WO2008018148A1 - Procédé servant à produire un composé aminé - Google Patents

Procédé servant à produire un composé aminé Download PDF

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WO2008018148A1
WO2008018148A1 PCT/JP2006/315937 JP2006315937W WO2008018148A1 WO 2008018148 A1 WO2008018148 A1 WO 2008018148A1 JP 2006315937 W JP2006315937 W JP 2006315937W WO 2008018148 A1 WO2008018148 A1 WO 2008018148A1
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catalyst
reaction
calcium
alcohol
copper
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PCT/JP2006/315937
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English (en)
Japanese (ja)
Inventor
Makoto Imabeppu
Kazunori Kiyoga
Shinji Okamura
Hiroshi Kimura
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Kokura Synthetic Industries, Ltd.
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Priority to PCT/JP2006/315937 priority Critical patent/WO2008018148A1/fr
Priority to JP2007162732A priority patent/JP2008044930A/ja
Priority to CNA2007101368025A priority patent/CN101121666A/zh
Publication of WO2008018148A1 publication Critical patent/WO2008018148A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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
  • 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.
  • a catalyst raw material 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.
  • 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.
  • Patent Document 4 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.
  • Patent Document 2 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 could't make it.
  • 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.
  • 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.
  • 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.
  • the starting material an amino alcohol
  • the starting material 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.
  • monoethanolamine, diethanolamine, methylethanolamine, methylethanolamine, dimethylethanolamine, jetylethanolamine, diisopropylethanolamine, and dibutylethanolamine can be used.
  • the starting amine as a starting material is ammonia, a primary amine represented by the general formula I ⁇ NH
  • 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
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the intramolecular copper complex examples include general chelate compounds containing no io, such as a cetylacetone complex and a dimethyldarioxime complex.
  • nickel carboxylate and nickel intramolecular complex are also reduced during the reduction activation process.
  • 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.
  • (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.
  • the carboxylic acid include those similar to the carboxylic acid.
  • 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.
  • 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.
  • a higher boiling higher alcohol can be used as the solvent for dissolving the catalyst raw material.
  • a highly concentrated catalyst solution can be produced by reducing the catalyst raw material in a solvent.
  • the amination reaction of polyhydric alcohol and amino alcohol can also be carried out.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the distillation of water is also stopped.
  • the amination reaction can be completed in 2 to 10 hours.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • the amination reaction can be performed batchwise, continuously, or offset.
  • a batch type for example, a normal stirred layer reactor, an injector type stirred reactor, a loop reactor, or the like can be used.
  • a special stirring device can be used as required, such as a gas stirring type reactor.
  • Examples of the amino compound obtained by the present invention include N, N, ⁇ ', ⁇ '-tetramethyl-1, 6-hexamethylenedian, ⁇ , ⁇ , ⁇ ', ⁇ , -tetramethyl-1, 8-Otatamethylenedian, ⁇ , ⁇ , ⁇ ', ⁇ , -Tetramethyl-1,9-nonamethylenedian, ⁇ , ⁇ , ⁇ ', ⁇ , -Tetramethyl-1,10-decamethylenedian, ⁇ , ⁇ , ⁇ ', ⁇ , -tetramethyl-1, 12-dodecamethylenedian, 12-hydroxy- ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylstearylamine, 12-—, ⁇ ⁇ ⁇ ⁇ dimethyl ⁇ ,, , -dimethylstearylamine, etc. And tertiary amino amines, and amino alcohols which are intermediates of these tertiary amines. These amino compounds are suitably used as catalysts
  • the catalyst 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.
  • 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.
  • 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.
  • it is also effective to increase the amount of stabilizer (alkali metal or alkaline earth metal (excluding calcium) component) among the catalyst components.
  • stabilizer alkali metal or alkaline earth metal (excluding calcium) component
  • 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.
  • 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.
  • 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.
  • 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.
  • a polyhydric alcohol having 2 to 8 carbon atoms having a high polarity for example, 1, 6-Hexanediol and 1,8-octanediol
  • 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.
  • the solvent a higher boiling higher alcohol can be used.
  • 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.
  • 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 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.
  • a solvent such as a higher alcohol aminated with a catalyst.
  • the produced amino compound was identified by gas chromatography and GCZMS (gas chromatography Z mass spectrometry).
  • 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.
  • 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.
  • 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 ' ⁇ 1] - 1) were each calculated.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • copper stearate 2 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reaction rate of the second stage mole 'h _1' mole _1 - [m ole 'h- 1] - 1
  • the di tertiary amine is N, N,, ', ⁇ '-tetramethyl-1, 12-dodecandiamine in Example 1 and Comparative Example 1.
  • Example 2 Comparative Example 2 and Comparative Example 3, it is ⁇ , ⁇ , ', —, -tetramethyl-1,10 decandiamin, and in Example 3, ⁇ , ⁇ , ⁇ ', ⁇ , monotetramethyl. 1, 9 nonanediamine, in Example 4, ⁇ , ⁇ , ⁇ ', ⁇ , —tetramethyl-1,8 octanediamine, and in Example 5, ⁇ , ⁇ , ⁇ ', ⁇ , —tetramethyl— 1,6-hexanediamine.
  • Example 6 it is 12- ⁇ , ⁇ dimethylmethylamino 1- ⁇ ,, ⁇ , and 1 dimethylstearylamine, and is expressed as mono tertiary amine.
  • Example 1 and Comparative Example 1 12- ⁇ , ⁇ dimethylamino-1-dode quinol, Example 2, In Comparative Example 2 and Comparative Example 3, 10- ⁇ , ⁇ dimethylamino-decanol-1 was used, in Example 3, 9- ⁇ , ⁇ -dimethylamino-nano-no-ru 1 was used, and in Example 4, 8— ⁇ , ⁇ ⁇ ⁇ ⁇ Dimethylaminooctanol 1; in Example 5, 6- ⁇ , ⁇ -dimethylamino-hexanol 1 In Example 6, it is 12-N, N dimethylaminostearyl alcohol.
  • Example 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.
  • Example 1 had a high conversion rate, and the target tertiary amine was obtained with high selectivity.
  • 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.
  • Example 2 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.
  • Example 2 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.
  • 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.
  • 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.
  • 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- ⁇ ′, N′-dimethylstearylamine can be produced, and the high catalytic activity of the calcium-containing colloidal catalyst used in the present invention was demonstrated.
  • 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.
  • Example 5 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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Abstract

L'invention concerne un procédé servant à produire un composé aminé dans lequel, en faisant réagir un polyol ou un aminoalcool avec de l'ammoniac ou une amine primaire ou une amine secondaire, on produit une amine tertiaire, un aminoalcool ou similaire correspondant. L'invention concerne un procédé servant à produire un composé aminé grâce auquel le coût de la production peut être réduit parce qu'on n'utilise pas de métal noble tel que le palladium ou le ruthénium en tant que catalyseur et on peut produire un composé aminé tel qu'une amine tertiaire qui est industriellement utile avec une vitesse de réaction élevée, un rendement de production élevé et une sélectivité élevée. L'invention utilise une structure dans laquelle on fait réagir un polyol et de l'ammoniac ou une amine primaire ou une amine secondaire en présence d'un catalyseur contenant du cuivre, du nickel, du calcium, un métal alcalin ou un métal alcalinoterreux (à l'exception du calcium) en tant que composant essentiel.
PCT/JP2006/315937 2006-08-11 2006-08-11 Procédé servant à produire un composé aminé WO2008018148A1 (fr)

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JP2007162732A JP2008044930A (ja) 2006-08-11 2007-06-20 アミノ化合物の製造方法
CNA2007101368025A CN101121666A (zh) 2006-08-11 2007-07-17 氨基化合物的制备方法

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CN101391964B (zh) * 2008-11-07 2011-06-01 天津大学 制备2-氨基-1-烷基醇的方法及催化剂制备方法
CN102614886B (zh) * 2012-02-27 2014-03-05 上海应用技术学院 一种用于制备手性氨基醇的催化剂及制备方法及应用
CN103288722A (zh) * 2013-05-08 2013-09-11 温州大学 一种仲胺的高选择性合成方法
CN106546067B (zh) * 2015-09-18 2022-08-19 海南椰国食品有限公司 细菌纤维素凝胶膜置换低温一体式干燥方法
CN105384706A (zh) * 2015-10-27 2016-03-09 中国科学院兰州化学物理研究所 一种n-丙酮基胺类化合物的制备方法
CN105622436A (zh) * 2016-03-01 2016-06-01 苏州艾缇克药物化学有限公司 一种以碳酸钙为催化剂的6-氨基-1-己醇制备方法
CN109395743A (zh) * 2018-12-18 2019-03-01 浙江工业大学 一种络合型的金属镍催化剂及其制备方法和应用
CN114874100B (zh) * 2022-06-07 2023-12-22 中国日用化学研究院有限公司 一种n,n,n`,n`-四甲基烷基二胺的制备方法
CN116099537A (zh) * 2022-12-08 2023-05-12 东南大学 一种Ni-NiO多相磁性催化剂及制备方法及其应用
CN116716031A (zh) * 2023-08-08 2023-09-08 广州市交通运输职业学校(广州市交通运输高级职业技术学校、广州市交通运输中等专业学校) 一种免喷漆速干车身修复材料及其制备方法

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