates, which comprises thermally decomposing carbamic acid esters in a gas phase using an oxide sintered body of one kind of element as a catalyst. 2. The method according to claim 1, wherein the catalyst is an oxide sintered body containing an alkali metal element and / or an alkaline earth metal element.