KR20220089387A - Catalyst for producing omega aminoalkanoic acid by simultaneous reductive amination and hydrolysis reaction and method for producing omega aminoalkanoic acid using the same - Google Patents

Abstract

The present invention relates to a catalyst for accelerating the reaction of producing omega aminoalkanoic acid from a natural material, a method for preparing the same, and a method for producing omega aminoalkanoic acid using the catalyst. Metathesis reaction of oleic acid-containing oil and transester It is characterized by synthesizing omega aminoalkanoic acid in high yield by simultaneously performing reductive amination of aldehyde and hydrolysis of ester on omega aldehyde ester prepared by reaction and hydroformylation reaction. Since the two-step reaction of the hydrolysis reaction step is performed simultaneously in a single reactor as one step, the hydrolysis reaction facility, separation and purification of the amine ester product, and the hydrolysis catalyst removal process are omitted, which is very economical and eco-friendly.

Description

Catalyst for producing omega aminoalkanoic acid by simultaneous reductive amination and hydrolysis reaction and method for producing omega aminoalkanoic acid using the same the same}

The present invention relates to a catalyst for producing omega aminoalkanoic acid using reductive amination and hydrolysis, and to aminoalkanoic acid production using the same, and more particularly, to polyamide (nylon) In the production of omega aminoalkanoic acid, which is a raw material, using omega aldehyde ester as a raw material, Raney Ni-M catalyst that can simultaneously promote reductive amination of aldehyde and hydrolysis of ester, and omega aminoalkanoic acid using the same it's about how

Polyamide 11 or nylon 11, known as Arkema Rilsan ^® , is synthesized by the condensation polymerization of carbon 11 omega aminoalkanoic acids. Nylon 11 is currently a bioplastic synthesized from castor oil, and has the lowest melting point, lowest specific gravity and the highest compared to petroleum-based nylon 6, nylon 6-6 and nylon 6-10. It has low moisture absorption. In addition, it has acid resistance, alkali resistance and oxidation resistance, so it is a high-quality engineering plastic, and is used in the automobile industry, fuel, electronics, and sports industries as cables, tubes, sporting goods, industrial fibers, powder coatings, and synthetic fibers.

Carbon 11 omega aminoalkanoic acid is industrially synthesized from the ricinoleic acid component of castor oil in five steps, and as shown in FIG. 1, castor oil is transesterified with methyl alcohol and converted to methyl lysinoleate. (I), methyl lysinoleate is thermally decomposed at high temperature to synthesize methyl undecyrenate and heptanaldehyde (II). The synthesized methyl undecyrenate is hydrolyzed to synthesize undecyrenic acid (III), and the undecyrenic acid (carbon 11 omega olefin acid) is reacted with hydrobromic acid under peroxide to synthesize carbon 11 omega bromoalkanoic acid ( IV). Thereafter, carbon 11 omega bromoalkanoic acid is subjected to a reductive amination reaction to finally synthesize carbon 11 omega aminoalkanoic acid (V). However, since the process may be harmful to the environment by using bromine, which is an environmentally toxic material and excessive energy consumption in the high-temperature pyrolysis step, a reduction in energy use and improvement to an eco-friendly process are required.

On the other hand, as a related prior art, U.S. Patent Publication No. 2016/0185705 A1 reports a method of synthesizing carbon 11 omega bromoalkanoic acid by reacting undecyrenic acid (carbon 11 omega olefinic acid) with hydrobromic acid under a peroxide, US Patent 8431728 In B2, a method of synthesizing carbon 11 omega aminoalkanoic acid by reductive amination reaction of carbon 11 omega bromoalkanoic acid, and in Chinese Patent CN103804209, a method of continuously performing bromination and amination were reported.

In addition to castor oil, a method for synthesizing carbon 11 omega aminoalkanoic acid by performing a six-step reaction of reduction, oxidation, oximation, Bachman rearrangement, Hoffman decomposition and hydrolysis from veronolic acid is described ( JAOCS, 1997, 74, pp531-538), but there are 6 more steps than the Arkema process, and process improvement is required due to the low yield in each step (see FIG. 2).

Meanwhile, in Korea Patent 10-1341888, carbon 11 omega aminoalkanoic acid is synthesized by continuously performing a reductive ozonolysis reaction of an oleic acid ester obtained from vegetable oil, a Knefenagel condensation reaction using cyanoacetic acid, and a two-step hydrogen reduction reaction. reported how to do it. Compared to the Arkema process, which uses castor oil as a raw material, various vegetable oils are used, and it is synthesized in four relatively small steps. is required 3 shows the reaction scheme in the above patent.

In Elevance, as in the reaction step shown in FIG. 4, methyl undecyrenate (carbon 10 omega olefinic acid methyl ester) has been developed and commercialized. Compared to the process synthesized from castor oil, it has the advantage of being able to use various inexpensive vegetable oils and a high-yield, low-energy cost process due to the low-temperature and low-pressure metathesis process rather than the pyrolysis process.

As a result of the present inventors' efforts to develop a method for producing carbon 11 omega aminoalkanoic acid, the monomer of polyamide 11, from a natural material, carbon 11 omega aldehyde prepared by metathesis reaction of oleic acid-containing oil, transesterification reaction, and hydroformylation reaction The present invention was completed by confirming that carbon 11 omega aminoalkanoic acid can be prepared in one step by simultaneously performing reductive amination of an aldehyde and hydrolysis of an ester to an ester in the presence of a specific catalyst.

US Patent Publication No. 2016/0185705 A1 (published on June 30, 2016) US Patent 8431728 B2 (2013.04.30. Announcement) China Registered Patent 103804209 B (2016.01.27. Announcement) Korean Patent Registration 10-1341888 B1 (2013.12.10. Announcement)

JAOCS, 1997, 74, 531-538

In order to solve the above problems, an object of the present invention is to provide a catalyst useful for simultaneously performing aldehyde reductive amination and ester hydrolysis of carbon 11 omega aldehyde esters and a method for preparing the same.

Another object of the present invention is to provide a method for preparing carbon 11 omega aminoalkanoic acid by simultaneously performing aldehyde reductive amination of carbon 11 omega aldehyde ester and hydrolysis of the ester.

In order to solve the above problems, the present invention provides a Raney Ni-M metal catalyst in which one or more metals M and Raney Ni selected from chromium, molybdenum, manganese, iron, and cobalt are mixed, wherein the Raney Ni content is 90 to 99.9 wt% And the content of M provides a catalyst for the production of omega aminoalkanoic acid from omega aldehyde ester, characterized in that 0.1 to 10wt%.

In the Raney Ni-M catalyst, the content of Ni analyzed by an Energy Dispersive X-ray Spectrometer (EDS) may be 80 to 99 wt%.

In one embodiment of the present invention, the metal M may be dispersed on the surface of Raney Ni.

In addition, the present invention comprises the steps of: a) dissolving a precursor of at least one metal M selected from among chromium, molybdenum, manganese, iron, and cobalt in a solvent to prepare a M precursor solution; b) adding Raney Ni to the M precursor solution, mixing, and drying; c) sintering Raney Ni containing the M precursor in a hydrogen atmosphere; provides a method for preparing a metal catalyst for preparing omega aminoalkanoic acid from omega aldehyde ester, comprising the steps of:

In step a), the solvent for dissolving the precursor of metal M may be at least one selected from methyl alcohol, ethyl alcohol, propyl alcohol, acetone, methyl ethyl ketone, dioxane, ethyl acetate, and toluene, and as the precursor of metal M, acetyl It may be an acetonate metal compound, a carbonyl metal compound, and an acetate metal compound.

In addition, the hydrogen atmosphere in step c) may be a hydrogen atmosphere diluted with nitrogen, and the firing temperature may be in the range of 200 to 500°C.

In addition, the present invention provides a method for preparing omega aminoalkanoic acid by simultaneously performing a reductive amination reaction and a hydrolysis reaction of an omega aldehyde ester in the presence of a catalyst according to the present invention.

The omega aldehyde ester may be obtained by hydroformylation of an omega olefin acid ester obtained by metathesis of oleic acid. It can be carried out under a hydrogen pressure of bar.

The catalyst according to the present invention can simultaneously perform reductive amination of aldehyde and hydrolysis of ester of omega aldehyde ester prepared by metathesis reaction of oleic acid-containing oil, transester reaction, and hydroformylation reaction, The method of the present invention for producing the used omega aminoalkanoic acid from a natural material is economical because the existing two-step reaction is simplified in one step, the reaction equipment in the first step, product separation and purification, and the catalyst removal process in the intermediate step are omitted, and also Eco-friendly.

1 shows a reaction scheme of five steps for industrially synthesizing aminoalkanoic acid from ricinoleic acid component of castor oil.
2 shows a reaction scheme for synthesizing carbon 11 omega aminoalkanoic acid from veronolic acid through a six-step reaction.
3 shows a reaction scheme for synthesizing carbon 11 omega aminoalkanoic acid by continuously performing a reductive ozonolysis reaction of an oleic acid ester, a Knefenagel condensation reaction using cyanoacetic acid, and a two-step hydrogen reduction reaction.
Figure 4 is a method of synthesizing methyl undecyrenate (carbon 10 omega olefinic acid methyl ester) in two consecutive steps of metathesis and transesterification of vegetable oils such as soybean oil, palm oil, canola oil and rapeseed oil by Elevance. The reaction formula is shown.
5 shows a reaction scheme for preparing an aminoalkanoic acid or a structural isomer thereof using a hydroformylation reaction.
6 shows a two-step scheme for synthesizing an aminoalkanoic acid from an aldehyde ester.
7 shows a reaction scheme for preparing aminoalkanoic acid from an aldehyde ester according to the present invention in one step.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the experimental methods described below are those well known and commonly used in the art.

The present invention is an efficient method for producing omega aminoalkanoic acid from natural materials. Reductive amination of aldehyde and hydrolysis of omega aldehyde ester prepared by metathesis reaction of oleic acid-containing oil, transester reaction, and hydroformylation reaction Omega aminoalkanoic acid can be prepared in one step using a catalyst that simultaneously promotes

The omega aldehyde ester in the present invention may be a carbon 11 omega aldehyde ester, and the omega aminoalkanoic acid may be a carbon 11 omega aminoalkanoic acid, a monomer of polyamide 11.

The carbon 11 omega aminoalkanoic acid prepared according to the embodiment of the present invention and its structural isomer are used as a monomer of polyamide, and may be polyamide having different physical properties depending on the ratio of each isomer. Structural isomers can be synthesized through the characteristics of the reaction in the hydroformylation step, and these isomers can produce carbon 11 omega aminoalkanoic acid through a series of reactions. Therefore, the present invention can be a new eco-friendly method for producing various polyamides.

In the method for preparing aminoalkanoic acid or its structural isomer using the hydroformylation reaction, an aldehyde ester is prepared by hydroformylation of an olefinic acid ester in the presence of a ligand and a catalyst, as shown in the reaction scheme shown in FIG. 5 .

The conventional method for synthesizing aminoalkanoic acid from the aldehyde ester obtained in the hydroformylation step undergoes a two-step reaction as shown in FIG. 6 below.

First, ammonia and hydrogen are added to the aldehyde ester in a first step to a predetermined pressure, and the aldehyde is selectively reductive amination using an amination catalyst such as Raney Nickel to synthesize an amino ester, and then the amination catalyst and unreacted ammonia. In the next two steps, water as a reactant and an acid catalyst for the hydrolysis reaction are added to the amino ester, and the amino ester is hydrolyzed by refluxing at atmospheric pressure to synthesize amino alkanoic acid.

In proceeding the reaction in two steps as described above, since the reductive amination reaction catalyst, reactant, and reaction conditions of the first step are very different from the hydrolysis reaction catalyst, the reactant, and the reaction conditions of the second step, each reaction when proceeding at the same time In the reaction, the unreacted and side reactions proceed greatly, resulting in a very low yield of the final aminoalkanoic acid. This is because the activity of each catalyst decreases due to action and poisoning.

However, in the present invention, a catalyst capable of simultaneously promoting the reductive amination reaction and the hydrolysis reaction has been developed, unlike the existing individual catalysts that promote each of the above reactions. When the catalyst of the present invention is used, FIG. As shown, the reductive amination reaction of an aldehyde and the hydrolysis reaction of an ester are simultaneously carried out using ammonia and water as raw materials to prepare an aminoalkanoic acid in one step.

In the present invention, ammonia and water used as raw materials for the reductive amination reaction and hydrolysis reaction of omega aldehyde esters are at least one organic selected from the group consisting of methanol, ethanol, propanol, butanol, benzene, toluene and xylene. It may be in a dissolved state in a solvent, and preferably, ammonia and water may be dissolved in methanol at the same time.

The ammonia may be added in an amount of 1 to 20 equivalents, preferably 1 to 10 equivalents. When ammonia is added in less than 1 equivalent, there is a problem that the reaction does not proceed completely, and when added in excess of 20 equivalents, there is a problem in that the treatment cost increases due to waste after the reaction.

The water may be added in an amount of 1 to 20 equivalents, preferably 1 to 10 equivalents. When less than 1 equivalent of water is added, there is a problem in that the hydrolysis reaction does not proceed completely, and when water is added in excess of 20 equivalents, there is a problem in that reductive amination reactivity is reduced.

The catalyst effective for the simultaneous reductive amination and hydrolysis reaction according to the present invention includes at least one metal M among chromium, molybdenum, manganese, iron, and cobalt and Raney Nickel, and in the present specification, the catalyst is It is expressed as “Raney Ni-M”.

Raney nickel, also called sponge nickel, is a fine-grained solid composed of nickel derived from a nickel-aluminum alloy. It melts and removes aluminum by applying a hot aqueous solution of sodium hydroxide to an alloy in which nickel and aluminum are approximately equal in amount. It is manufactured by leaving The Raney Nickel may contain up to about 10 wt% of Na, Al, or the like.

In the Raney Ni-M catalyst, the Raney Ni content may be 90 to 99.9 wt%, preferably 95 to 99.9 wt%, and the M content may be 0.1 to 10 wt%, preferably 1 to 5 wt%.

As described above, since the Raney Ni may also contain Al, Na, etc. depending on the manufacturing method, the Raney Ni-M catalyst according to the present invention was analyzed using an Energy Dispersive X-ray Spectrometer (EDS). The content may be in the range of 80 to 99 wt%, preferably in the range of 90 to 95 wt%.

In the Raney Ni-M catalyst of the present invention, it is determined that the Raney Ni component is active in the reductive amination reaction, and the metal M component is active in the hydrolysis reaction. In the Raney Ni-M catalyst of the present invention, M is preferably chromium and/or molybdenum.

The Raney Ni-M metal catalyst of the present invention comprises: a) dissolving a precursor of at least one metal M selected from chromium, molybdenum, manganese, iron, and cobalt in a solvent to prepare a M precursor solution; b) adding Raney Ni to the M precursor solution, mixing, and drying; c) It can be synthesized through the step of calcining Raney Ni containing M precursor under a reducing gas atmosphere.

As a solvent for dissolving the precursor of metal M in step a), at least one solvent selected from among methyl alcohol, ethyl alcohol, propyl alcohol, acetone, methyl ethyl ketone, dioxane, ethyl acetate, and toluene is preferable, and the amount of the solvent used is determined by the mass of the precursor. 2 to 10 times the contrast is preferred. If the amount of the solvent used is less than 2 times, the precursor is not uniformly dissolved and the M component is not uniformly dispersed, so that the reaction activity and selectivity decrease. The drying time is greatly increased, and since the uniform and rapid loading of the precursor is not performed, non-uniform dispersion of the M component occurs, thereby reducing the reaction activity and selectivity.

As a precursor of the M metal component, an acetylacetonate metal compound, a carbonyl metal compound, and an acetate metal compound are preferable, and specifically, chromium acetylacetonate (Cr(acac) ₃ ), chromium carbonyl (Cr(CO) ₆ ), Chromium acetate (Cr(OAc) ₃ ), molybdenum acetylacetonate (MoO ₂ (acac) ₂ ), molybdenum carbonyl (Mo(CO) ₆ ), molybdenum acetate dimer (Mo ₂ (OAc) ₄ ), manganese acetylacetonate (Mn(acac) ₂ , Mn(acac) ₃ ), manganesecarbonyl (Mn ₂ (CO) ₁₀ ), manganese acetate (Mn(OAc) ₃ , Mn(OAc) ₂ ), iron acetylacetonate (Fe(acac) ) ₃ ), iron carbonyl (Fe ₃ (CO) ₁₂ ), iron acetate (Fe(OAc) ₂ ), cobaltacetylacetonate (Co(acac) ₂ , Co(acac) ₃ ), cobaltcarbonyl (Co ₂ ) (CO) ₈ ), cobalt acetate (Co(OAc) ₂ ), and the like.

In step b), Raney Ni is added to the M precursor solution, mixed, and then dried. The Raney Ni is mixed with the M precursor solution in a powder state. Mixing may be performed using a conventional mixing means, and drying is usually performed in a temperature range of 40 to 80°C.

Step c) is a step of calcining Raney Ni containing M precursor obtained in step b) under a hydrogen atmosphere.

In the hydrogen atmosphere, the calcination is carried out under a hydrogen atmosphere alone, preferably under a diluted hydrogen atmosphere, and more preferably under a hydrogen atmosphere diluted with nitrogen. The hydrogen content in the diluted hydrogen gas is preferably 5 vol% to 30 vol%.

The firing temperature is preferably 200°C to 500°C. Firing at less than 200 °C does not cause sufficient bonding and activation of the M precursor and Raney Ni, causing mutual collision and poisoning between the properties of the two catalyst components, resulting in reduced reaction activity and selectivity. The effective active site for each reaction is decreased due to over-bonding or sintering between the component and the Raney Ni component, or a metal complex that causes a side reaction is generated, thereby reducing the reaction yield.

The firing time may vary depending on the conditions, but it is generally carried out for 3 to 10 hours. The Raney Ni-M catalyst obtained through calcination is in a state in which particles of metal M are dispersed on the surface of Raney Ni.

After firing, it is cooled to room temperature and stored in water for use. At this time, the metal content of the Raney Ni-M metal catalyst aqueous slurry stored in water is usually 40 to 50 wt%.

The present invention also provides a method for preparing omega aminoalkanoic acid by simultaneously performing a reductive amination reaction and a hydrolysis reaction of an omega aldehyde ester under the catalyst of the present invention. The method for preparing aminoalkanoic acid may be to perform the reaction for about 3 to 12 hours at a reaction temperature of 60 to 150° C. and a hydrogen pressure of 10 to 100 bar.

cooling the reaction mixture after the reductive amination and hydrolysis reactions; lowering the pressure in the reactor; It may further comprise the step of filtering the product.

Hereinafter, the present invention will be described in more detail through examples. These examples are for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

<Synthesis of aldehyde ester by hydroformylation of olefinic acid ester>

The carbon 10 omega olefin acid ester (methyl 9-dodecenoate) synthesized by the metathesis reaction of vegetable oil oleic acid was subjected to a hydroformylation reaction as follows to synthesize a carbon 11 omega aldehyde ester. Using 0.1 mol% of a rhodium catalyst [Rh(CO) ₂ (acac), Aldrich) and 0.4 mol% of triphenylphosphine (PPh ₃ , Aldrich), CO/H ₂ 18 at 40 bar, 60°C The hydroformylation reaction was carried out for a period of time. After the reaction, the product was quantitatively analyzed by ¹ H-NMR, and the reaction analysis result is shown in Synthesis Example 1 in Table 1. In addition, the reaction results using the ligand as bis(2-diphenylphosphinophenyl)ether (DPEphos, Aldrich) under the same reaction conditions are shown in Synthesis Example 2 in Table 1.

When triphenylphosphine [PPh ₃ ] was used as a ligand, the carbon 10 omega olefinic acid ester showed a conversion rate of 99%, and a linear to branched aldehyde ratio (l/b) of 1.9 was confirmed. The hydrogenation product as an addition reaction was confirmed to be 13%. And the bidentate ligand, DPEphos ligand, showed a conversion rate of 99%, but a linear to branched aldehyde ratio of 0.8.

As a result of this hydroformylation reaction, it was found that the monodentate ligand has better reactivity than the bidentate ligand, and the ratio of the resulting linear and branched aldehydes can be controlled depending on the ligand. The ratio (l/b) of linear and branched aldehydes could be controlled from 0.8 to 1.9.

In the table below, products A, B, C, and D are the products of FIG. 5, and specifically, A is methyl 11-oxoundecanoate, B is methyl 9-methyl-10-oxodecanoate, C is methyl 8-formyldecanoate, D is methyl decanoate .

Synthesis example Ligand Conv.
(%) l/b Yield (%) A B C D Synthesis Example 1 PPh ₃ >99 1.9 57 24 6 13 Synthesis Example 2 DPEphos >99 0.8 45 37 17 One

<Example 1>

Raney Ni-Mo metal catalyst synthesis

The Raney Ni-Mo metal catalyst was synthesized as follows. Molybdenum acetylacetonate (MoO ₂ (acac) ₂ , Aldrich Co.) was used as the Mo metal precursor, and as Raney Ni, Metalyst ^™ MC 111 (Ni 93wt%, Evonik) was used. 3.26 g (0.01 mol) of molybdenum acetylacetonate (MoO ₂ (acac), Aldrich) was added to 15 g of a mixed solvent of ethyl alcohol and toluene (alcohol and toluene weight ratio of 1:1) was dissolved at 50° C., and then the molybdenum acetyl aceto Add 49 g of Raney Ni Metalyst ^™ MC 111 to the solution in which the nitrate is dissolved and mix. The mixed slurry is dried at 60°C for 4 hours. After drying, it is placed in a kiln and calcined at 350° C. for 6 hours under a nitrogen atmosphere containing 10% hydrogen. After firing, it is cooled to room temperature and stored in water for use. As a result of analyzing the synthesized Raney Ni-Mo (91-2) catalyst sample with an Energy Dispersive X-ray Spectrometer (EDS), the Ni content was 91wt% and the Mo content was 1.9wt% it was In the notation of Raney Ni-Mo (91-2), the number 91-2 in parentheses indicates the content of Ni and Mo analyzed by EDS, respectively. Hereinafter, the catalyst content was indicated in the same manner.

Simultaneous reductive amination and hydrolysis reactions in one-pot reactor

In order to convert the carbon 11 omega aldehyde ester to the carbon 11 omega aminoalkanoic acid, the reductive amination reaction of the aldehyde and the hydrolysis reaction of the ester were simultaneously performed in a single reactor. The specific method is as follows. In a 100ml stainless steel high pressure reactor (Autoclave), 20 g (0.11 mole) of the synthesized carbon 11 omega aldehyde ester, 2 g of Raney Ni-Mo (91-2) catalyst (10 wt% compared to aldehyde ester), 7M ammonia methyl alcohol solution (Aldrich) ) 31g (1.5 equivalents compared to aldehyde ester), 5.9g water (3 equivalents compared to aldehyde ester), 40 bar of hydrogen, and reacted at 90° C. for 6 hours. After completion of the reaction, the reaction vessel is cooled to 60°C, the pressure of the reactor is lowered to atmospheric pressure, and the Raney Ni-Mo (91-2) catalyst is removed through a hot filtration silica filter at 60°C. , The used methanol was distilled off to obtain a milky white solid carbon 11 omega aminoalkanoic acid. Quantitative analysis of the sample was analyzed by ¹ H-NMR, and the reaction analysis results are shown in Example 1 of Table 2.

<Example 2 ~ Example 6>

A Raney Ni _- Cr (91-2) metal catalyst was synthesized in the same manner as in Example ₁ , and as an M metal precursor, chromium acetylacetonate (Cr ( acac) ₃ ) 6.4 g was used. And the results of performing the reductive amination and hydrolysis reaction under the same reaction conditions as in Example 1 are shown in Example 2 of Table 2.

Raney Ni-Mn (91-2) catalyst was synthesized using 6.1 g of manganese acetylacetonate (Mn(acac) ₃ ) as a metal precursor, and Raney Ni-Fe (91-2) catalyst was synthesized using iron acetylacetonate as a metal precursor. Nitrate (Fe(acac) ₃ ) was synthesized using 6.1 g, and the Raney Ni-Mo-Cr (91-1-1) catalyst is a metal precursor molybdenum acetylacetonate (MoO ₂ (acac) ₂ , Aldrich) 1.63 g and chromium acetylacetonate (Cr(acac) ₃ ) was synthesized using 3.2 g, and Raney Ni-Mo (92-1) is an M metal precursor molybdenum acetylacetonate (MoO ₂ (acac) ₂ , Aldrich Corporation) 1.63 g was used for synthesis. The results of reductive amination and hydrolysis of the Raney Ni-M metal catalyst under the same reaction conditions as in Example 1 are shown in Examples 2 to 6 of Table 2.

<Comparative Example 1, Comparative Example 2>

A Raney Ni(93) metal catalyst was synthesized in the same manner as in Example 1, but without using an M metal precursor, and the Raney Ni-Mo(78-12) catalyst was molybdenum acetylacetonate (MoO ₂ (acac) ₂ , Aldrich) 19.6 g and ethyl alcohol and toluene mixed solvent (alcohol and toluene weight ratio 1:1) were used for synthesis using 60 g. The results of performing reductive amination and hydrolysis reactions using the catalyst synthesized in Comparative Example 1 and under the same reaction conditions as in Example 1 are shown in Comparative Examples 1 to 2 in Table 2

Example Catalyst Conv.
(%) Yield (%) C11 Amino ester C11 Amino alkanoic acid Example 1 Raney Ni-Mo (91-2) 99 6 91 Example 2 Raney Ni-Cr (91-2) 99 3 90 Example 3 Raney Ni-Mn (91-2) 99 10 84 Example 4 Raney Ni-Fe (91-2) 99 8 87 Example 5 Raney Ni-Mo-Cr (91-1-1) 99 4 90 Example 6 Raney Ni-Mo (92-1) 99 9 86 Comparative Example 1 Raney Ni(93) 99 89 6 Comparative Example 2 Raney Ni-Mo (78-12) 78 31 38

In the synthesis of carbon 11 omega aminoalkanoic acid from carbon 11 omega aldehyde ester as shown in Examples 1 to 6 of Table 2, Raney Ni-M (M = Mo, Cr, Mn, Fe according to the present invention) ) When a metal catalyst is used, the reductive amination reaction of the aldehyde and the hydrolysis reaction of the ester are simultaneously performed in a single reactor to obtain a yield of 84-91% of carbon 11 omega aminoalkanoic acid at a conversion rate of 99% of carbon 11 omega aldehyde ester. could achieve

However, as in Comparative Example 1, if there was no M (M = Mo, Cr, Mn, Fe) metal component, the yield of the amino ester proceeded by the reductive amination reaction alone was 89%, and the yield of the amino alkanoic acid was very low as 6%. , in the case of the Ni-Mo (78-12) catalyst of Comparative Example 2 in which the M component is excessive, the aminoester yield is 31% and the aminoalkanoic acid yield is 38%. The target yield of carbon 11 omega aminoalkanoic acid is 40% or less it was

As described above, in the comparative example in which the catalyst of the present invention is not used, the carbon 11 omega aminoester product that has undergone only the reductive amination reaction without the hydrolysis reaction is synthesized in a yield of 31-89%, so an additional hydrolysis reaction is required. do.

Therefore, through the method of the present invention, an effective Raney Ni-M metal catalyst was obtained to simultaneously perform the reductive amination reaction and hydrolysis reaction of omega aminoalkanoic acid from omega aldehyde ester in a single reactor in one step, and high yield can synthesize omega aminoalkanoic acid.

As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the present invention be defined by the claims and their equivalents.

Claims (11)

A catalyst for use in the reaction of omega aldehyde esters to omega aminoalkanoic acids, comprising:
The catalyst is a Raney Ni-M catalyst in which at least one metal M selected from chromium, molybdenum, manganese, iron, and cobalt and Raney Ni are mixed, the Raney Ni content is 90 to 99.9 wt%, and the M content is 0.1 to 10 wt% % Catalyst for the production of omega aminoalkanoic acid from omega aldehyde ester, characterized in that it is.
According to claim 1,
Catalyst for preparing omega aminoalkanoic acid from omega aldehyde ester, characterized in that the metal M is dispersed on the surface of Raney Ni.
According to claim 1,
In the Raney Ni-M, the content of Ni analyzed by an Energy Dispersive X-ray Spectrometer (EDS) is 80 to 99 wt% for production of omega aminoalkanoic acid from omega aldehyde ester, characterized in that catalyst.
a) preparing a M precursor solution by dissolving a precursor of at least one metal M selected from chromium, molybdenum, manganese, iron, and cobalt in a solvent;
b) adding Raney Ni to the M precursor solution, mixing, and drying;
c) calcining Raney Ni containing M precursor in a hydrogen atmosphere;
5. The method of claim 4,
In step a), the solvent for dissolving the precursor of metal M is omega amino from omega aldehyde ester, characterized in that at least one selected from among methyl alcohol, ethyl alcohol, propyl alcohol, acetone, methyl ethyl ketone, dioxane, ethyl acetate, and toluene. A method for preparing a catalyst for the production of alkanoic acid.
5. The method of claim 4,
The method for producing a catalyst for the production of omega aminoalkanoic acid from an omega aldehyde ester, characterized in that the precursor of the metal M is an acetylacetonate metal compound, a carbonyl metal compound, and an acetate metal compound.
5. The method of claim 4,
The hydrogen atmosphere in step c) is a method for preparing a catalyst for preparing omega aminoalkanoic acid from omega aldehyde ester, characterized in that it is a hydrogen atmosphere diluted with nitrogen.
5. The method of claim 4,
The method for preparing a catalyst for preparing omega aminoalkanoic acid from omega aldehyde ester, characterized in that the calcination temperature of step c) is in the range of 200 to 500°C.
A method for preparing an omega aminoalkanoic acid from an omega aldehyde ester, the method comprising:
In the presence of the catalyst of any one of claims 1 to 3 or the catalyst prepared by the method of any one of claims 4 to 8, the reductive amination reaction and hydrolysis reaction of the omega aldehyde ester A method for producing omega aminoalkanoic acid from omega aldehyde ester, characterized in that by simultaneously performing the omega aminoalkanoic acid.
10. The method of claim 9,
The omega aldehyde ester is a method for producing an omega aminoalkanoic acid from an omega aldehyde ester, characterized in that it is obtained by hydroformylation of an omega olefinic acid ester obtained by metathesis of oleic acid.
10. The method of claim 9,
The method for producing omega aminoalkanoic acid from omega aldehyde ester, characterized in that the reductive amination reaction and hydrolysis reaction of the omega aldehyde ester is carried out at 60 ~ 150 °C and under a hydrogen pressure of 10 ~ 100 bar.

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