JP2764081B2 - Method for producing alicyclic-aliphatic diisocyanate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing an alicyclic-aliphatic diisocyanate from an alicyclic-aliphatic diamine as a starting material.

[Conventional technology]

Obtaining isocyanates by reacting the corresponding amines or salts thereof with phosgene has long been practiced.
When the amine is aromatic, the reaction rate between the amine and isocyanate, which is a side reaction, is relatively suppressed because the reaction rate between the amine and phosgene is high. However, when the amine is alicyclic-aliphatic, In this case, urea is easily generated by the reaction between the amine and the isocyanate, which is a main cause of the decrease in the yield.

Further, when the amine is alicyclic-aliphatic, a reaction between urea and phosgene produced as a by-product occurs, and a compound in which the -NCO group of the target isocyanate is substituted with -C1 is produced as a by-product. These compounds are difficult to separate and are often present as impurities in the target isocyanate, and are not preferred because they act as hydrolyzable chlorine.

In addition, the by-produced urea reacts with phosgene to produce other impurities containing hydrolyzable chlorine. These hydrolyzable chlorine-containing substances often hinder the use of diisocyanates in terms of quality.

As described above, preventing the reaction between the amine and the isocyanate is particularly important in the alicyclic-aliphatic phosgenation reaction, and thus, the reaction with the isocyanate is protected by protecting the amine as a salt such as hydrochloric acid. Delay,
The preferential reaction with phosgene has been practiced for a long time.

However, in this case, there are the following problems.

[Problems to be Solved by the Invention] For the reasons described above, a salt-forming reaction of converting an amine into a salt such as a hydrochloride is performed prior to the phosgenation reaction. It does not dissolve and becomes a slurry. However, in the case of an alicyclic-aliphatic amine, salts formed during the salt-forming reaction aggregate in an organic solvent to form solid particles having a large diameter, which hinders the progress of the salt-forming reaction or converts the amine into particles. It is often involved in preventing salt formation from being completed.

Further, if the phosgenation reaction is carried out in the presence of such large-diameter solid particles, the yield will decrease and the amount of hydrolyzable chlorine will increase.

Further, as a solvent for the salt-forming reaction, for example, when a fatty acid ester which is prepared by a smooth preparation of the hydrochloride salt of an amine and does not agglomerate is used, the boiling point is low, and when the next phosgenation reaction is directly performed at normal pressure, Not enough reaction temperature can be reached. When the reaction temperature of the phosgenation is lower than a predetermined value, the reaction time becomes longer, so that not only efficiency is poor, but also the production of by-products increases and the yield decreases.

Although the reaction temperature can be increased by increasing the pressure of the phosgenation reaction, the operating pressure of a device for handling toxic phosgene is increased, which is not preferable for safety and security.

On the other hand, as solvents for the phosgenation reaction, hydrocarbons,
There are fatty acid esters, chlorinated hydrocarbons, etc., and solvents with a relatively high boiling point at normal pressure include chlorobenzene and ortho-dichlorobenzene. However, there was a disadvantage that the salt formation reaction did not proceed smoothly.

As described above, the types of solvents suitable for the salt formation reaction and the phosgenation reaction are different, so after the salt formation reaction is completed, the solvent is removed, the amine salt is taken out as a solid, and this is converted into a solvent suitable for phosgenation. In some cases, phosgenation is carried out by dispersion. In this case, operations such as handling solids are complicated and costly. In addition, since the solvent is replaced with a solvent for phosgenation in the form of a salt, solidification and the like of the solids occur at this point, deteriorating the liquid properties.

Therefore, it is necessary to find a production method in which both the salt formation reaction and the phosgenation reaction proceed smoothly continuously.

[Means for solving the problem]

The inventors of the present application have conducted intensive studies to solve the above-described problems, and as a result, have found the following facts.

The present invention relates to a method for producing an isocyanate by reacting an alicyclic-aliphatic amine compound with phosgene via a hydrochloride, which is preferably used for both salt formation and reaction with phosgene, that is, phosgenation. An object of the present invention is to provide a method for producing an alicyclic-aliphatic diisocyanate, which comprises continuously reacting both steps of salt formation and phosgenation by using a usable solvent.

That is, "Formula [I] (Where k = 0 to 2, j, m = 1 to 5, n = 0 to 2) In the method for producing an alicyclic-aliphatic diisocyanate represented by the formula (II) (Where k, j, m, and n are the same as those of the formula [I]), and the alicyclic-aliphatic diamine represented by the formula [I] is used as a starting material. Formula (III) from a cyclic aliphatic diamine and hydrogen chloride (Here, k = 0 to 2, j, m = 1 to 5, n = 0 to 2) A salt-forming step for producing an alicyclic-aliphatic diamine hydrochloride [III].

And a phosgenation step of reacting the formula (III) with phosgene to produce the structural formula [I] as a second step reaction.

In the salt formation step, a solvent that forms a uniform slurry (hereinafter referred to as solvent A) is selected from the inert solvents used in the salt formation step and the phosgenation step. In the case where the reaction temperature is 145 ° C. or higher when the reaction is carried out at normal pressure, the boiling point at normal pressure is 1
A solvent having a temperature of 45 ° C. or higher (hereinafter referred to as “solvent B”) is selected, and a mixture of the solvent A and the solvent B is prepared so that the ratio of the solvent B is 50% by weight or more and 90% by weight or less. A process for producing an alicyclic-aliphatic diisocyanate, wherein the step of producing a salt and the step of phosgenation are successively reacted by using the salt and a solvent for phosgenation. .

Formula (II) as starting material (Where k, j, m, and n are the same as those of the formula [I]), the alicyclic-aliphatic diamine represented by k = 0, n = 0, 1,3-di (amino Methyl) -cyclohexane, 1,4-di (aminomethyl) -cyclohexane, 1,3-di (aminoethyl) -cyclohexane, 1,4-di (aminoethyl)
-Cyclohexane, 1-aminomethyl-3, (4) -aminoethyl-cyclohexane, 1-aminomethyl-3,
(4) -aminopropyl-cyclohexane, 1-aminomethyl-3, (4) -aminobutyl-cyclohexane, 1
-Aminomethyl-3, (4) -aminopentyl-cyclohexane, 1-aminoethyl-3, (4) -aminopropyl-cyclohexane, 1-aminoethyl-3, (4) -aminobutyl-cyclohexane, 1-amino Methyl-3,
(4) -aminopentyl-cyclohexane and the like, where k = 0, n = 1, 3 (4), 7 (8) -di (aminomethyl) bicyclo [4,3,
0 ^1,6 ] nonane, 3 (4) -aminomethyl-7 (8) -aminoethylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -aminoethyl-7 (8) -aminomethyl Bicyclo (4,3,0
^1,6 ] nonane, 3 (4) -aminomethyl-7 (8) -aminopropylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4)-
Aminopropyl-7 (8) -aminomethylbicyclo [4,
3,0 ^1,6 ] nonane, 3 (4) -aminomethyl-7 (8)-
Aminobutylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4)-
Aminobutyl-7 (8) -aminomethylbicyclo [4,3,
0 ^1,6 ] nonane, 3 (4) -aminomethyl-7 (8) -aminopentylbicyclo [4,3,0 ^1,6 ] nonane, 3 (4)-
Aminopentyl-7 (8) -aminomethylbicyclo [4,
3,0 ^1,6 ] nonane, 3 (4), 7 (8) -di (aminoethyl) bicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -aminoethyl-7 (8)- Aminopropyl bicyclo [4,3,0 ^1,6 ]
Nonane, 3 (4) - aminopropyl -7 (8) - aminoethyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - aminoethyl -7 (8) - aminobutyl bicyclo [4,3 , 0 ^1,6 ]
Nonane, 3 (4) - aminobutyl -7 (8) - aminoethyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - aminoethyl -7 (8) - amino pentylbicyclo [4,3 , 0 ^1,6 ]
Nonane, 3 (4) - aminopentyl -7 (8) - aminoethyl bicyclo [4,3,0 ^1,6] nonane can be mentioned, k = 1,
Assuming that n = 0, 2,5 (6) -di (aminomethyl) bicyclo [2,2,1] heptane, 2-aminomethyl-5
(6) -aminoethylbicyclo [2,2,1] heptane, 2
-Aminomethyl-5 (6) -aminopropylbicyclo [2,2,1] heptane, 2-aminomethyl-5 (6) -aminobutylbicyclo [2,2,1] heptane, 2-aminomethyl-5 ( 6) -Aminopentylbicyclo [2,2,1] heptane, 2,5 (6) -di (aminoethyl) bicyclo [2,
2,1] heptane, 2-aminoethyl-5 (6) -aminopropylbicyclo [2,2,1] heptane, 2-aminoethyl-5 (6) -aminobutylbicyclo [2,2,1] heptane, 2-aminoethyl-5 (6) -aminopentylbicyclo [2,2,1] heptane and the like.

Assuming that k = 2, n = 0, 2,5 (6) -di (aminomethyl) bicyclo [2,2,2] octane, 2-aminomethyl-5 (6) -aminoethylbicyclo [2,2 , 2] octane, 2-aminomethyl-5 (6)
-Aminopropylbicyclo [2,2,2] octane, 2-aminomethyl-5 (6) -aminobutylbicyclo [2,2,
2] octane, 2-aminomethyl-5 (6) -aminopentylbicyclo [2,2,2] octane, 2,5 (6) -di (aminoethyl) bicyclo [2,2,2] octane, 2- Aminoethyl-5 (6) -aminopropylbicyclo [2,2,2]
Octane, 2-aminoethyl-5 (6) -aminobutylbicyclo [2,2,2] octane, 2-aminoethyl-5
(6) -Aminopentylbicyclo [2,2,2] octane and the like.

Assuming that k = 1 and n = 1, 3 (4), 8 (9) -di (aminomethyl) tricyclo [5,
2,1,0 ^2,6 ] decane, 3 (4) -aminomethyl-8 (9)
-Aminoethyltricyclo [5,2,1,0 ^2,6 ] decane, 3
(4) - aminomethyl-8 (9) - aminopropyl tricyclo [5,2,1,0 ^2,6] decane, 3 (4) - aminomethyl-8 (9) - aminobutyl tricyclo [5, 2,1,0 ^1,6 ] decane, 3 (4) -aminomethyl-8 (9) -aminopentyltricyclo [5,2,1,0 ^2,6 ] decane, 3 (4), 8
(9) -Di (aminoethyl) tricyclo [5,2,1,0 ^2,6 ]
Decane, 3 (4) - aminoethyl -8 (9) - aminopropyl tricyclo [5,2,1,0 ^2,6] decane, 3 (4) - aminoethyl -8 (9) - aminobutyl tricycloalkyl (5,2,
1,0 ^2,6 ] decane, 3 (4) -aminoethyl-8 (9)-
Aminopentyltricyclo [5,2,1,0 ^2,6 ] decane;

Formula [I] which is the target substance (Here, k = 0 to 2, j, m = 1 to 5, n = 0 to 2) Examples of the alicyclic-aliphatic diisocyanate include the following.

Assuming that k = 0 and n = 0, 1,3-di (isocyanatomethyl) -cyclohexane, 1,4-di (isocyanatomethyl) -cyclohexane, 1,3-di (isocyanatoethyl) -cyclohexane, 1,4-di (isocyanatoethyl) -cyclohexane, 1-isocyanatoamino-3 (4) -isocyanatoethyl-cyclohexane, 1-isocyanatomethyl-3,
(4) -isocyanatopropyl-cyclohexane, 1-
Isocyanatomethyl-3, (4) -isocyanatobutyl-
Cyclohexane, 1-isocyanatomethyl-3, (4)-
Isocyanatopentyl-cyclohexane, 1-isocyanatoethyl-3, (4) -isocyanatopropyl-cyclohexane, 1-isocyanatoethyl-3, (4) -isocyanatobutyl-cyclohexane, 1-isocyanatomethyl-3, (4) -isocyanatopentyl-cyclohexane and the like.

as for k = 0, n = 1, 3 (4), 7 (8) - di (isocyanatomethyl) bicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatomethyl -
7 (8) - isocyanatoethyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatoethyl -7 (8) - isocyanatomethyl-bicyclo [4,3,0 ^1,6] nonane , 3 (4)
- isocyanatomethyl -7 (8) - isocyanatopropyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatopropyl -7 (8) - isocyanatomethyl-bicyclo [4,3,0 ^1,6 ] nonane, 3 (4) -isocyanatomethyl-
7 (8) - isocyanatobutyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatomethyl-butyl -7 (8) - isocyanatomethyl-bicyclo [4,3,0 ^1,6] nonane , 3 (4)
- isocyanatomethyl -7 (8) - isocyanatomethyl-pentylbicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatomethyl-pentyl-7 (8) - isocyanatomethyl-bicyclo [4,3,0 ^1,6 ] nonane, 3 (4), 7 (8) -di (isocyanatoethyl) bicyclo [4,3,0 ^1,6 ] nonane, 3 (4)-
Isocyanatoethyl -7 (8) - isocyanatopropyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatopropyl -7 (8) - isocyanatoethyl bicyclo [4,
3,0 ^1,6 ] nonane, 3 (4) -isocyanatoethyl-7
(8) - isocyanatobutyl bicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatomethyl-butyl -7 (8) - isocyanatoethyl bicyclo [4,3,0 ^1,6] nonane, 3 (4)-
Isocyanatoethyl -7 (8) - isocyanatomethyl-pentylbicyclo [4,3,0 ^1,6] nonane, 3 (4) - isocyanatomethyl-pentyl-7 (8) - isocyanatoethyl bicyclo [4,
3,0 ^1,6 ] nonane.

Assuming that k = 1 and n = 0, 2,5 (6) -di (isocyanatomethyl) bicyclo [2,2,
1] heptane, 2-isocyanatomethyl-5 (6) -isocyanatoethylbicyclo [2,2,1] heptane, 2-isocyanatomethyl-5 (6) -isocyanatopropylbicyclo [2,2,1] Heptane, 2-isocyanatomethyl-
5 (6) -isocyanatobutylbicyclo [2,2,1] heptane, 2-isocyanatomethyl-5 (6) -isocyanatopentylbicyclo [2,2,1] heptane, 2,5 (6) -di (Isocyanatoethyl) bicyclo [2,2,1] heptane,
2-isocyanatoethyl-5 (6) -isocyanatopropylbicyclo [2,2,1] heptane, 2-isocyanatoethyl-5 (6) -isocyanatobutylbicyclo [2,2,
1] heptane, 2-isocyanatoethyl-5 (6) -pentylbicyclo [2,2,1] heptane and the like.

Assuming that k = 2 and n = 0, 2,5 (6) -di (isocyanatomethyl) bicyclo [2,2,
2] octane, 2-isocyanatomethyl-5 (6) -isocyanatoethylbicyclo [2,2,2] octane, 2-isocyanatomethyl-5 (6) -isocyanatopropylbicyclo [2,2,2] Octane, 2-isocyanatomethyl-
5 (6) -isocyanatobutylbicyclo [2,2,2] octane, 2-isocyanatomethyl-5 (6) -isocyanatopentylbicyclo [2,2,2] octane, 2,5 (6) -di (Isocyanatoethoxy) bicyclo [2,2,2] octane, 2-isocyanatoethyl-5 (6) -isocyanatopropylbicyclo [2,2,2] octane, 2-isocyanatoethyl-5 (6)- Isocyanatobutyl bicyclo [2,
2,2] octane, 2-isocyanatoethyl-5 (6)-
And isocyanatopentylbicyclo [2,2,2] octane.

Assuming that k = 1 and n = 1, 3 (4), 8 (9) -di (isocyanatomethyl) tricyclo [5,2,1,0 ^2,6 ] decane, 3 (4) -isocyanatomethyl -8 (9) -isocyanatoethyltricyclo [5,2,1,
0 ^2,6 ] decane, 3 (4) -isocyanatomethyl-8
(9) -isocyanatopropyltricyclo [5,2,1,
0 ^2,6 ] decane, 3 (4) -isocyanatomethyl-8
(9) -isocyanatobutyltricyclo [5,2,1,0 ^2,6 ]
Decane, 3 (4) -isocyanatomethyl-8 (9) -isocyanatopentyltricyclo [5,2,1,0 ^2,6 ] decane,
3 (4), 8 (9) -di (isocyanatoethyl) tricyclo [5,2,1,0 ^2,6 ] decane, 3 (4) -isocyanatoethyl-8 (9) -isocyanatopropyltricyclo (5,2,
1,0 ^2,6 ] decane, 3 (4) -isocyanatoethyl-8
(9) -isocyanatobutyryltricyclo [5,2,1,
0 ^2,6 ] decane, 3 (4) -isocyanatoethyl-8
(9) -isocyanatopentyltricyclo [5,2,1,
0 ^2,6 ] decane.

Solvent A suitable for hydrochloride salt formation includes fatty acid esters and aromatic hydrocarbons, and specifically, ethyl acetate,
Examples include propyl acetate, n-butyl acetate, n-amyl acetate, isoamyl acetate, ethyl propionate, n-ethyl butyrate, toluene, and xylene. Of these, n-butyl acetate, n-amyl acetate, and isoamyl acetate having relatively high boiling points are particularly preferred.

Suitable solvents B for phosgenation include hydrocarbons, fatty acid esters and chlorinated hydrocarbons, such as toluene, xylene, tetralin, ethyl acetate, propyl acetate, n-butyl acetate, n-amyl acetate, isoamyl acetate. , Ethyl propionate, n-ethyl butyrate, ethyl phthalate, diethyl-isophthalate, diethyl carbitol, monochlorobenzene, orthodichlorobenzene, and trichlorobenzene. Among them, chlorinated hydrocarbons are most suitable as the inert solvent having a high boiling point, and include ortho-dichlorobenzene and trichlorobenzene.
Ortho-dichlorobenzene is most suitable especially when a reaction temperature of 145 ° C. or higher is desired.

The mixing ratio of the solvent A and the solvent B is, of course, to increase the ratio of A in order to advantageously perform salt formation, and to increase the ratio of B when phosgenation is prioritized.
In the present invention, in order to increase the reaction temperature of phosgenation as much as possible, the ratio of B is set to 50% or more, and even when the ratio of B is set to 75% or more, A
Is a point that determines the mixing ratio, that is, "a uniform slurry can be smoothly obtained by salt formation."

That is, the solvent is selected so that the boiling point of the mixed solvent at normal pressure is as high as possible and the salt formation is carried out smoothly as described above.
A, B and their mixing ratio must be determined.

Further, other factors that determine the solvents A and B and the mixing ratio thereof include volumetric efficiency. The solvents listed as candidates for the above-mentioned solvents A and B have a wide specific gravity (d ²⁰ ) of 0.87 to 1.25, and the volumetric efficiency of the reactor or the like is important for the selection of the solvent and the determination of the amine concentration in the solvent. Must be taken into account. In general, it can be said that increasing the ratio of a solvent having a large specific gravity, such as a chlorinated hydrocarbon, is advantageous in terms of volumetric efficiency under the condition that the same reaction results are obtained.

Such a solvent preferably contains a solvent (solvent B) having a boiling point of 145 ° C. or higher as a main component, that is, 50% by weight or higher, such that phosgenation at normal pressure proceeds at an appropriate rate.
This is obtained by mixing another solvent (solvent A) that forms a uniform slurry in the salt formation of the hydrochloride of an alicyclic-aliphatic amine compound.

 The reaction according to the method of the present invention will be described.

(Hydrochloride salt-forming reaction) First, a chlorinated hydrocarbon, for example, ortho-dichlorobenzene (hereinafter abbreviated as ODCB) was selected as a solvent suitable for the phosgenation reaction. On the other hand, a fatty acid ester, for example, isoamyl acetate was selected as a solvent suitable for the salt-forming reaction, and isoamyl acetate was added in such an amount that the boiling point (179 ° C.) of CDCB at normal pressure (179 ° C.) did not decrease by 20 ° C. or more. The mixing ratio of isoamyl acetate satisfying such conditions is preferably 30% or more, more preferably 25% or more.
% (% Is% by weight, and the same applies hereinafter unless otherwise specified).

If the mixing ratio of isoamyl acetate is 10% or less, the properties of the slurry are unfavorable because the hydrochloride aggregates into solid particles having a large diameter as in the case of CDCB alone, and stirring cannot be performed as expected. Therefore, a mixed solvent containing 76% of ODCB and 24% of isoamyl acetate was prepared, and an alicyclic-fatty amine was dissolved in the mixed solvent at 25 ° C., and then hydrogen chloride gas was blown thereinto to perform a salt formation reaction. Isoamyl acetate 100%
In the same manner as in the case of the above, the salt formation reaction was able to be performed extremely smoothly. As described above, it is surprising when compared with the fact that, with the ODCB of 100%, solid particles having a large diameter were formed by the salt formation reaction and did not react smoothly.

(Phosgenation reaction) Next, the internal temperature of the flask is raised to a predetermined temperature, 145 ° C or higher, preferably 150 to 160 ° C over 50 to 80 minutes, and the internal temperature after or during the temperature increase is 80 ° C or higher. From the time
Phosgenation reaction is performed by blowing phosgene. Blowing of phosgene is 0.5 to phosgene mol / raw amine mol · H.
1.0. If phosgene is blown at such a flow rate and the reaction temperature is maintained at 150 to 160 ° C., the reaction becomes clear at 5 to 7 H from the start of phosgene blowing, indicating that the phosgenation reaction has been completed.

Thereafter, the reaction temperature is maintained at 150 to 160 ° C., and N ₂ gas is introduced to perform degassing. After degassing for 80 to 90 minutes, the mixture is cooled to room temperature, desolventized and rectified to obtain the desired product.

Thus, in the method for producing an alicyclic-aliphatic isocyanate by phosgenation of an alicyclic-aliphatic amine compound by the hydrochloride method, which is an object of the present invention, the method wherein “the solvent B is 50% by weight or more and 90% by weight or less” By using a mixture of the solvent A and the solvent B as a solvent for the formation of the hydrochloride and the phosgenation so that the ratio of the solvent A and the solvent B is obtained, the two steps of the salt formation and the phosgenation are continuously reacted. A process for producing an alicyclic-aliphatic diisocyanate ”.

〔Example〕

 Hereinafter, a specific example will be described in detail.

Example 1 Production of 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane (BCHI) using mixed solvent Isoamyl acetate solvent as solvent A and ODCB as solvent B
Was used.

687 g of isoamyl acetate and 2189 g of ODCB were mixed and prepared as a solvent for salt formation and phosgenation (hereinafter referred to as a mixed solvent). In this case, the ratio of the ODCB corresponding to the solvent B is 76.1%.

1126 g of the mixed solvent was put into a four-necked flask 3 and cooled to 5 ° C. with ice water while stirring. Hydrogen chloride gas was blown into this at a rate of 1.6 Nl / min for 30 minutes, and then 250.0 g (1.62 mol) of separately prepared raw material diamine 2,5 (6) -diaminomethyl-bicyclo [2,2,1] heptane was added. Mixed solvent 1750
The solution dissolved in g (raw material diamine concentration: 12.5% by weight) was dropped into the liquid in the flask over 2 hours. The temperature inside the flask was maintained at 10 to 15 ° C while cooling was continued during the dropwise addition.

The blowing of hydrogen chloride gas was continued at a rate of 1 Nl / min. After the addition of the raw material diamine solution was completed, the blowing of hydrogen chloride gas was continued at a rate of 0.4 Nl / min for 2 hours while maintaining the inside temperature of the flask at 25 ° C. to complete the salt formation reaction.

In the salt-forming reaction, agglomeration of hydrochloride particles did not occur, the transition was extremely smooth, and a slurry of white uniform fine particles was obtained.

After completion of the salt-forming reaction, the temperature inside the flask is increased from 25 ° C to 160 ° C
The phosgene reaction was started by gradually blowing phosgene from 100 ° C. while the temperature was raised in 0 minutes. The phosgene blowing was continued at a rate of 100 g / h to 120 g / h while adjusting the internal temperature to 160 ± 1 ° C. with a mantle heater.

After about 6 hours from the start of phosgene blowing, the property of the reaction solution changed from a slurry (white) to clear (red), and then phosgene gas was blown at a rate of 50 g / h for 30 minutes, and the phosgenation reaction was terminated. did. The phosgenation reaction time was 6.5 hours in total. The phosgene gas used was about 2.2 times the theoretical amount.

Thereafter, N ₂ gas was blown into the reaction solution in the flask at a rate of 1.3 Nl / min for 80 minutes to perform degassing. During this time, the liquid temperature was 16
0 ± 1 ° C. After the reaction solution was degassed and cooled to remove a trace amount of solids, the reaction solution was filtered through filter paper (5C). After removing the filtrate, the filtrate was rectified under vacuum to obtain 306.5 g of a main fraction at 110 to 116 ° C / 0.4 to 0.6 torr. The analysis of this product was as follows.

NCO% 40.72 Hydrolysable chlorine (abbreviated as HC) 0.032% Gas chromatographic purity% 99.8 HC 0.202g / 100g-BCHl elemental analysis after desolvation CHN Calculated% 64.06 6.84 13.58 Actual% 64.11 6.89 13.47 Elemental analysis, The main fraction obtained from the results of IR spectrum, NMR spectrum and the like was confirmed to be the target product. The yield of the main fraction was 91.7% of the theoretical value (1.62 mol, 334.2 g).

Example 3 (4), 8 (9) -Diisocyanatomethyl-tricyclo [5,2,1,0 ^2,6 ] decane (TCDI) with mixed solvent
Production of butyl acetate as solvent A and ODCB as solvent B were used.

212 g of butyl acetate and 1555 g of ODCB were mixed and prepared as a solvent for salt formation and phosgenation (hereinafter referred to as a mixed solvent).
In this case, the ratio of the ODCB corresponding to the solvent B is 88.0% by weight.

667 g of the mixed solvent was placed in a 3 L four-necked flask, and cooled to 20 ° C. with ice water while stirring. Add hydrogen chloride gas to this.
After blown at a rate of 5 nl / min 30 minutes, the raw material diamine 3 prepared separately (4), 8 (9) - -diaminomethyl - mixing tricyclo [5,2,1,0 ^26] decane 194.3 g (1.0 mol) A solution (concentration of the raw material diamine: 15.0% by weight) dissolved in 1100 g of the solvent was dropped into the liquid in the flask over 1.75 hours. The temperature inside the flask was kept at 25 ° C. or lower while cooling was continued during the dropwise addition. The blowing of hydrogen chloride gas was continued at a rate of 0.5 Nl / min.

After the addition of the raw material diamine solution was completed, the blowing of hydrogen chloride gas was continued at a rate of 0.3 Nl / min for 1 hour while maintaining the internal temperature of the flask at 25 ° C. or lower to complete the salt formation reaction. In the salt-forming reaction, agglomeration of hydrochloride particles did not occur, the transition was extremely smooth, and a slurry of white uniform fine particles was obtained.

After completion of the salt-forming reaction, phosgene was gradually blown in from the point of 90 ° C. to start the phosgenation reaction while the temperature inside the flask was raised from 25 ° C. to 150 ° C. in one hour. Blowing of phosgene was continued at a rate of 75 g / h while adjusting the internal temperature to 150 ± 1 ° C. with a mantle heater. Approximately 5.5 hours after the start of phosgene injection, the reaction liquid changes to a slurry (white)
Since phosgene gas was blown at a rate of 50 g / h for another 30 minutes, the phosgenation reaction was terminated. The phosgenation reaction time was a total of 6 hours.

During this period, the properties of the reaction solution were free from abnormalities such as precipitation of solids, and the stirring and the like were performed smoothly. The phosgene used was about 2.2 times the theoretical amount.

Thereafter, N ₂ gas into the flask was at a rate of 1.3Nl / min 8
Blowing degassing was performed for 0 minutes. During this time, the liquid temperature is 160 ± 1 ℃
And

After degassing the reaction solution and cooling it to remove trace amounts of solids,
The mixture was filtered with filter paper (5C). After the filtrate was desolvated, it was rectified under vacuum to obtain 215.8 g of a main fraction of 144 to 155 ° C./0.4 to 0.% torr. The analysis of this main fraction was as follows.

NCO% 34.10 (theoretical 34.12) HC% 0.043 Elemental analysis CHN Calculated% 68.21 7.31 11.37 Actual% 68.26 7.58 11.27 Gas chromatographic purity 99.8 .

The yield of the main fraction was 87.6% of the theoretical value (1.0 mol, 246.3 g).

Comparative Example 1 2,5 with a single solvent (isoamyl acetate)
Production of (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane (BCHI) (from the formation of hydrochloride salt to phosgenation using isoamyl acetate solvent corresponding to solvent A) 863 g of isoamyl is placed in a three-necked flask of 3,
It was cooled to 3-5 ° C with ice water while stirring. After injecting hydrogen chloride gas at a rate of 1.6 Nl / min for 30 minutes,
A solution prepared by dissolving 246.5 g (1.60 mol) of a separately prepared raw material diamine 2,5 (6) -diaminomethyl-bicyclo [2,2,1] heptane in 1355 g of isoamyl acetate (raw material diamine concentration: 1
(5.4% by weight) The solution was dropped into the liquid in the flask over 1.5 hours.
During the dropping, the temperature in the flask was kept at 25 ° C. while cooling was continued. The blowing of hydrogen chloride gas was continued at a rate of 0.5 Nl / min.

After the addition of the raw material diamine solution was completed, the blowing of hydrogen chloride gas was continued at a rate of 0.5 Nl / min for 1 hour while maintaining the internal temperature of the flask at 25 ° C. or lower to complete the salt formation reaction. In the salt formation reaction, agglomeration of hydrochloride particles did not occur, and the transition was extremely smooth, and a slurry of fine particles having a uniform salt color was obtained. After completion of the salt-forming reaction, phosgene blowing was started while the temperature inside the flask was raised from 25 ° C. to 160 ° C. in 50 minutes.However, in order to make the inside of the flask almost at normal pressure, the reaction solution temperature was only up to 142 ° C. Did not go up. Inevitably, phosgene gas was added at 100-
When the gas was blown at a rate of 0 g / h, even after about 8 hours from the start of the blowing of phosgene, the properties of the reaction solution were still turbid (yellow), indicating that the reaction was not completed.

Furthermore, after about 10 hours from continuing the phosgene blowing, it became almost transparent (red-brown). 100 g of phosgene for an additional 40 minutes
After blowing at a rate of / h, the phosgene ring reaction was terminated.
The phosgenation reaction time was a total of 12 hours.

Thereafter, into the flask the reaction mixture was subjected to 80 minutes blown degassed N ₆ gas at a rate of 1.3Nl / min. During this time, the liquid temperature
139 ± 1 ° C. After the reaction solution was degassed and cooled to remove a trace amount of solids, the reaction solution was filtered through filter paper (5C). After desolvation of the filtrate, rectified under vacuum to obtain 0.48.4 torr main fraction 278.4 g
I got The analysis of this product was as follows.

NCO% 40.74 HC 0.031% GC purity 99.8 The ratio of the HC 0.322 g / 100 g-BCHI main fraction after desolvation is based on the theoretical value (1.60 mol, 329.0 g).
84.6%.

Comparative Example 2 2,5 (6) -diisocyanatomethyl-bicyclo [2,2,1] heptane (BCHI) with a single solvent (CDCB)
(In the case where the process from salt formation to phosgenation was performed using an ODCB solvent corresponding to solvent B) 900 g of ODCB was placed in a three-necked three-necked flask, and cooled to 5 ° C. with ice water to 5 ° C. while stirring. . Add hydrogen chloride gas to this
After blowing at a rate of 0.8 Nl / min for 30 minutes, a solution prepared by dissolving 201.3 g (1.31 mol) of separately prepared raw material diamine 2,5 (6) -diaminomethyl-bicyclo [2,2,1] heptane in 1400 g of ODCB ( (Raw material diamine concentration: 12.6% by weight) was dropped into the liquid in the flask over 2 hours. Lumps were formed due to aggregation of the hydrochloride during the dropping, and stirring was not performed smoothly. The frequency of stirring was reduced, and the temperature of the liquid in the flask was raised to 40 to 60 ° C. by heating with a mantle heater. As the dropping was continued in this manner, the lump gradually became soft near the end of the dropping, and the stirring became possible.
Because of such a trouble, it took a total of 5 hours to drop the starting diamine.

During the dropping, hydrogen chloride gas was blown at 0.8 Nl / min.
Continued at the rate of After dropping, keep the inside temperature of the flask at 40-60 ° C and blow hydrogen chloride at 0.4N.
The reaction was continued for 1 hour at a rate of 1 / min to complete the salt formation reaction.

After completion of the salt-forming reaction, the temperature inside the flask is increased from 25 ° C to 160 ° C
The phosgene reaction was started by gradually blowing phosgene from 100 ° C. while the temperature was raised in 0 minutes. Blowing of phosgene was continued at a rate of 100 g / h while adjusting the internal temperature to 160 ± 1 ° C. with a mantle heater. After about 6 hours from the start of phosgene blowing, the property of the reaction solution changed from a slurry (white) to clear (red), and then phosgene gas was blown at a rate of 50 g / h for 30 minutes, and the phosgenation reaction was terminated. did. The phosgenation reaction time was 6.5 hours in total. The phosgene gas used was about 2.5 times the theoretical amount.

Thereafter, N ₂ gas was blown into the reaction solution in the flask at a rate of 1.3 Nl / min for 80 minutes to perform degassing. During this time, the liquid temperature was 16
0 ± 1 ° C. After the reaction solution was degassed and cooled to remove a trace amount of solids, the reaction solution was filtered through filter paper (5C). After removing the filtrate, the filtrate was rectified under vacuum to obtain 237.3 g of a main fraction of 0.4 to 0.6 torr. The analysis of this product was as follows.

NCO% 40.71 HC 0.029% GC purity% 99.8 The ratio of the HC 0.322 g / 100 g-BCHI main fraction after desolvation was 88.2% of the theoretical value (1.31 mol /, 269.1 g).

〔The invention's effect〕

Conventionally, as raw materials for polyurethane resins and polyurea resins, foams, elastic bodies, synthetic leather, paints, adhesives, diisocyanates used in various fields such as films, tolylene diisocyanate, diphenylmethane diisocyanate Such aromatic diisocyanates and 1,6
-Aliphatic diisocyanates such as hexamethylene diisocyanate are mainly used, and aromatics have heat resistance and mechanical strength better than aliphatics, but have weaknesses such as weather resistance and yellowing resistance. is there. After that, there is an aromatic-aliphatic diisocyanate (in which two aromatic rings are substituted with the same or different two isocyanatoalkyl groups) such as xylylene diisocyanate. Inferior to all aliphatics due to radical modification.

On the other hand, an alicyclic compound represented by the structural formula (I)
Aliphatic diisocyanates (in which two places of an aliphatic cyclic hydrocarbon are substituted with two identical or different isocyanatoalkyl groups) have an aliphatic cyclic hydrocarbon as a skeleton,
Since it is an aliphatic isocyanate, it is an excellent diisocyanate having both weather resistance and non-group-modified because it is an aliphatic isocyanate.

However, these alicyclic-aliphatic diisocyanates, while being characterized by their performance advantages, have been difficult to use industrially alongside aromatic diisocyanates, etc., because of their low cost. This is because no production method has been found.

For example, when Example 1 of the present invention is compared with Comparative Examples 1 and 2 of the prior art, there is a difference in yield of 3.5 to 7.1% even though the production method is almost the same. This difference will provide a very cost-effective manufacturing method for these.

In Comparative Example 1, not only the yield but also the reaction time was required to be 1.8 times, the efficiency was low, and the production equipment was excessive. Comparative Example 2
It is presumed that troubles occur in the salt formation process, the operation becomes complicated, and the equipment and control become complicated.

In the present invention, in both the salt formation and phosgenation steps, by finding a solvent that can react under optimum conditions, the reaction is performed with good selectivity and with good yield, and the reaction is continuously performed because it is a common solvent. Thus, the cost of equipment and utilities is significantly reduced, and as a result, a method for industrially advantageously producing this alicyclic-aliphatic diisocyanate has been provided.

Claims (2)

(57) [Claims] 1. A first-stage reaction comprising the steps of reacting an alicyclic-aliphatic diamine represented by the structural formula (II) with hydrogen chloride: (Where k = 0 to 2, j, m = 1 to 5, n = 0 to 2) The alicyclic-aliphatic diamine hydrochloride represented by the structural formula [III] (Where k = 0 to 2, j, m = 1 to 5, n = 0 to 2), and as a second step reaction, the hydrochloride [III] is reacted with phosgene. Alicyclic-aliphatic diisocyanate represented by the structural formula (I) (Where k = 0 to 2, j, m = 1 to 5, n = 0 to 2). In the salt formation step, the phosgenation reaction with the A solvent that forms a uniform slurry is usually performed. A mixture of a solvent B having a boiling point of 145 ° C. or more at a pressure of not less than 50% by weight and not more than 90% by weight as a solvent in a salt-forming step and a phosgenation step. A process for producing both alicyclic-aliphatic diisocyanates. 2. The process for producing an alicyclic-aliphatic diisocyanate according to claim 1, wherein the solvent A is a fatty acid ester and the solvent B is a chlorinated aromatic hydrocarbon.