WO2008018148A1 - Process for producing amino compound - Google Patents

Abstract

It relates to a process for producing an amino compound in which by reacting a polyhydric alcohol or an amino alcohol with ammonia or a primary amine or a secondary amine, a corresponding tertiary amine, amino alcohol or the like is produced. It is intended to provide a process for producing an amino compound by which the running cost can be suppressed because a noble metal such as palladium or ruthenium is not used as a catalyst and an amino compound such as a tertiary amine which is industrially useful can be produced at a high reaction rate, high yield and high selectivity. The invention is provided with a structure in which a polyhydric alcohol and ammonia or a primary amine or a secondary amine are reacted in the presence of a catalyst containing copper, nickel, calcium, an alkali metal or an alkaline earth metal (except for calcium) as an essential component.

Description

 Specification

 Method for producing amino compounds

 Technical field

 [0001] The present invention relates to an amino compound for producing a corresponding tertiary amine namino alcohol by reacting a polyhydric alcohol namino alcohol with ammonia or a primary or secondary amine. It is related with the manufacturing method.

 Background art

 [0002] One of the amino compounds, N, N, N, N, -tetramethyl-oc, ω-alkylene diamine, is an industrially important tertiary amine represented by the general formula (Α). It is used as a catalyst for the production of urethane foam, and is mainly manufactured and sold with η = 2, 3 or 6.

 Me N- (CH) n-NMe

 2 2 2

 In addition, the intermediate amino alcohol represented by the general formula (B) is called a reactive urethane catalyst, and has a worse irritating odor and ocular mucosa than the tertiary ammine represented by the general formula (A). In addition to reducing the irritation and improving the working environment, it also has active hydrogen (hydroxyl), so it reacts with isocyanate, which is a urethane raw material, and is incorporated into the polyurethane resin skeleton, thereby suppressing the transpiration of the urethane catalyst. Therefore, polyurethane resin is an important amino compound with high V, because it can improve the fogging resistance, vinyl cysteine resistance and heat resistance of urethane foam.

 Me N- (CH) n-OH-"(B)

 twenty two

 [0003] Here, as a general production method of the tertiary amine represented by the general formula (A), there are a reductive methylation method of the corresponding primary amine represented by the general formula (C), There is an amination reaction method of a polyhydric alcohol represented by the reaction formula (D). Here, dihydric alcohol (diol) is exemplified as the polyhydric alcohol.

 H N- (CH) n-NH-"(C)

 2 2 2

 HO- (CH) n-OH → Me N— (CH) n-NMe + 2H O · · · (D)

 2 2 2 2 2

The amination reaction of the chemical reaction formula (D) proceeds by the sequential reaction of the chemical reaction formulas (E) and (F), and the speed of the second stage reaction shown by the chemical reaction formula (F) is higher than that of the conventional catalyst. Generally slow! It has been.

 HO— (CH) n— OH + Me NH → Me N— (CH) n— OH + H O "-(E)

 2 2 2 2 2

Me N— (CH) n— OH + Me NH → Me N— (CH) n— NMe + H O--(F)

 2 2 2 2 2 2 2

 [0004] The former reductive methylation reaction method, as described in, for example, (Patent Document 1), requires an excessive amount of formaldehyde in the reaction, and thus requires post-treatment of unreacted formaldehyde. It is industrially disadvantageous. On the other hand, the latter amination reaction method represented by the chemical reaction formula (D) is an industrially advantageous production method from the viewpoint of green chemistry because only reaction water is generated in addition to the tertiary amine. .

 Therefore, a method for producing an amino compound such as tertiary amine by amination reaction using polyhydric alcohol as a starting material has been developed.

 [0005] As a conventional technique, for example, (Patent Document 2) states that “polyhydric alcohol and cyclic primary or secondary amine are (a) copper carboxylate or copper intramolecular complex as copper complex. A cetylacetone complex, and (b) one or more of a cetylacetone complex as a carboxylic acid salt or an intramolecular complex of a group 8 element, manganese and zinc power of the periodic table, and (c) a carboxylic acid Or in the presence of a catalyst obtained by reducing a mixture of one or two or more of carboxylic acid alminium metal salt or aralkyl earth metal salt with a mixture of hydrogen and amine or other reducing agent; A process for producing a tertiary amine that is reacted at a temperature of 300 ° C. is disclosed.

 (Patent Document 3) states that “polyalcohol and primary or secondary amines can be produced in the presence of a copper 1-Neckel Group 8 platinum element catalyst while removing water produced by the reaction. A process for producing a tertiary amine in which the reaction is carried out at a temperature of 150 ° C. to 250 ° C. under a pressure of 5 atm or less at atmospheric pressure ”is disclosed.

 (Patent Document 4) and (Patent Document 5) state that “diol and primary amine are mixed in the presence of a copper-nickel-group 8 platinum element catalyst while removing the water produced by the reaction. A technique for producing an amino alcohol by reacting at a temperature of from C to 250 ° C. is disclosed.

 Patent Document 1: JP 2000-159731 A

 Patent Document 2: Japanese Patent Publication No. 60-11020

 Patent Document 3: Japanese Patent Publication No. 3-4534

Patent Document 4: Japanese Patent Laid-Open No. 5-39338 Patent Document 5: JP-A-5-93031

Disclosure of the invention

Problems to be solved by the invention

 However, the conventional techniques described above have the following problems.

 (1) (Patent Document 2) does not include a description of an example in which a polyhydric alcohol power tertiary amine was produced, so that the present inventors described copper stearate, nickel stearate, barium stearate according to the description in the specification. As a catalyst raw material, a follow-up test was conducted in which 1,6-hexanediol (polyhydric alcohol) was reacted with dimethylamine (secondary amine) instead of morpholine. He was unable to achieve an efficient amination reaction. These catalyst raw materials are not effectively activated in highly polar polyhydric alcohols, and even if activated, the stability of the catalyst is insufficient and the catalyst cannot be activated sufficiently. Therefore, they were unable to efficiently aminate polyhydric alcohol.

 (2) Example 13 in (Patent Document 3) discloses an example in which 1,6-xandiol is aminated using a copper-nickel-ruthenium-based catalyst (Patent Document 3). The group 8 platinum element of the catalyst was expensive, and the production cost of the catalyst was high, which had the problem of being industrially disadvantageous. Furthermore, as a result of reexamination of the activity of the catalyst of the patent, it was confirmed that the catalyst activity (reaction rate) per unit weight of copper, which is the basis of the catalyst production cost, is low and the productivity is poor.

 (3) The technologies disclosed in (Patent Document 4) and (Patent Document 5) also use a Group 8 platinum element such as palladium as a cocatalyst, which increases the manufacturing cost of the catalyst and is industrially disadvantageous. The problem was. In addition, since the activity of the catalyst is low, the amount of the catalyst used for the polyhydric alcohol is very high at 24 wt%, which has a problem of requiring a large running cost.

(4) Since the amination reaction of the polyhydric alcohol that proceeds in a sequential reaction has very low reactivity at the second stage represented by the chemical reaction formula (F), (Patent Document 2) to (Patent Document 5) The catalyst disclosed in 1) has low activity and requires a long time to complete the reaction, and a large amount of by-products (aldol condensates) are produced. Therefore, the desired amine amino alcohol is obtained in a high yield with high selectivity. I couldn't make it. [0007] The present invention solves the above-described conventional problems, and since no precious metal such as palladium or ruthenium is used as a catalyst, it is possible to suppress running cost and to select a high yield with a high reaction rate. It is an object of the present invention to provide a method for producing an amino compound capable of producing an amino compound such as tertiary amine which is highly useful and industrially useful.

 Means for solving the problem

[0008] In order to solve the above conventional problems, the method for producing an amino compound of the present invention has the following constitution.

 The method for producing an amino compound according to claim 1 of the present invention comprises a step of mixing a polyhydric alcohol and an ammonia, a primary amine, or a secondary amine with copper, nickel, calcium, alkali metal or alkaline earth metal (calcium The reaction is carried out in the presence of a catalyst that is an essential component.

 With this configuration, the following effects can be obtained.

 (1) By reacting in the presence of a catalyst containing copper, nickel, calcium, alkali metal or alkaline earth metal (excluding calcium) as an essential component, it can be industrially produced with high reaction rate and high selectivity. Useful amino compounds such as tertiary amines can be produced. In particular, in the amination reaction, the reaction rate of the second stage represented by the chemical reaction formula (F) is extremely low, but the reaction rate of the second stage is extremely high and highly active as compared with the conventional case. Wakatsuta o

 (2) Since the catalyst is highly active, the reaction conditions are mild, and the reaction can be completed in a short time with a small amount of catalyst.

 (3) Since noble metals such as palladium and ruthenium are used for the catalyst, the running cost of the catalyst can be suppressed.

 (4) The disproportionation reaction of the raw material amine and the product amine derived from the precious metal content is greatly suppressed, and the selectivity of the product amine can be improved.

Here, the starting polyhydric alcohol includes 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol. 1,9-nonanediol, 1,10-decanediol, 1,12-dodecandiol, 12-hydroxystearyl alcohol, ethylene glycolol, triethyleneglycol And dihydric alcohols such as propylene glycol and trihydric alcohols such as glycerin are used. 1,10-decanediol can be produced by hydrogen reduction of sebacic acid or its dimethyl ester produced by castor oil alkaline acid, and 12-hydroxycysteallyl alcohol can be produced by hydrogenation of ricinoleic acid. Can be manufactured.

 [0010] The starting material, an amino alcohol, is an intermediate of the sequential reaction of the chemical reaction formulas (E) and (F), and has an amino group and a hydroxyl group obtained by amination of the polyhydric alcohol. For example, monoethanolamine, diethanolamine, methylethanolamine, methylethanolamine, dimethylethanolamine, jetylethanolamine, diisopropylethanolamine, and dibutylethanolamine can be used.

 [0011] The starting amine as a starting material is ammonia, a primary amine represented by the general formula I ^ NH

 2

Secondary amines represented by the general formula R ² NH are used.

 2

Here, R ¹ is an alicyclic hetero ring such as a straight chain or branched chain having 1 to 6 carbon atoms, an alicyclic alkyl group, or a morpholyl group, and examples of the primary amine include methylamine, ethylamine, propylene. Examples include luamine and cyclohexylamine. R ² is a linear alkyl group having 1 to 4 carbon atoms, and examples of the secondary amine include dimethylamine, jetylamine, dipropylamine, and dibutylamine. Other raw material amines include aromatic amines such as aline and benzylamine, alicyclic amines such as cyclohexylamine, heteroaromatic amines such as furfurylamine, pyrrolidine, piperidine, piperazine, Examples include cyclic amines such as pyrrolidone.

[0012] As a catalyst raw material for a catalyst comprising copper, nickel, calcium and alkaline earth metal (excluding calcium) as essential components, (a) one or two of a copper carboxylate or a copper intramolecular complex (B) one or more of nickel carboxylate or nickel intramolecular complex, (c) one or more of calcium carboxylate or calcium complex, (d) Al One or a mixture of two or more carboxylates of metals or alkaline earth metals (except calcium) are used.

In order to carry out the amination reaction, it is first necessary to reduce and activate the catalyst raw material. For example, the catalyst raw material is heated and dissolved in the starting polyhydric alcohol or amino alcohol. Then, after introducing hydrogen or another reducing agent to activate the reduction (hereinafter referred to as reduction activation treatment), the amination reaction can be advanced by introducing the raw material amine. Also, the catalyst raw material is heated and dissolved in a solvent such as higher alcohol, and after the reduction activation treatment, the amination reaction proceeds by introducing the starting raw material polyhydric alcohol Namino alcohol and the raw material amine. Can do. The catalyst obtained by the reduction activity treatment is an apparently uniform colloidal catalyst (copper Z nickel particle diameter is about 1 nm).

[0013] In the catalyst raw material, (a) the copper carboxylate and the intramolecular complex of copper are reduced to copper metal in the course of the reduction activation treatment. The carboxylic acid forming the copper carboxylate may be aromatic or branched as long as it has a carboxyl group in the molecule. May have other substituents. , Stearic acid, oleic acid and the like. Preferred are carboxylic acids having 6 or more carbon atoms, and particularly preferred are carboxylic acids having 12 or more carbon atoms.

 This is because a carboxylate having 5 or less carbon atoms is liable to agglomerate metal colloid due to the influence of the liberated carboxylic acid during the reduction, and the activity tends to decrease. Examples of the intramolecular copper complex include general chelate compounds containing no io, such as a cetylacetone complex and a dimethyldarioxime complex.

 [0014] In the catalyst raw material, (b) nickel carboxylate and nickel intramolecular complex are also reduced during the reduction activation process. Examples of the carboxylate and the intramolecular complex include the same organic ligands as the carboxylic acid and the intramolecular complex. The carboxylic acid preferably has 6 or more carbon atoms. This is because a carboxylate having a carbon number of 5 or less is likely to agglomerate the metal colloid and reduce its activity due to the effect of the free carboxylic acid during the reduction.

[0015] In addition, (c) calcium carboxylate and calcium complex in the catalyst raw material are gradually reduced during the amino acid reaction, and exhibit a strong catalytic action together with copper and nickel. Examples of the carboxylic acid include those similar to the carboxylic acid. Examples of the calcium complex include V general chelate compounds having no inorganic anion, such as a cetylacetone complex and a dimethyldaridioxime complex. The carboxylic acid preferably has 6 or more carbon atoms. This is because, as in the case of copper and nickel, carboxylic acid is liberated, and the copper Z nickel metal colloid is easily aggregated and the activity is easily reduced.

 [0016] The copper nickel-calcium colloid in which (d) carbonates of alkali metals or alkaline earth metals (except calcium) are not reduced during the reduction activation treatment and amination reaction. Functions as a catalyst stabilizer. Of these, alkaline earth metal carboxylates, particularly barium carboxylates are effective. Norium is a power that functions particularly effectively as a stabilizer that maintains the activity of a catalyst that is particularly difficult to be reduced compared to copper and nickel.

 Examples of the carboxylate include the same ones as described above, and examples thereof include sodium stearate, barium laurate, and sodium stearate. Of these, stearic acid, behenic acid, lignoceric acid and the like having 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, particularly 18 to 24 carbon atoms are preferably used. As a result of experiments conducted by the present inventors, a carboxylate having 8 to 30 carbon atoms has a high catalytic activity due to the effect of inhibiting the aggregation of copper Z nickel metal colloid due to the chain length effect of the carboxyl group. It is also a powerful force to give. The carboxylate of copper, nickel, alkali metal, and alkaline earth metal can be produced by a known method described in JP-B-59-27617.

[0017] As a reducing agent other than hydrogen used in the reduction activation treatment of the catalyst raw material, A1 (C H)

 twenty five

, (C H) Al (OC H), or the like can be used.

 3 2 5 2 2 5

 As the solvent for dissolving the catalyst raw material, a higher boiling higher alcohol can be used. A highly concentrated catalyst solution can be produced by reducing the catalyst raw material in a solvent. In this catalyst solution, the amination reaction of polyhydric alcohol and amino alcohol can also be carried out.

In the reduction activation treatment of the catalyst raw material, the catalyst raw material is charged into a polyhydric alcohol / amino alcohol / solvent, and a reducing agent such as hydrogen is continuously supplied simultaneously with the temperature rise. The reduction of divalent copper begins around 160 ° C, and the activation of the catalyst is completed at less than 200 ° C. After the reduction activation treatment, the color tone of the reaction mixture containing the colloidal catalyst changes from pale yellow (transparent) to black as the amination reaction proceeds, and gradually changes to a reddish brown uniform colloidal catalyst. And develops high activity. Early pale yellow force The period of black state is a transition period to a highly active colloidal catalyst, which is a kind of induction period. Polyhydric alcohols and higher chain length of such alcohol as the shorter (e.g. 1, _9-1 nonanediol, 8 Okutanjioru etc.), since the tendency of the induction period becomes longer observed, the polyhydric alcohol is more chain length long The chain length of the higher alcohol as a solvent immediately after the reaction is long in terms of boiling point.

 [0018] After the reduction activation treatment, the reactor is set to 100 to 250 ° C, preferably 150 to 220 ° C, more preferably 180 to 220 ° C. Introduce gaseous raw material amine such as secondary amine to start amination reaction. The reaction rate tends to decrease as the reaction temperature becomes lower than 180 ° C, and this tendency becomes remarkable as the reaction temperature becomes lower than 150 ° C. Side reactions tend to be accelerated as the reaction temperature rises above 220 ° C, and the reaction temperature becomes pronounced when the reaction temperature rises above 250 ° C.

 The amination reaction is suitably carried out in the range of −5 to 100 atm, preferably −0.5 to: LO atm, more preferably normal to 5 atm. This is because the amination reaction is a dehydration reaction, so that the reaction rate is reduced under pressure.

 In the amination reaction, when starting amines such as primary amines and secondary amines are introduced, water begins to distill after the induction period of several minutes, and the progress of the reaction can be confirmed. The reaction proceeds even under conditions where hydrogen is not introduced. The active hydrogen generated by the dehydrogenation of polyhydric alcohol and amino alcohol is also used for the reaction. However, it is preferable to introduce hydrogen and carry out the reaction in the presence of hydrogen. This is because the reaction time can be shortened slightly and the introduced hydrogen helps to carry water out of the system. In order to efficiently transport water out of the system, hydrogen, nitrogen, inert gas, etc. for transporting water introduced into the reactor are not consumed. Therefore, instead of hydrogen or mixed with hydrogen, nitrogen or rare This can be done by introducing an inert gas such as a gas into the reactor.

Since the oil component, which is a product, is distilled together with the generation of water, the oil-water separation is performed by a conventional method, and the oil component is returned to the reactor as necessary to proceed with the amination reaction. The progress of the reaction can be followed by amine value, hydroxyl value, or gas chromatography analysis. When the amination reaction is completed, the distillation of water is also stopped. Depending on the reaction temperature, catalyst concentration, and amine feed rate, the amination reaction can be completed in 2 to 10 hours.

[0020] The concentration of the catalyst is preferably 0.001 to 10 wt% (relative to the starting material alcohol), preferably 0.01 to 5 wt%, more preferably 0.05 to 2 wt%, based on metallic copper. It is. As the concentration becomes lower than 0.05 wt%, the reaction rate tends to decrease. When the concentration is lower than 0.001 wt%, productivity is remarkably lost. The side reaction tends to be promoted as the concentration is higher than 2 wt%, and it is not preferable because it becomes remarkable when the concentration exceeds 10 wt%.

 As the composition of the catalyst, the optimal atomic ratio is copper: nickel: calcium: alkali metal or alkaline earth metal (excluding calcium) = 5: 1: 1: 1: 1. In the catalyst composition, the atomic ratio of alkali metal or alkaline earth metal (excluding calcium) to calcium is preferably 0.1 to LO. This is because if the ratio is less than 0.1, the stability of the metal colloid system is drastically reduced, the aggregation of the metal colloid is promoted and the catalyst is deactivated, and if it exceeds 10, the reaction rate is greatly reduced.

 In the catalyst composition, the ratio of calcium to copper is preferably 0.1 to 0.5 in terms of atomic ratio. When the ratio is less than 0.1 or exceeds 0.5, the reaction rate is greatly reduced.

 [0022] In the amination reaction, the feed rate per unit time (LZ time) of the raw material amine (ammonia, primary amine, secondary amine) supplied into the reactor is the standard starting material. Per mole of hydroxyl group of alcohol: 0.01 to: LOO mol Z time, preferably 0.1 to 10 mol Z time, particularly preferably 0.2 to 5 mol Z time. Less than 0.01 mol Z time is not preferable because the reaction rate is slow and the productivity is extremely poor. Exceeding the loo mol Z time is not preferable because catalyst poisoning by the raw material amine becomes prominent, resulting in a decrease in reaction rate and yield, and further disproportionation is greatly promoted.

[0023] The amination reaction can be performed batchwise, continuously, or offset. In the case of a batch type, for example, a normal stirred layer reactor, an injector type stirred reactor, a loop reactor, or the like can be used. Even in the case of a continuous type, a special stirring device can be used as required, such as a gas stirring type reactor. [0024] Examples of the amino compound obtained by the present invention include N, N, Ν ', Ν'-tetramethyl-1, 6-hexamethylenedian, Ν, Ν, Ν', Ν, -tetramethyl-1, 8-Otatamethylenedian, Ν, Ν, Ν ', Ν, -Tetramethyl-1,9-nonamethylenedian, Ν, Ν, Ν', Ν, -Tetramethyl-1,10-decamethylenedian, Ν , Ν, Ν ', Ν, -tetramethyl-1, 12-dodecamethylenedian, 12-hydroxy- Ν, ジ メ チ ル -dimethylstearylamine, 12-—, ジ メ チ ル dimethyl Ν,, ，, -dimethylstearylamine, etc. And tertiary amino amines, and amino alcohols which are intermediates of these tertiary amines. These amino compounds are suitably used as catalysts for the production of polyurethane and urethane foam.

 [0025] After completion of the amination reaction, the catalyst can be filtered and separated by cooling the reaction mixture and adsorbing it on an adsorbent such as activated carbon. However, it is necessary to keep the catalyst in a reduced state during adsorption.

 However, a colloidal catalyst (copper-nickel particle size is about 1 nm) cannot be separated by a normal filtration operation, and therefore, it is preferable to separate it into a fraction and a residue by a normal distillation operation. Since the catalyst is present in the residue and can be reused as it is for the next reaction, it is excellent in workability without the need for a catalyst filtration step required for a solid catalyst.

 It was confirmed that the catalyst of the present invention was extremely stable with respect to a polar solution after the reduction activity treatment, and that the catalyst did not aggregate even when left as a acetonitrile solution for 1 week. In order to further improve the resistance to polarities, it is also effective to increase the amount of stabilizer (alkali metal or alkaline earth metal (excluding calcium) component) among the catalyst components. In addition, even if the reaction was repeated, the performance of the catalyst hardly decreased.

[0026] The invention according to claim 2 of the present invention is the method for producing an amino compound according to claim 1, wherein the catalyst is (a) a copper carboxylate or a copper intramolecular complex 1. Or (b) one or more of nickel carboxylates or nickel intramolecular complexes; and (c) one or more of calcium carboxylates or calcium complexes. And (d) a mixture of one or more of alkali metal or alkaline earth metal (excluding calcium) carboxylates in the polyhydric alcohol or amino alcohol or solvent. Alternatively, it may have a structure that has been reduced with another reducing agent.

With this configuration, in addition to the operation obtained in claim 1, the following operation can be obtained. (1) Since the raw material of the catalyst is metal sarcophagus, productivity is eliminated because complicated processes such as metal hydroxide production, water washing, drying, pulverization, and classification required for producing a solid catalyst are unnecessary. Remarkably excellent.

 (2) Since the catalyst reduced with polyhydric alcohol or the like is colloidal, it can be applied to batch and continuous methods, and can be easily adapted to small-scale production, and has excellent flexibility.

 [0027] The invention according to claim 3 of the present invention is the process for producing an amino compound according to claim 1 or 2, wherein the polyhydric alcohol and the ammonia or The first grade amine or the second grade amine is continuously supplied.

 With this configuration, in addition to the effects obtained in claim 1 or 2, the following actions can be obtained.

 (1) A polyhydric alcohol having 2 to 8 carbon atoms having a high polarity (for example, 1, 6-Hexanediol and 1,8-octanediol) were also found to have completely eliminated the induction period. As a result, the amination reaction can be started at the same time as the supply of raw materials to the solvent, which can significantly increase productivity and produce a variety of amines that were previously considered impossible. The applicability is remarkably excellent. In contrast, a method in which a catalyst raw material is dissolved in a highly polar polyhydric alcohol having 2 to 8 carbon atoms and subjected to a reducing activity treatment, and then an amine such as a primary amine is supplied thereto. There was a tendency for the catalyst to agglomerate in the monohydric alcohol, and the fact that the original activity was not expressed and an induction period of several hours was sometimes observed.

[0028] Here, as the solvent, a higher boiling higher alcohol can be used. By reducing and activating the catalyst raw material in the solvent, a high concentration catalyst solution in which the catalyst is uniformly dissolved in the solvent can be produced.

The amination reaction can be carried out by continuously supplying polyhydric alcohol, amino alcohol and amine to this catalyst solution in the same way as the fixed bed process. The obtained amino compound can be continuously distilled by utilizing the fact that the boiling point is lower than that of the catalyst solution. it can.

 As the higher alcohol used as the solvent, stearyl alcohol, behenyl alcohol, lignoalcohol and the like having 12 to 40 carbon atoms, preferably 18 to 24 carbon atoms, are preferably used. Reduction The activity of the colloidal catalyst after the activation treatment is high, so the amination reaction proceeds with almost no induction period, and the boiling point is high. Because it does not.

 The invention's effect

 As described above, according to the method for producing an amino compound of the present invention, the following advantageous effects can be obtained.

 According to the invention of claim 1,

 (1) By reacting in the presence of a catalyst containing copper, nickel, calcium, alkali metal or alkaline earth metal (excluding calcium) as an essential component, it can be industrially produced with high reaction rate and high selectivity. A method for producing an amino compound capable of producing a useful amino compound such as tertiary amine can be provided.

 (2) Since the catalyst is highly active, the reaction conditions are mild, and the reaction can be completed in a short time with a small amount of catalyst. Thus, a method for producing an amino compound that is remarkably excellent in productivity can be provided.

 (3) Since noble metals such as palladium and ruthenium are used as the catalyst, it is possible to provide a method for producing an amino compound that can suppress the running cost of the catalyst.

 (4) The disproportionation reaction of the raw material amine and the product amine derived from the precious metal content is greatly suppressed, the selectivity of the product amine can be improved, and an excellent method for producing an amino compound can be provided.

 [0030] According to the invention of claim 2, in addition to the effect of claim 1,

 (1) Since the raw material of the catalyst is metal sarcophagus, productivity is eliminated because complicated processes such as metal hydroxide production, water washing, drying, pulverization, and classification required for producing a solid catalyst are unnecessary. In addition, it is possible to provide a method for producing an amino compound that is remarkably excellent.

(2) Since the catalyst reduced with polyhydric alcohol is colloidal, it can be applied to batch and continuous methods, and can easily be applied to small-scale production. A method for producing a compound can be provided. [0031] According to the invention of claim 3, in addition to the effect of claim 1 or 2,

 (1) The amination reaction is started immediately at the same time as the supply of the raw material to the solvent by continuously supplying the polyhydric alcohol, which is the starting material, to a solvent such as a higher alcohol aminated with a catalyst. Thus, the productivity can be remarkably enhanced, and a variety of amines, which have been considered impossible in the past, can be produced, and a method for producing an amino compound that is remarkably excellent in applicability can be provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. The produced amino compound was identified by gas chromatography and GCZMS (gas chromatography Z mass spectrometry).

 (Example 1)

 In a 500 mL flask equipped with a condenser and separator to separate the produced water, a reaction mixture sampling device, an exhaust gas outlet tube, a raw gas introduction tube (porous glass sparger), a stirrer, and a thermometer, 200 g of 1,12-dodecanediol was added as polyhydric alcohol, and copper stearate 2. Og (copper metal 0.1 wt% with respect to polyhydric alcohol) and nickel stearate 0.4 g (metal with respect to polyhydric alcohol) were used as catalyst raw materials. Nickel (0.02 wt%), calcium stearate (0.4 g) (metallic calcium with respect to polyhydric alcohol, 0.02 wt%) and barium stearate (0.4 g) (metal barium with respect to polyhydric alcohol (0.02 wt%)) The vessel was rotated, the inside of the flask was replaced with nitrogen, and the temperature was raised. The four kinds of metal stalagmites used as catalyst raw materials were uniformly dissolved by the time the temperature reached 100 ° C. When the temperature reached 100 ° C, the nitrogen was switched to hydrogen, and hydrogen gas was bubbled into the flask through a flow meter at a flow rate of 22 LZ hours for reduction activity treatment. The characteristic green color of divalent copper and nickel gradually faded at 170-190 ° C, and the catalyst raw material was reduced to an apparently uniform colloidal catalyst. The reaction temperature was maintained at 210 ° C, and secondary dimethylamine was continuously supplied as a mixed gas with hydrogen (flow rate: 22 LZ hours) at normal pressure and at a flow rate of 20-30 L Z hours.

After an induction period of several minutes, the amination reaction proceeded with water distillation. At the beginning of the reaction, the hue of the reaction mixture in the flask was black. As the reaction progressed, the catalyst in the flask became a complete brown colloidal shape, and the reaction rate rapidly increased. Reaction at 1 hour intervals The mixture was sampled and analyzed by gas chromatography, and the conversion rate, product ratio, yield and reaction rate were calculated. The reaction rate is the reaction rate per unit mol of copper and per unit supply rate of dimethylamine unit for the first step reaction shown by chemical reaction formula (E) and the second step reaction shown by chemical reaction formula (F). ^{(mole 'h _1' mole _1} - [mole 'Ι 1] - 1) were each calculated.

 The analysis conditions for gas chromatography are as follows.

 Model: GC — 14B, Shimadzu Seisakusho Ramen: 0.32mm X 30m, Carrier gas: Nitrogen 30mLZ, Packing agent: DB-17, Column temperature: 100 to 270 ° C, 270 ° C for 13 minutes Holding time, heating rate: 10 ° CZ min, detector: FID, sample concentration: 10%, split ratio: 20.

[0033] (Example 2)

 The amination reaction was carried out in the same manner as in Example 1 except that 1,10-decanediol was used as the polyhydric alcohol and dimethylamine was supplied at a flow rate of 28 L / hour.

[0034] (Example 3)

Using 1, _9-1 nonanediol polyhydric alcohol, except that supplied the Jimechiruamin at a flow rate of 28L / time, was carried out an amination reaction in the same manner as in Example 1.

 [0035] (Example 4)

 The amination reaction was carried out in the same manner as in Example 1 except that 1,8-octanediol was used as the polyhydric alcohol and dimethylamine was supplied at a flow rate of 28 L / hour.

 [0036] (Example 5)

A 500 mL flask equipped with a condenser and separator for separating the produced water, a reaction mixture sampling device, an exhaust gas outlet tube, a raw gas inlet tube, a stirrer, and a thermometer, was charged with behenyl alcohol (carbon 200 g of the number 22) is charged, and copper stearate as the catalyst raw material 4. Og (copper metal 0.2 wt% with respect to the higher alcohol of the solvent), nickel stearate 0.8 g (metal nickel with respect to the higher alcohol 0.04 wt%), calcium stearate Add 0.8 g (0.04 wt% metal calcium to higher alcohol) and 0.8 g barium stearate (0.04 wt% metal to higher alcohol), rotate the stirrer, and add nitrogen to the flask. The temperature was increased after replacement. The four types of metal sarcophagus used as catalyst raw materials were uniformly dissolved by the time the temperature reached 100 ° C. When 100 ° C is reached, switch the nitrogen to hydrogen and flow hydrogen gas. Reduction treatment was performed by publishing in a flask through a volume meter at a normal pressure and a flow rate of 22 LZ hours. At 170-190 ° C, the characteristic green color of divalent copper and nickel gradually faded, and the catalyst raw material was reduced to an apparently uniform colloidal catalyst. The reaction temperature was maintained at 210 ° C, and secondary ammine dimethylamine was continuously supplied as a mixed gas with hydrogen (flow rate 22LZ hours) at a flow rate of 20-30LZ at normal pressure for 3 hours, and behenyl alcohol was aminated. Thus, a catalyst solution in which N, N-dimethylbe-lamine was produced was obtained. The conversion rate of behenyl alcohol was 100%.

 1,6-Hexanediol as a polyhydric alcohol was continuously added to the catalyst solution maintained at 210 ° C at a feed rate of 0.48 mol Z hours, and dimethylamine was used as a secondary amine at normal pressure. Then, it was continuously published as a mixed gas with hydrogen gas at a feed rate of 1.0 mol Z hours. The hydrogen gas supply rate was 22 LZ hours.

 With the start of the supply of 1,6-hexanediol, the amination reaction proceeded with water distilling immediately. The induction period was not observed at all. After reaching steady state (average residence time 2.1 hours), sampling and gas chromatographic analysis were performed to calculate conversion, product ratio, yield, and reaction rate.

[0037] (Example 6)

 The amination reaction was carried out in the same manner as in Example 1 except that 12-hydroxystearyl alcohol was used as the polyhydric alcohol and dimethylamine was supplied at a flow rate of 17 LZ hours.

[0038] (Example 7)

 Copper stearate as catalyst raw materials 2. Og (0.1% by weight of metallic copper to polyhydric alcohol), 0.4g of nickel stearate (0.02% by weight of metallic nickel to polyhydric alcohol), calcium stearate 0.lg (multivalent Example except that 0.005 wt% metal calcium to alcohol, 0.05 calcium metal metal ratio to metal copper, and 0.4 g barium stearate (0.02 wt% metal metal to polyvalent alcohol) were used. The amination reaction was carried out in the same manner as in 1.

[Example 8]

As catalyst raw materials, copper stearate 2. Og (metal copper 0.1 wt% with respect to polyhydric alcohol), nickel stearate 0.4 g (metal nickel with respect to polyhydric alcohol 0.02 wt%), Calcium thetearate 0.2 g (metallic calcium to polyhydric alcohol 0.01 wt%, metallic calcium to metal copper ratio 0.1), barium stearate 0.4 g (polynium alcohol to polyhydric alcohol 0.02 wt% ) Was added in the same manner as in Example 1 except that a) was added.

 [0040] (Example 9)

 Copper stearate as catalyst raw material 2. Og (0.1% by weight of metallic copper to polyhydric alcohol), 0.4 g of nickel stearate (0.02% by weight of metallic nickel to polyhydric alcohol), 1.0 g of calcium stearate (multivalent) Except for the addition of 0.04wt% metallic calcium to alcohol, 0.5% metallic calcium to metal copper ratio, and 0.4g barium stearate (0.02wt% metallic norm to polyvalent alcohol). The amination reaction was carried out in the same manner as in Example 1.

 [Example 10]

 As catalyst raw materials, 2.0 g of copper stearate (0.1% by weight of metal to polyhydric alcohol), 0.4 g of nickel stearate (0.02% by weight of metal to polyhydric alcohol), 1.2 g of calcium stearate (multivalent) Except for the addition of 0.06 wt% metal calcium to alcohol, 0.6 calcium metal metal ratio to metal copper, and 0.4 g barium stearate (0.02 wt% metal polyhydric alcohol). The amination reaction was carried out in the same manner as in Example 1.

 [0042] (Comparative Example 1)

 As catalyst raw materials, copper stearate 2.0 g (copper metal 0.1% by weight relative to polyhydric alcohol), nickel stearate 0.4 g (metal nickel relative to polyhydric alcohol 0.02 wt%), barium stearate 0.4 g The amination reaction was carried out in the same manner as in Example 1 except that the metal barium (0.02 wt% relative to the dihydric alcohol) was removed. Comparative Example 1 is different from Example 1 in that calcium stearate is added as a catalyst raw material.

 [0043] (Comparative Example 2)

According to Example 1 described in (Patent Document 3), a three-way catalyst of copper nickel-platinum group element supported on synthetic zeolite (Cu: Ni: Ru = 4: l: 0.01, the support is Y-type zeolite, The supported amount was 50 wt%) based on the metal oxide. 1, 10 decane as polyhydric alcohol in a 500 mL flask equipped with a condenser and separator for separating the produced water, reaction mixture sampling device, exhaust gas outlet tube, source gas inlet tube, stirrer and thermometer 200 g of diol and 0.62 g of the prepared catalyst (0.1% by weight of metallic copper with respect to polyvalent alcohol) were charged and the temperature in the flask was increased by replacing the atmosphere with nitrogen. When the temperature reached 100 ° C, the nitrogen was switched to hydrogen, and hydrogen gas was blown into the flask at a flow rate of 22 LZ hours at atmospheric pressure through a flow meter, and the temperature was raised to 210 ° C. The reaction temperature was maintained at 210 ° C, and secondary ammine, dimethylamine, was continuously fed as a mixed gas with hydrogen (flow rate: 22 LZ hours) at a flow rate of 27 LZ hours, and the reaction was followed using gas chromatography.

 [0044] (Comparative Example 3)

 The amination reaction of 1,10-decanediol was carried out under exactly the same conditions as in Comparative Example 2, except that the catalyst support was synthetic zeolite MS-13X.

[0045] Table 1 shows the reaction time (hours) of Examples 1 to 6 and Comparative Examples 1 to 3, the conversion rate from polyhydric alcohol to amino compound (%), and the sampled reaction mixture. Polyhydric alcohol ratio (%), di tertiary amine ratio (%), mono tertiary amine ratio (%), high boiling point ratio (%), low boiling point ratio (%), amination reaction 1st stage When the reaction rate of the second stage ^{(mole 'h _1' mole _1} - [m ole 'h- 1] - 1) are collectively shown. In Table 1, the di tertiary amine is N, N,, ', Ν'-tetramethyl-1, 12-dodecandiamine in Example 1 and Comparative Example 1. In Example 2, Comparative Example 2 and Comparative Example 3, it is Ν, Ν, ', —, -tetramethyl-1,10 decandiamin, and in Example 3, Ν, Ν, Ν', Ν, monotetramethyl. 1, 9 nonanediamine, in Example 4, Ν, Ν, Ν ', Ν, —tetramethyl-1,8 octanediamine, and in Example 5, Ν, Ν, Ν', Ν, —tetramethyl— 1,6-hexanediamine. In Example 6, it is 12-Ν, Ν dimethylmethylamino 1- Ν,, Ν, and 1 dimethylstearylamine, and is expressed as mono tertiary amine. In Example 1 and Comparative Example 1, 12-Ν, ァ dimethylamino-1-dode quinol, Example 2, In Comparative Example 2 and Comparative Example 3, 10-Ν, Ν dimethylamino-decanol-1 was used, in Example 3, 9-Ν, Ν-dimethylamino-nano-no-ru 1 was used, and in Example 4, 8—Ν, ジ メ チ ル Dimethylaminooctanol 1; in Example 5, 6-Ν, Ν-dimethylamino-hexanol 1 In Example 6, it is 12-N, N dimethylaminostearyl alcohol.

 [table 1]

[0047] In Table 1, when Example 1 and Comparative Example 1 are compared, in Example 1, the conversion rate is 99.9% after 7 hours of reaction, and each of di-tertiary amine and mono-tertiary amine S is 84. 2%, 10.8% (total 95.0%), high-boiling products and low-boiling products were 4.2% and 0.6%, respectively, whereas in Comparative Example 1, the reaction time was 3-5 hours. However, the conversion is 94.0%, di tertiary amine and mono tertiary amine are 70.4%, 12.3% (total 82.7%), high boilers and low boilers are 9.8% each, The ratio was 0.8%, and it was revealed that Example 1 had a high conversion rate, and the target tertiary amine was obtained with high selectivity. In addition, also in the reaction rates of the first and second stages, it was found that the reaction in Example 1 proceeded at an extremely high reaction rate 3 to 4 times that of Comparative Example 1.

 In Comparative Example 1, the catalyst raw material calcium stearate is not supported, and the catalyst is a three-way catalyst of copper-keke loubarium. Therefore, the catalytic activity is much lower than 1Z3 or less of the catalyst of Example 1. Thus, the superiority of the calcium-containing colloidal catalyst was clearly confirmed.

[0048] Next, when Example 2 and Comparative Example 2 are compared, in Example 2, the conversion rate is 100% after 7 hours of reaction, di-tertiary amine and mono-tertiary amine are 88.3%, 5. Compared to 7% (total 94.0%), in Comparative Example 2, the conversion rate was 34.0% at the 6th hour of reaction, and di-tertiary amine and mono-tertiary amine were 2.9% each. 29. 1% (32.0% in total), and in Example 2, it was revealed that the target tertiary amine was obtained with high selectivity because of a high conversion rate. In addition, when the reaction rates of the second stage were compared, it was found that in Example 2 the reaction proceeded at an extremely high reaction rate of 40 times or more compared to Comparative Example 2. In Comparative Example 3, the amination reaction rate in the second stage was greatly improved as compared with Comparative Example 2, but as is clear from the comparison with Example 2, the calcium-containing colloidal used in the present invention was used. It was revealed that the catalyst had an overwhelmingly higher catalytic activity.

 [0049] In Examples 3 and 4, the conversion rate at reaction 19 hours was almost 100%, and the total of di-tertiary amine and mono-tertiary amine was about 90%. It became clear that the target tertiary amine was obtained with high selectivity.

In addition, according to Example 6, the conversion rate in a reaction of 16 hours, 12 hydroxy l-N, N dimethylstearylamine (mono-tertiary amine) and 12-N, N dimethylamino-1-N, N production ratio of dimethyl stearylamine (di tertiary Amin), respectively 94.7%, 61.6%, was 1% 33., amination reaction rate of the first stage (mole'h ^_1 'mole ^_1 - [ mole · h " ¹ ]" ¹ ) was 13, and the second stage amination reaction rate (unit is already described) was 4. Based on the above, by using a calcium-containing colloidal catalyst, a stable 12-hydroxyl group can be aminated by simply producing 12-hydroxy-1-N, N dimethylstearylamine from 12-hydroxystearyl alcohol. 12-N, N dimethylamino 1-Ν ′, N′-dimethylstearylamine can be produced, and the high catalytic activity of the calcium-containing colloidal catalyst used in the present invention was demonstrated.

[0050] Further, in Example 5 in which polyhydric alcohol and dimethylamine were continuously supplied to the catalyst solution, the average residence time (reaction time) that does not require any induction period was observed. 99.5% ratio, di tertiary amine and mono tertiary amine S 85.9%, 11.8% (97.7% in total), high boiling point and low boiling point 1.2%, It was found that it was possible to achieve a high conversion and selectivity, and extremely low high-boiling substances. It was also revealed that the reaction rate was extremely high.

 In addition, when the same amination reaction of 1,6 hexanediol as in Example 5 was carried out in the same batch reaction as in Examples 1 to 4 without using a continuous process (without using a catalyst solution), The reaction time was 5.5 hours, the conversion rate was 20%, and the total yield of di-tertiary amine and mono-tertiary amine was 20%.

Further, when the continuous process performed in Example 5 was applied to the amination reaction of 1,9 nonanediol and 1,8 octanediol in Examples 3 and 4, it was the same as in Example 5. In the same way, the induction period was completely extinguished.

 This showed the overwhelming advantage of the continuous process performed in Example 5.

[0051] The production ratios of the di-tertiary amine and mono-tertiary amine of Examples 7 and 10 and the production ratios of di-tertiary amine and mono-tertiary amine of Examples 8 and 9 in 1 hour of reaction In comparison, Examples 7 and 10 were significantly lower than Examples 8 and 9. According to this example, it was confirmed that when the ratio of calcium to copper is out of the range of 0.1 to 0.5 in the composition of the catalyst, the catalyst activity decreases.

[0052] In Examples 1 to 5, instead of copper stearate, stearic acid-kelke and calcium stearate as catalyst raw materials, copper myristate, copper acetylethylacetone, copper dimethyl daroxime, nickel dimethyl When using darioxime, nickel pelargonate, nickel acetylacetone, or calcium laurate, a conversion rate of almost 100% was obtained, and the same tendency was confirmed. Further, in Examples 1 to 5, when barium laurate and sodium stearate were used instead of barium stearate, a conversion rate of almost 100% was obtained, and the same tendency was confirmed. However, it was confirmed that the reaction rate was slightly lower when barium laurate and sodium stearate were used than when barium stearate was used. This indicates that a metal salt of stearic acid, which has a longer chain length than lauric acid, is superior to lauric acid in inhibiting the aggregation of copper / nickel metal colloids. In addition, the stearates of nor- um indicate that the aggregation inhibition effect of the copper Z nickel metal colloid is superior to that of sodium stearate.

[0053] As described above, according to this example, a high yield was obtained by reacting with a catalyst containing copper, nickel, calcium, alkali metal or alkali earth metal (excluding calcium) as an essential component. It became clear that tertiary amines can be obtained with high selectivity. It was also found that the reaction can be completed at an extremely high reaction rate even in the second-stage amination reaction, which is the rate-limiting step. Furthermore, by continuously supplying polyhydric alcohol and jetylamine to the catalyst solution, the original activity of the catalyst can be expressed, an extremely high reaction rate without any induction period can be obtained, and an extremely high selectivity. It became clear that can be realized. As a result, it is possible to produce a variety of amins that were previously considered impossible, and to provide a method for producing an amino compound that is remarkably excellent in applicability. Industrial applicability

 The present invention relates to a process for producing an amino compound, which comprises reacting a polyhydric alcohol namino alcohol and ammonia or a primary or secondary amine to produce a corresponding tertiary amine namino alcohol or the like. In this regard, since no precious metals such as palladium and ruthenium are used in the catalyst, the running cost can be greatly reduced, and the amination reaction of the present invention basically does not require hydrogen (reduction activity of the catalyst raw material). Since the combined use of calcium as a catalyst component has strengthened its effect, it is highly useful for amino acids such as tertiary amines that are industrially useful at high reaction rates and high yields. It is possible to provide a method for producing an amino compound capable of producing a product.

Claims

The scope of the claims  [1] Polyhydric alcohol and Z or an amino alcohol obtained by aminating the polyhydric alcohol, and ammonia, primary amine, or secondary amine, copper, nickel, calcium, alkali metal, or alkaline earth metal A method for producing an amino compound, which comprises reacting in the presence of a catalyst containing (except calcium) as an essential component. [2] The catalyst is (a) one or more of a copper carboxylate or a copper intramolecular complex, and (b) one or two of a nickel carboxylate or a nickel intramolecular complex. And (c) one or more of calcium carboxylate or calcium complex, and (d) one or more of alkali metal or alkaline earth metal (excluding calcium) carboxylate And the mixture of the above and the polyhydric alcohol or the amino alcohol or a solvent obtained by reduction treatment with hydrogen or another reducing agent. Method.  [3] Continuously supplying the polyhydric alcohol and Z or the amino alcohol and the ammonia, the primary amine, or the secondary amine to the solvent aminated with the catalyst. The method for producing an amino compound according to claim 1, wherein the amino compound is produced.