JPH0227979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing tertiary amines having long-chain alkyl groups, and more specifically, a method for producing tertiary amines having long-chain alkyl groups, and more specifically, a method for producing tertiary amines having long-chain alkyl groups, and more specifically, a method for producing tertiary amines having long-chain olefins, carbon monoxide, hydrogen, and primary or secondary amines. The present invention relates to a method for producing tertiary amines having one or two chain alkyl groups. By using the method of the present invention, it is possible to prevent deterioration in the performance of reusable catalysts, and to produce tertiary amines with a high recovery rate of expensive catalysts. Higher amines having long-chain alkyl groups and their derivatives are useful substances that have a variety of uses depending on their structure, such as emulsifiers, rust preventives, and intermediates for fiber softening agents. Conventionally, most of the tertiary amines having a long-chain alkyl group have been produced using natural fatty acids such as coconut oil, palm oil, and beef tallow as raw materials. but,
Since this method uses natural fatty acids as raw materials, there are limitations in terms of raw material supply, and there are problems such as a large number of manufacturing steps. For this reason, long-chain olefins, carbon monoxide,
A method for producing tertiary amines directly in one step by catalytically reacting hydrogen and primary or secondary amines has also been proposed (for example, Japanese Patent Publication No.
9527, JP 49-88812, JP 53-116307, JP 55-
102520 and US Pat. No. 3,947,458). However, these methods produce a large amount of alcohol as a by-product and are not necessarily effective for producing the desired tertiary amines, or it is difficult to recover and reuse the expensive group metals such as rhodium and ruthenium used commercially. However, it is a problem when manufacturing
There is a problem that this point is not mentioned. The present inventors have previously disclosed a method for solving the above problems in Tokkō No. 56-201986 (Tokukō 1-12263).
Publication No.) was proposed. Compared to other catalyst recovery methods, such as distillation separation, this method does not require heating the catalyst solution, which not only saves heat, but also avoids denaturation and deterioration of the catalyst due to heat. It has the advantage that it can be recovered together with the solvent and used again in the reaction without any modification, but because it uses a phase separation method, a very small amount of the expensive catalyst such as rhodium is released into the tertiary amines during this operation. It has the disadvantage that it elutes into the main amine layer. This is one of the causes of catalyst performance deterioration when the catalyst is used repeatedly. Therefore, recovering the small amount of catalyst in the produced amine layer not only prevents deterioration of catalyst performance but also reduces the loss of expensive catalysts such as rhodium, establishing an inexpensive method for producing tertiary amines. This is extremely important for the future. The present inventors conducted studies to improve the drawbacks of the above-mentioned Japanese Patent Application No. 56-201986 (Japanese Patent Publication No. 1-12263), and found that in the above method for producing tertiary amines, elution into the amine layer. The present invention was completed by discovering that even trace amounts of catalyst can be recovered without impairing its performance. That is, the present invention provides a process in which a long-chain olefin having 8 to 30 carbon atoms, carbon monoxide, hydrogen, and a primary or secondary amine are reacted in the presence of a catalyst whose main component is a compound containing rhodium and/or ruthenium. , monohydric alcohols having 1 to 3 carbon atoms as solvent, 2 carbon atoms
~6 dihydric alcohols, trihydric alcohols having 3 to 6 carbon atoms, or intermolecular dehydration condensates of dihydric or trihydric alcohols having 2 to 3 carbon atoms, or an alcohol and water. the reaction product is phase separated into an amine layer containing the product tertiary amine and a solvent layer containing the catalyst, the latter being recycled to the reaction zone;
In a method for recovering tertiary amines having long-chain alkyl groups from the former, after adding to the former polyalkylene glycols and/or polyglycerols having a boiling point higher than that of the tertiary amine produced, the tertiary amines are recovered. The present invention provides a method for producing tertiary amines, which comprises recovering amines by distillation. The method of the present invention is an improvement on the method of Japanese Patent Application No. 56-201986 (Japanese Patent Publication No. 1-12263), which was previously filed by the present inventors, and is described in the specification of the patent. It uses everything. The process of the present invention is characterized in particular by phase separation of the reaction product into an amine layer containing the produced tertiary amine and a solvent layer containing the catalyst, with the latter being recycled to the reaction zone and the long chains removed from the former. When recovering tertiary amines having an alkyl group, after adding polyalkylene glycols and/or polyglycerols having a boiling point higher than that of the generated tertiary amine to the former amine layer, the tertiary amine The objective is to recover the substances by distillation. The following polyalkylene glycols and/or polyglycerols having a boiling point higher than that of the produced tertiary amine are used in the method of the present invention. That is, polyalkylene glycols include polyethylene glycol, polypropylene glycol, or block or random copolymers of ethylene oxide and propylene oxide with a molecular weight of about 2,000 to 194, particularly polyethylene glycols with an average molecular weight of 400 to 1,000. is preferred. Examples of polyglycerin include diglycerin and triglycerin. A polyalkylene glycol and/or polyglycerin solvent having a boiling point higher than that of the tertiary amine produced is added prior to distillation recovery of the tertiary amine produced. The amount of these solvents added to the produced amine layer containing unreacted olefin and tertiary amine as main components and a trace amount of catalyst should generally be 30 parts by weight or less per 100 parts by weight of the produced amine layer. Preferably it is in the range of 5 to 20 parts by weight. Although it is possible to use a larger amount of added solvent, if the amount is larger than the above amount, the catalyst concentration in the recovered catalyst solution obtained after distillation will be low, and the recovered catalyst solution must be added in some way before being recycled to the reaction zone. This brings about the inconvenience of having to concentrate. The tertiary amine produced is recovered by distillation after adding the above solvent to the produced amine layer, but in this case,
It is desirable to carry out the reaction at a pot temperature of 200° C. or lower, preferably 150° C. or lower, in order to maintain the activity of the catalyst recovered as pot residue. By providing the above characteristics of the method of the present invention, the following advantages of the method of the present invention arise. That is, the first advantage is polyalkylene glycols,
Due to the presence of polyglycerin, etc., catalyst deterioration and
The advantage is that there is almost no noticeable deterioration, and the trace amounts of catalyst eluted into the produced amine layer can be recovered almost quantitatively without deteriorating performance. The second advantage is that the phase-separated amine layer is subjected to distillation concentration and liquid-liquid extraction at the same time, so even though the catalyst concentration in the produced amine layer is extremely low, it is possible to achieve a relatively high concentration. A catalyst solution is obtained and can be circulated to the reaction system without any need for concentration operations or the like. The third advantage is that the presence of a substance with a higher boiling point than the product tertiary amines improves the distillation recovery rate of tertiary amines, and at the same time improves the distillation recovery rate of amines containing long-chain alkyl groups. There is also the advantage that the foaming phenomenon at this time is suppressed by the presence of polyalkylene glycols, etc., and smooth distillation operation becomes possible. The catalyst used in the method of the present invention is one whose main component is a compound containing rhodium and/or ruthenium. In addition to this catalyst, the raw material long-chain olefin used in the method of the present invention, the solvent for phase-separating the reaction product, the reaction conditions, etc.
-12263) is used. The present invention will be explained in more detail by giving Examples and Comparative Examples below. Example 1 400 g of 1-dodecene, 200 g of diethylamine and RhCl ₃ .
Prepare 380g of polyethylene glycol with an average molecular weight of 600, containing 100mg of 3H 2 O and 260mg _of RuCl _{3.3H 2} O.
A mixed gas with a hydrogen:carbon monoxide ratio of 1.8:1.0
The reaction was carried out for 3 hours at 150° C. and 100 Kg/cm ² . After the reaction, the reaction is cooled to form an amine layer (Rh2ppm, Ru9ppm) containing unreacted dodecene and the product tridecyldiethylamine as the main components, and a solvent layer (Rh95ppm, Ru9ppm) containing substantially most of the catalyst.
Take out the contents that have phase-separated into Ru236ppm).
The composition analysis of the former resulted in an olefin conversion rate of 67.
%, and the yield of the desired product, tridecyldiethylamine, was 65%. 60 g of polyethylene glycol with an average molecular weight of 600 was added to 560 g of this amine layer, and the light boilers, unreacted dodecene, and tertiary amine produced were distilled off under conditions of a pressure of 2 to 3 mmHg and a pot temperature of 136 to 145°C, and the polyethylene glycol was 80 g of a pot residue (Rh 12 ppm, Ru 56 ppm) was obtained, which consisted of the following: and a part of the produced tertiary amine. No insoluble matter was observed. The amount of tridecyldiethylamine obtained by distillation was 380 g, in which Rh and Ru were not present. Meanwhile, in an electromagnetic induction stirring autoclave, the remaining liquid from the above pot, 80 g of 1-dodecene, and diethylamine were added.
40 g was added and the reaction was carried out under the same conditions as above. After the reaction, we analyzed the composition of the amine layer, which mainly consists of unreacted olefin and the product tridecyldiethylamine, and found that the olefin conversion rate was 52% and the tridecyldiethylamine yield was 46%, indicating good catalytic performance. I found out what happened. Comparative Example 1 All of the results were the same as in Example 1 except that when distilling and recovering the produced amine from the amine layer containing unreacted olefin and the product tridecyldiethylamine as the main components, polyethylene glycol was not added.
The method described in 1 was followed. A small amount of black insoluble material mainly composed of Rh and Ru metals was observed in the bottom liquid (Rh4ppm, Ru27ppm) after distillation recovery of unreacted dodecene and tridecyldiethylamine. As a result of carrying out the reaction using the bottom liquid as a catalyst, the reaction started after an induction period of about 1.5 hours, unlike in Example-1, and the olefin conversion rate reached only 28% even after 3 hours. The product also had an aldehyde yield of 6% and an amine yield of only 20%, and about 1/2 of the amines were unsaturated amines. Examples 2 to 5 Various treatments shown in Table 1 were applied to 100 g of an amine layer mainly consisting of unreacted decene and product undecyl diethylamine obtained using 1-decene as a raw material according to the method described in Example 1. 15 g each of polyalkylene glycols and diglycerin were added, and unreacted dodecene and produced tertiary amine were distilled and recovered.
Using the resulting pot residue as a catalyst, 60 g of 1-decene and 30 g of diethylamine were added, and the reaction was carried out at 140° C. and 110 kg/cm ² for about 3 hours. The results are shown in Table 1.

[Table] Example 6 To 70 g of the catalyst-containing solvent layer (layer mainly composed of polyethylene glycol #600) of the reaction solution obtained in Example-1, 60 g of 1-dodecene and 30 g of diethylamine were added, and 1-electromagnetic The mixture was placed in an autoclave with induction stirring, and the reaction was carried out at 150°C and 120 kg/cm ² using a mixed gas of hydrogen:carbon monoxide of 1.7:1.0. Gas consumed during the reaction was continuously supplied, and the reaction was continued for about 3 hours. Using the catalyst-containing solvent layer after the reaction, as above,
1-dodecene and diethylamine were added again to repeat the reaction, and Table 2 shows the reaction results calculated based on the results of compositional analysis of the produced amine layer. This result shows that the catalyst recovered in Example-1 can still be used for repeated reactions.

【table】

Claims (1)

[Claims] 1 A long-chain olefin having 8 to 30 carbon atoms, carbon monoxide, hydrogen, and a primary or secondary amine in the presence of a catalyst containing a compound containing rhodium and/or ruthenium as a solvent. 1
~3 monohydric alcohols, dihydric alcohols having 2 to 6 carbon atoms, trihydric alcohols having 3 to 6 carbon atoms, or intermolecular dehydration condensates of dihydric or trihydric alcohols having 2 to 3 carbon atoms The reaction product is phase-separated into an amine layer containing the produced tertiary amine and a solvent layer containing the catalyst, and the latter is reacted with an alcohol selected from the group consisting of: In a method for recycling tertiary amines having long-chain alkyl groups to the zone and recovering them from the former, polyalkylene glycols and/or polyalkylene glycols having a boiling point higher than the tertiary amine produced are added to the former.
Or a method for producing tertiary amines, which comprises adding polyglycerols and then recovering tertiary amines by distillation.