NL8302367A - CATALYTIC PREPARATION OF CARBONAMIDES. - Google Patents

Description

. «V. * τ R 7000 (R) - 1 -

Catalytic preparation of carbonaraides

The application relates to a process for the catalytic preparation of carbon amides starting from carboxylic acid and ammonia and / or amine at a higher temperature and optionally higher pressure under a catalytic influence of a 5. metal compound.

Such methods are already known from Dutch patent 171,156 as well as from British patent 1,396,615. In both documents, an organometallic compound soluble in the reaction mixture is used, in amounts of 0.1 to 10% by weight, based on the reaction mixture.

There are certain drawbacks to the use of soluble organometallic catalysts. For example, after completion of the conversion it is necessary to chemically convert and remove the organometallic compound, e.g. by converting it into an insoluble metal compound and filtering the latter. Thus, at least one additional process run is required and, moreover, the catalyst can also be used only once.

According to the present invention, carboxamide is prepared by converting carboxylic acid and / or ammonia or amine in the presence of a catalytic amount of a metal compound of a Group IV a, IV b or V a metal of the Periodic System which is insoluble in the reaction mixture. Preferably, the metal has an atomic number below 75. Preferred metal compounds are hydrated oxides, especially metal compounds of titanium, zirconium, tin and tantalum are excellent catalysts and their oxides are practically insoluble in the reaction mixture (the solubility is usually less than about 15 parts per million and that is the detection limit of the analytical technique followed --------— m 8302367 I. Λ - 2 - R 7000 (R). The use of these insoluble metal catalysts has the advantage that the removal is very simple, e.g. by filtration. Repeated use of the catalyst for this reaction is also possible and the reaction can for instance be carried out continuously in a fixed bed, which is also a great process advantage.

Incidentally, other insoluble catalysts for this conversion of carboxylic acid and ammonia or amine were already known, such as various silicates. However, they are less active than the Group IV metal derived catalysts and exhibit other disadvantages and / or give a higher nitrile percentage.

According to the present invention, hydrated oxide preferably uses hydrated dioxide, more in particular hydrated titanium dioxide. During the reaction, some water will also escape from the hydrated metal oxide. Sometimes it has been advantageous to deposit the metal oxide catalyst on a support e.g. Apply Dicalite.

Preferably, the hydrated titanium dioxide (TiC> 2 * xi ^ O) consists predominantly of orthotitanoic acid having the formula Ti (OH. More in particular, preference is given to using freshly precipitated hydrated titanium dioxide, such as, for example, by conversion of titanium tetrachloride or another soluble inorganic titanium compound with aqueous ammonia as e.g.

Titanium sulfate or basic titanium sulfate can be formed.

The amount of metal compound used can vary within very wide limits depending on the process run. With single use, the amount is usually between 0.05 and 10%, but with reuse and continuous 8302367 r-3 ~ R 7000 (R) processes it is considerably higher. However, the total amount of carbonamide prepared with it is at least hundreds of times the weight amount of catalyst. However, the catalyst is very active and in that respect is at least completely comparable to soluble organometallic compounds. Hydrated titanium dioxide is more active than e.g. tetrabutyl orthotitanate (TBT) especially at the end of the reaction.

Shorter conversion times are therefore possible.

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The reaction is preferably carried out at a pressure higher than atmospheric, especially if volatile amines or ammonia are used. Then the pressure is usually between 100 and 1000 K.Pa. The reaction temperature used depends, inter alia, on the carboxylic acid to be converted, the activity of the catalyst, etc.

As a rule, it is between 120 and 240 ° C, preferably between 150 and 200 ° C. It is necessary in order to complete the reaction to remove formed reaction water during the reaction, e.g. by regularly ventilating the autoclave (by blowing off and then reintroducing ammonia or amine). Also, the ammonia or the volatile amine can be recycled in a cycle, removing the reaction water formed, e.g. by one or more 25 steps.

It is possible according to the invention to use a starting material consisting of carboxylic acid and / or ammonia or amine and the new catalyst 30, but this mixture can also be partially prepared e.g. non-catalytic or using a little active catalyst such as e.g. convert a silicate, partially into carbonamide.

Thereafter, a rapid further conversion to carbonamide according to the present invention can then be efficiently effected by adding actively hydrated 8302367 • ** - 4 - R 7000 (R)

Group IV or V a metal oxide and further react with ammonia and / or amine.

This two or more step process is also excellent for continuous operation. The course of the reaction can be easily monitored via the acid number. Partially converted amide carboxylic acid which can be used as starting material often has an acid number of 5-40, preferably 10-30 mg KOH / g. According to the invention, products with amide contents of 97 to 99% of the theory can be obtained.

The carboxylic acids or their derivatives converted according to the invention are preferably C10 -C24 monocarboxylic acids which are saturated or contain one or more carbon-carbon double bonds. Often, technical stearic acid, lauric acid, oleic acid, elaxdic acid, erucic acid or linoleic acid are converted and, optionally, mixtures thereof. Preferably mononsaturated carboxylic acids are converted. Esters, in particular lower alkyl (C 1 -C 6) esters of these fatty acids, are also suitable. Preferably ammonia is used. A C1 - C6 primary or secondary alkyl amine can also be used. For example, methylamine, dimethylamine, ethylamine, cyclohexylamine and ethylenediamine can be used.

The carbonamide thus prepared is light in color and, according to the amide content, it is very pure, while the nitrile content is low. This amide is used for various purposes, e.g. as a "slip agent" for polyalkylene, as a washing aid, as a textile aid and as a lubricant additive.

Example 1: 10 grams of titanium tetrachloride were carefully poured into 35 8302367-5 R 7000 (R) 400 grams of distilled water. A finely divided white precipitate was formed by hydrolysis. After warming to 50 ° C, 50 grams of ammonia (approx. 25% NH4) was added with stirring. Then it was stirred at 80 ° for 5 minutes. After filtration on a Büchner 5, it was washed with warm water and aspirated.

The moist (undried) precipitate was mixed in 2000 g of olein (technical oleic acid containing approximately 80% mono unsaturated fatty acid). This mixture was withdrawn into 2q a pressure vessel. The vacuum was then filled with nitrogen. The mixture was heated to 180 ° C with stirring while passing nitrogen. An open valve in the vapor space of the autoclave allowed the water vapor generated from the moist catalyst to escape. At 170 ° C, the vapor barrier was closed and ammonia gas was introduced to 0.3 MPa and subsequently reacted at 180 ° C with stirring under 0.38 MPa. The pressure was released every 45 minutes in order to drain the reaction water.

2q After 6 hours of reaction, the acid number was 13.5 mg KOH / g. After 12 hours of reaction, the acid number was 2.4. After stirring in 1% filter aid (Dicalite 478), the amide was filtered at 100 ° C under 0.1 MPa gauge pressure. The amide is a solid with melting range of 67-70 ° C and 6 Gardner color. The amide content of the final product was 98%. The nitrile content was 0.6%.

Comparative Example 1A; 2000 grams of technical oleic acid were withdrawn into a pressure vessel. No addition was made. The reaction conditions for the amidation with ammonia were the same as in Example 1.

After 6 hours of reaction, the acid number was 22 mg KOH / g. After 12 hours 8302367 R 7000 (R) - 6 reaction, the acid number was 10.2 rag KOH / g, the amide content was 94% and the Gardner color 6. If the amidation was continued to obtain a higher amide content, many hours of further reaction were required, thereby significantly deteriorating the color.

Example 2;

In the same manner as described in Example 1, 10 g of 10 TiCl 2 titanium-containing catalyst was prepared. The moist (undried) precipitate was mixed in 2000 grams of 90% oleylamide at about 100 ° C with acid number 18 and withdrawn in a pressure vessel.

NOTE: The 90% amide was obtained by reaction without catalyst of olein with ammonia under 0.4 MPa at 180 ° C.

The vacuum was filled with nitrogen. The contents of the pressure vessel were heated to 180 ° C under nitrogen passage. Between 100 and 150 ° C, the water vapor formed from the moist catalyst could escape from the pressure vessel through an open valve.

As soon as 150 ° C was reached, amidation was started by admitting 0.3 MPa ammonia gas. After reaching 180 ° C, the reaction was carried out under 0.38 MPa ammonia pressure.

The pressure was released every 45 minutes to remove the water of reaction formed in the form of water vapor. After 7 1/2 reaction, the acid value of the amide had dropped to 2.4. After stirring in 1% filter aid (dicalite 478), the amide was filtered at 100 ° C under 0.1 MPa Nj overpressure.

The amide content of the final product was 98%. The nitrile content was 0.4%.

8302367 V ^ - 7 - R 7000 (R)

Samples taken after 1 1/2, 3 and 7 1/2 reaction were filtered at 90 ° C. The titanium contents in these filtered samples were less than 15 mg / kg. A part of the sample after 1 1/2 hours was also filtered at 180 ° C (i.e. at reaction temperature). The filtered amide also contained less than 15 mg Ti per kg. Due to the amount of catalyst added to the 90% amide, 1260 mg of titanium per kg of amide was present. This amount of titanium was almost entirely in undissolved form.

Comparative Example 2A: 2000 grams of 90% oleylamide acid number 18 (the same raw material as in Comparative Example 1A Example 2) was withdrawn into a pressure vessel. No addition was made.

The reaction conditions for the ammonia amidation were further the same as those of Example 3. After 7 1/2 reaction, the acid value was 8 mg KOH / g. After 13 hours of reaction at 180 ° C under 0.38 MPa, the acid value of the reaction mixture had fallen to 2q. 6.0 mg KOH / g.

Comparative example 2B:

Stir in 4.2 grams of titanium dioxide Kronos R 1053 (rutile form) in 2000 grams of molten oleylamide acid number 18 (the same raw material as in example 2} was stirred. This mixture was withdrawn into a pressure vessel and amidated in the same manner as described in example 7. After The acid number had fallen to 7.5 after 1/2 hour reaction.

30

Comparative example 2C:

In 2000 grams of molten oleylamide acid number 18 (the same raw material as in example 2) was stirred in 4.2 grams of 25 titanium dioxide Kronos AD (anatase form). This mixture was amidated at 8302367-8-R 7000 (R) in the same manner as described in Example 7. After 7 1/2 reaction, the acid number had dropped to 7.6.

Example 3: 5

In the same manner as described in Example 1, 10 g of TiCl 2 titanium-containing catalyst were prepared. However, the resulting filter cake was dried at 110 ° C under vacuum for 15 hours. The dried precipitate was stirred in 2000 grams of oleylamide acid number 18 (the same raw material as in Example 2) and withdrawn in a pressure vessel. After this, the vacuum in the pressure vessel was filled with nitrogen. Then it was reacted with ammonia at 180 ° C under 0.38 MPa as described in Example 3. After 7 1/2 hours of reaction, the acid number had dropped to 6.7 mg KOH / g.

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Example 4;

The filter cake of 1825 grams of unfiltered end product of Example 3 was stirred in 1800 grams of molten oleylamide with acid number 18 as in Example 2 at about 100 ° C. This mixture was withdrawn into a pressure vessel. The vacuum was then filled with nitrogen. The contents of the pressure vessel were heated to 180 ° C while passing nitrogen.

25

At ISO C, ammonia was admitted to 0.3 MPa in the reactor. After reaching 180 ° C, it was reacted with ammonia below 0.38 MPa. The pressure was released every 45 minutes. After 7 1/2 hours of reaction, the acid number of the reaction mixture had fallen to 2.7. The amide was filtered at 100 ° C under 0.1 MPa nitrogen overpressure. The amide content in the final product was 98%. The nitrile content was 0.8%.

Comparative example 4A:

20 grams of dicalite 478 were stirred in 2000 grams of molten oleylamide with acid number 18 (the same 35 8302367 R 7000 (R) - 9 raw material as in Example 2). This mixture was withdrawn into a pressure vessel. The vacuum was then filled with nitrogen. The contents of the pressure vessel were heated to 180 ° C while passing nitrogen. At 150eC, ammonia was admitted to 0.3 MPa in the reactor. After reaching 180 µg, the reaction was carried out with ammonia under 0.38 MPa. The pressure was released every 45 minutes. After 7 1/2 hours of reaction, the acid value of the reaction product had dropped to 6.8 mg KOH / g.

10

Example 5:

In a manner similar to that described in Example 1, 2 g of TiCl 2 titanium-containing catalyst was prepared.

^ The wet (undried) precipitate was mixed in 2000 grams of oleylamide with acid number 18 (the same raw material as in Example 2). This mixture was withdrawn into a pressure vessel. The vacuum was filled with nitrogen. The contents of the pressure vessel were heated to 180 ° C under nitrogen pass-through.

20

Between 100 and 150 ° C, the water vapor generated from the moist catalyst could escape from the pressure vessel through an open valve. The amidation was carried out in the same manner as in Example 3. After 7 1/2 reaction, the acid number had dropped to 6.2 mg KOH / g.

Example 6

20g of filter aid (Dicalite) 478 was dispersed in 800 g of distilled water. 10.2 g of tin tetrachloride was slowly added to this dispersion with stirring.

It was then heated to 90 ° C. At this temperature, 50 g of ammonia (25%) was added dropwise with stirring and stirring was continued for a further 5 minutes.

8302367 35 - 10 - R 7000 (R)

Stirring was then stopped for 5-10 minutes to allow the precipitate to settle somewhat. The top layer was decanted onto a Büchner funnel and then the settled precipitate was filtered on the same Büchner and washed 5 times with warm water. The moist, undried filter cake was mixed in 2000 g of 90% oleylamide at about 100 ° C and acid value of 18 mg KOH / g "(cf. Ex 2). The mixture was withdrawn into a pressure vessel, the vacuum filled with nitrogen, the contents heated to 180 ° C under nitrogen flow. Between 100 and 150 ° C, the water vapor formed from the catalyst could escape through the opened valve. As soon as 150 ° C was reached, the amidation was started by admitting 0.3 MPa ammonia gas. After reaching 180 ° C, it was governed under 0.38 MPa ammonia pressure.

The pressure was released every 45 minutes to remove the water of reaction formed. After 7 1/2 hours of reaction time, the amidation was stopped and filtered at 100 ° C under 0.1 * MPa nitrogen overpressure. The acid value of the final product was 4.3 mg KOH / g.

8302367

Claims (14)

Process for the preparation of ammonia and / or amines of carbon amides by reaction of carboxylic acids or derivatives of carboxylic acids with ammonia and / or amines in the presence of a metal compound, characterized in that the carboxylic acid is reacted with amine or ammonia in the presence of a insoluble metal compound of a Group IVa, IVb or Va element of the Periodic Table. A method according to claim 1, characterized in that the metal is a Group IVa element. Process according to claim 1 or 2, characterized in that the hydrated oxide consists predominantly of hydrated dioxide. 4. Process according to claim 1, 2 or 3, characterized in that the hydrated oxide consists predominantly of orthotitanoic acid. Process according to claim 1, 2, 3 or 4, characterized in that the preparation is carried out with freshly precipitated orthotitanoic acid. Process according to any one of claims, characterized in that the amount of hydrated metal oxide (calculated as metal oxide on the reaction mixture) is between 0.05 and 10% by weight. Process according to any one of the preceding claims, characterized in that the reaction is carried out at higher than atmospheric pressure. 8302367 r '' R 7000 (R) · *. · * ·· - 12 - A method according to any one of the preceding claims, with. characterized in that the reaction mixture is reacted at a temperature above 100 ° C. Process according to any one of the preceding claims, characterized in that a reaction mixture consisting of carboxylic acid and amine or ammonia partially converted into carbon amide is used as starting material together with ammonia and / or amine. Process according to claim 9, characterized in that the partially converted reaction mixture has an acid number between 5 and 40, preferably between 10 and 30 mg KOH / g. Process according to any one of the preceding claims, characterized in that a carbonamide derived from a C 1 to C 24 saturated or unsaturated fatty acid is formed. Process according to any of the preceding claims, characterized in that a mono-unsaturated carboxylic acid is converted. The process according to any one of the preceding claims, wherein the reaction is carried out batchwise with the catalyst being reused. A method according to any one of claims 4 to 12, characterized in that the reaction is carried out continuously. 8302367