KR101916540B1 - Method of manufacturing muconate from mucic acid using ionic liquid - Google Patents

Abstract

The present invention relates to a process for preparing dibutyl muconate from a biomass-derived mucic acid, and more particularly to a process for producing dibutyl muconate from a biomass, and more particularly, to a process for producing a dibutyl muconate from a biomass, (B) a step of reacting the prepared reaction solution with deoxydehydration (DODH); and (c) a step of reacting the prepared reaction solution with (D) concentrating and purifying the recovered organic solvent layer to obtain dibutyl muconate more effectively, and (d) recovering the separated organic solvent layer by adding an organic solvent and concentrating the reacted reaction solution, And isolating and obtaining. According to the manufacturing method of the present invention, adipic acid, which is a raw material for nylon 66, is produced from biomass such as marine resources, and is environmentally friendly. Further, adipic acid having low efficiency and high efficiency is obtained through a simpler process than the conventional production method It is advantageous that it can be manufactured.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for producing muconic acid from muconic acid using an ionic liquid,

The present invention relates to a novel process for producing muconate which is an intermediate of adipic acid which is widely used as raw material for nylon used as an automobile engine chassis injection component, , The synthesis of mucic acid from galactose derived from marine resources as a biomass, the production of mucic acid diester through esterification of muconic acid, The present invention relates to a novel process for preparing muconate through a deoxydehydration (DODH) reaction and separating muconate easily by using an ionic liquid as a reaction medium.

Due to the continued population growth and industrial development, it is clear that petroleum resources are the most dependable resource for humanity, accounting for approximately 95% of the compounds currently produced. However, in the face of the finite amount of reserves and the environmental problems necessarily caused by the use, it is in urgent need to prepare alternatives. Therefore, various alternatives for this purpose have been researched. Among them, biomass derived from plant resources, which are produced repeatedly every year in nature such as corn, sugar cane, woody plant resources, palm and seaweed, It is becoming an important resource to replace petroleum resources because of its friendliness.

The importance of biomass research and development, which can be regarded as a futuristic resource in terms of automobile parts and materials industry, is closely emphasized in the same context. It is true that the bio-materials business is still small and the economic efficiency is lower than that of petrochemical materials. However, recent reports from Utrecht University of the Netherlands with the request of European Bio Plastic Association and EPNOE (European Polysaccharide Network of Excellence) Predicts that the use of biomaterials will surge in the next 10 years, and specifically predicts marketability to replace up to 90% of petroleum extraction materials.

Currently, automobile interior and exterior injection parts are made of polypropylene, nylon, polycarbonate, and acrylonitrile butadiene styrene (ABS). Of these, polypropylene is the most widely used, followed by nylon about 15 kg per car. Therefore, if the manufacturing technology of nylon is converted into a biomass base, a considerable ripple effect can be expected. Actually, researches on biomass-based nylon materials are actively underway.

Among the various nylon materials, nylon 66, which is a typical nylon material together with nylon 6, is in great demand due to its excellent physical properties, but the process technology for producing biomass as raw material has not yet been established. Therefore, the development of a process for producing bio nylon 66 can be expected to have a remarkable ripple effect not only from the economic point of view but also from the environmental point of view.

Nylon 66 is used for parts requiring high temperature characteristics among automobile parts because it has excellent heat resistance, abrasion resistance, and chemical resistance. Nylon 66 is used after nylon 6 used for automobile parts. Nylon 66 is produced by dehydration polymerization of hexamethylenediamine and adipic acid. Adipic acid, which is used as a monomer, is produced from benzene (benzene ) Through chemical synthesis processes using cyclohexanone as an intermediate.

However, this technology and manufacturing process are causing problems such as oil price instability, the use of benzene as a toxic substance, and the production of environmental pollution byproducts including nitrogen oxides (NOx), thus necessitating a substitution with bioprocess technology. Therefore, the production of nylon using bioprocess can simultaneously reduce the dependence of raw materials on petroleum and reduce the occurrence of environmental pollutants.

In the development of the nylon 66 bioprocess, the technology of synthesizing adipic acid, which is a monomer of nylon 66, from biomass is the most important. However, these technologies have remained at the R & D level yet, but they have not reached commercialization.

A number of patents have been published on glucaric acid (intermediate), a highly efficient and environmentally friendly method for producing adipic acid necessary for making nylon.

Specifically, Korean Patent Laid-Open No. 10-2003-0012426 discloses a method for producing D-glucaric acid derived from algae as a currently known known technology. The present invention relates to a method for producing D-glucuronic acid by using a green algae derived saccharide, and more particularly, to a method for producing D-glucuronic acid by using a recombinant microorganism into which a D- (D-glucuronic acid) into D-glucuronic acid. The method includes drying and crushing a green algae powder to granulate the green algae; Acid hydrolyzing the algae powder to produce a monosaccharide; And converting the produced monosaccharide into D-glucuronic acid using recombinant microbial fermentation with a D-glucaric acid-producing gene inserted therein. Thus, it is possible to obtain industrially useful value by using green algae resources that have not been used industrially It is known that it is a novel fermentation process for producing high chemical products. However, it is a metabolic engineering technique for producing glucaric acid by utilizing saccharification technology for producing monosaccharide from algae seeds and subsequent recombinant microorganisms, .

An existing study on the production of biomass-derived D-glucaric acid has produced D-glucaric acid using D-glucose as a raw material (Moon, TS et al. 2009) Appl. Environ. Microbiol. 75: 589-595). The above-described technique for producing D-glucuronic acid using D-glucose is a method of producing phosphoenolpyruvate-dependentphosphotransferase system (PPS), myo-inositol-1-phosphate synthase, phosphatase ), Myo-inositol oxygenase and uronic acid dehydrogenase, D-glucaric acid is produced. Therefore, the process is complicated and the amount of added glucose - The yield of glucaric acid is less than 17.4% and its productivity is very low.

There is also U.S. Patent Publication No. 2013-0157343, which discloses the technology of Verdezyne, which manufactures adipic acid in a biotechnological way. This technique discloses a method for preparing adipic acid from a renewable fatty acid feedstock and a genetically modified microorganism such as yeast that enables such production, and also U.S. Patent No. 8,343,752 discloses a process for producing adipic acid from a fatty acid feedstock A genetically modified yeast comprising a POX5 polypeptide and a POX4 polypeptide or promoter thereof, a FAT1 polypeptide or promoter thereof, and an ACS1 polypeptide deleted or knocked out, Discloses a method for producing adipic acid from a fatty acid raw material, and U.S. Patent No. 8,241,879 discloses a method for producing adipic acid from a fatty acid raw material through a fermentation process.

However, since Verdezyne's technology is manufactured in a biotechnological way, the process is complicated compared with a chemical synthesis method, and the manufacturing cost is expensive.

U.S. Patent Publication No. 2013-0157343 U.S. Patent No. 8,343,752 U.S. Patent No. 8,241,879

Moon, T. S. et al. (2009) Appl. Environ. Microbiol. 75: 589-595

In order to solve the above problems, the present invention provides a simple and economical method for producing adipic acid from a biomass such as a marine resource, which is an eco-friendly material, as an economical adipic acid from galactose derived from marine resources, acid was prepared and then mucic acid diester was prepared through ester reaction in order to increase the solubility of the muconic acid in the reaction solvent and then deoxydihydration of the diester through the catalytic chemical reaction , DODH) reaction to produce muconate efficiently, but it is more efficient to manufacture muconate than the conventional method which can easily separate the product in which the reactant is dissolved during the catalytic chemical reaction using the ionic liquid The purpose.

According to one aspect of the present invention, there is provided a method for producing a muconate comprising the steps of:

Specifically, (a) an esterified mucic acid diester represented by the following formula (2), a catalyst for the dioxydihydration reaction, an acid catalyst and an acid catalyst for improving the solubility of the muconic acid in the reaction solvent, (B) a step of reacting the prepared reaction solution with deoxydehydration (DODH); (c) reacting the reaction solution obtained in the step (b) And the organic solvent which does not mix with the ionic liquid can be melted and mixed, and the organic solvent layer of the upper layer among the organic solvent layer of the lower layer and the organic solvent layer of the upper layer is collected And (d) concentrating and purifying the recovered organic solvent layer to obtain a muconate of the following formula (3) after separation All.

In the general formulas (2) and (3), R is a linear or branched alkyl having 1 to 20 carbon atoms.

The method may further include a step of reacting mucic acid with 1 to 10 carbon atoms to prepare a mucic acid diester before the step (a).

The ionic liquid is a room temperature molten salt composed of a cation and an anion, and examples of the cation include imidazolium, piperidinium, pyrrolidinium, pyrazolium, pyridinium ), Phsphonium, non-cyclic alkyl ammonium, and cholinium. The anion is selected from the group consisting of Br ^- , Cl ^- , I ^- , Al ₂ Cl ₇ ^- , Al ₃ Cl ₁₀ ^- Sb ₂ F ₁₁ ^- , Fe ₂ Cl ₇ ^- , Zn ₂ Cl ₅ ^- , Zn ₃ Cl ₇ ^- , CuCl ₂ ^- , SnCl ₂ ^- , NO ₃ ^- , PO ₄ ^3- , BF ₄ ^- , PF ₆ ^{- _{4 -, NO 3 -, AlCl}} 2 -, Al 2 Cl 7 -, AsF 6 -, Sb 2 F 11, Fe 2 Cl 7, Zn 2 Cl 5, Zn 3 Cl 7, CH 3 COO - (OAc), CF ₃ COO ^-, CH ₃ CH (OH) CO ₂ ^-, RSO ₃ ^- (R = C 1 a to 3 alkyl), RSO ₄ ^- sulfonate as a (R = alkyl having 1 to 3 carbon atoms), trifluoromethyl (CF ₃ SO ₃ ^-, OTf), methane sulfonyl imide trifluoromethyl _{(CF 3 SO 2) 2 N} -, TFSI), 2 N is sulfonyl fluoro imide ^{_{(FSO 2) -, FSI)}} , (CF 3 SO ₂ ) _{^{3 C -, (C 2 F}} 3 CF 2 SO 2) 2 N - which is selected from ^{_{-, C 4 F 9 SO 3}} -, C 3 F 7 COO -, (CF 2 SO 2) (CF 3 CO) N And specifically an ionic liquid represented by the following formula (5).

[Chemical Formula 5]

In the formula (5), R ₁ , R ₂ , R ₃ and R ₄ of the imidazolium are reactors composed of alkyl or alkoxy having 0 to 8 carbon atoms, and include piperidinium, pyrrolidinium, pyrazolium, R ₁ and R ₂ of indium are reactors composed of alkyl or alkoxy having 1 to 8 carbon atoms and R ₁ , R ₂ , R ₃ and R ₄ of phosphonium and noncrystalline alkylammonium are reacted with alkyl having 1 to 8 carbon atoms And R ₁ , R ₂ and R ₃ of the colinium are reactors composed of alkyl having 1 to 8 carbon atoms. And X ^- is an anion of the ionic liquid described above.

In the present invention, the ionic liquid is most preferably 1-butyl-3-methylimidazolium trifluoromethane sulfonate ([C ₄ mim] OTf).

Examples of the catalyst for the dioxidization reaction include rhenium oxide (Re ₂ O ₇ ) and L _x MO _{y wherein} L is an amine, halogen, phenylsiyl, phosphine, alkoxy of 1 to 10 carbon atoms, (R), vanadium (V), tungsten (W) or molybdenum (Mo), x and y are each independently 0 to 7 , And x + y = 7).

As the catalyst for the dioxidization reaction, a rhenium catalyst containing a metal such as rhenium (Re) can be preferably used. As the rhenium catalyst, for example, rhenium oxide (Re ₂ O ₇ ), methyltriox Methyltrioxorhenium (MTO), ammonium perrhenate (APR), Re ₂ O ₅ , ReCl ₃ , ReCl ₄ , ReCl ₅ and ReCl ₆ .

The acid catalyst may be a known catalyst such as Amberlyst-15, 2,4-dinitrosulfonic acid, sulfuric acid, benzenesulfonic acid, trifluoromethanesulfonic acid, Examples of the solvent include trifluoromethanesulfonic acid, methylsulfonic acid and para-toluene sulfonic acid, boron trifluoride, aluminum chloride, zinc chloride, , Hydrochloric acid (HCl), and acetic acid (AcOH). Of these, para-toluene sulfonic acid may be preferably used.

The reaction solvent is used as a reaction solvent for the dioxydihydration (DODH) reaction and serves as a reducing agent for converting the catalyst into an active state. The reaction solvent may be selected from the group consisting of primary alcohols having 1 to 10 carbon atoms and secondary alcohols, preferably 1-butanol, 3-pentanol, 1-heptane Can be used, and among these, 1-butanol can be most preferably used.

In the step (a), the ionic liquid and the reaction solvent may be mixed in a volume ratio of 1: 1 to 1: 200.

In the step (b), the reaction solution may be subjected to deoxydehydration (DODH) by reflux stirring at 100 ° C to 200 ° C for 12 to 72 hours.

The step (c) may dissolve the muconate, which is a product contained in the reaction solution in step (b), and an organic solvent that does not mix with the ionic liquid may be added. When stirring is stopped after the water is stirred, Of an ionic liquid layer containing a catalyst for the dioxydihydration reaction and an acid catalyst and an organic solvent layer containing muconate of an upper layer. Then, the organic solvent layer in the upper layer is selectively recovered from the separated layers.

Examples of the organic solvent used in step (c) include acetone, dichloromethane, chloroform, ethyl acetate, acetonitrile, diethyl ether, Hexane, tetrahydrofuran, benzene, toluene, and xylene. Of these, diethyl ether (preferably diethyl ether), diethyl ether diethyl ether may be used.

Next, in step (d), the organic solvent layer separated in step (c) is subjected to a chemical purification process by separating the organic solvent layer separated in step (c) through a column chromatography or distillation And then the muconate is produced.

Here, the purification method is not limited thereto and can be carried out through various purification methods known in the art.

According to the method for producing muconate of the present invention as described above, muconate can be efficiently produced with high efficiency by selectively obtaining muconate more effectively than the conventional method of producing muconic acid in mucic acid diester.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart schematically illustrating a method for producing a muconate of the present invention. FIG.
2 is a flowchart of a method for producing muconate according to an embodiment of the present invention.
Figure 3 is a schematic representation of the process for preparing muconates of the present invention.
FIG. 4 shows a reaction scheme for sequentially producing mucic acid dibutyl ester and dibutyl muconate from mucic acid according to an embodiment of the present invention.
Figure 5 is hydrogen atom nuclear magnetic resonance ( ¹ H NMR) data of dibutyl muconate, a muconate prepared according to one embodiment of the present invention.

Hereinafter, a method for producing a muconate according to the present invention will be described in detail with reference to the accompanying drawings. It is to be understood that the present invention may be embodied in many other specific forms without departing from the spirit or essential characteristics thereof, The present invention is not limited thereto.

It is to be understood that the terms such as " comprises " or " adding ", as used herein, are not necessarily to be construed as necessarily including the various elements or steps described in the specification, Some steps may not be included and should be construed as further including additional components or steps.

In addition, the number of repetitions of each step to be described, the process conditions, and the like are not particularly limited as long as they do not depart from the object of the present invention.

As shown in FIG. 1, the method for producing a muconate of the present invention comprises the steps of (S110) preparing a mucic acid diaster, (a) preparing a reaction solution (S120), (b) A step of performing a deoxydehydration (DODH) reaction (S130), (c) dissolving the product muconate in the reaction solution in which the reaction is performed, adding an organic solvent which is immiscible with the ionic liquid, (S140) of recovering the upper organic solvent layer out of the two layers, and (d) concentrating and purifying the recovered organic solvent layer to obtain muconate (S150).

The step (S110) of producing the mucic acid diastere is a step of preparing a mucic acid diester, which is a starting material for preparing the muconate of the present invention, to increase the solubility of the muconic acid in the reaction solvent, It is a necessary step to increase efficiency.

As shown in Reaction Scheme 1, muconic acid is produced from galactose used as a raw material. The galactose used herein is preferably biomass, and galactose derived from marine resources may be used. However, The galactose used can be used.

In this process for producing muesic acid, mucic acid of formula (1) can be prepared by oxidizing galactose with nitric acid (HNO ₃ ) by nitric acid reaction as shown in Reaction Scheme 1, The step of preparing the ester can be carried out not only by the nitric acid reaction but also by applying ordinary reactions and various oxidation reactions known in the art using another catalyst.

[Reaction Scheme 1]

In step S110, galactose is oxidized with nitric acid (HNO ₃ ) to obtain a micamic acid of formula (1), as shown in Reaction Scheme 1 above.

The muconic acid thus obtained is reacted with an ester in the presence of an alcohol and an acid catalyst to prepare a mucic acid diester of the formula (2)

As the alcohol used herein, an alcohol having 1 to 10 carbon atoms can be used. As the acid catalyst, any one selected from the group consisting of a zeolite catalyst, a heteropoly compound, an ion exchange resin, niobia, silica, alumina and silica- But is not limited thereto.

The step of preparing the reaction solution (S120) comprises mixing the mucic acid diester, the catalyst for the dioxydihydration reaction, the acid catalyst and the ionic liquid prepared in the step S110, do.

At this time, the reaction solvent may be any one selected from the group consisting of primary alcohols having 1 to 10 carbon atoms and secondary alcohols, preferably 1-butanol, 3-pentanol, And 1-heptanol may be used.

As described above, the catalyst for the dioxidization reaction is a mixture of rhenium oxide (Re ₂ O ₇ ) and L _x MO _y (wherein L = amine, halogen, phenylsilyl, phosphine, alkoxy having 1 to 10 carbon atoms, (R), vanadium (V), tungsten (W) or molybdenum (Mo), x and y are each independently An integer of 0 to 7, and x + y = 7).

The catalyst for the dioxidization reaction is preferably a rhenium catalyst comprising rhenium (Re), wherein the rhenium catalyst is most preferably selected from the group consisting of rhenium oxide (Re ₂ O ₇ ), methyltrioxorhenium , MTO), ammonium perrhenate (APR), and the like.

The ammonium perrhenate (APR, NH ₄ ReO ₄ ) is a substance which exists in a salt form at room temperature and is a very stable substance which does not change even when exposed to air. Can be displayed together.

[Chemical Formula 6]

The acid catalyst may be a known catalyst such as Amberlyst-15, 2,4-dinitrosulfonic acid, sulfuric acid, benzenesulfonic acid, trifluoromethane And sulfonic acids including trifluoromethanesulfonic acid, methyl sulfonic acid and para-toluene sulfonic acid, or by using at least one selected from the group consisting of boron triblurea And at least one selected from the group consisting of boron trifluoride, aluminum chloride, zinc chloride, hydrochloric acid (HCl), and acetic acid (AcOH).

The ionic liquid is a room-temperature molten salt composed of a cation and an anion. Examples of the cation include imidazolium, piperidinium, pyrrolidinium, pyrazolium, pyridinium, , Phosphonium non-cyclic alkylammonium and cholinium, and the anion is any one selected from Br ^- , Cl ^- , I ^- , Al ₂ Cl ₇ ^- , Al ₃ Cl ₁₀ ^- , Sb ₂ F ₁₁ ^- , Fe ₂ Cl ₇ ^- , Zn ₂ Cl ₅ ^- , Zn ₃ Cl ₇ ^- , CuCl ₂ ^- , SnCl ₂ ^- , NO ₃ ^- , PO ₄ ^3- , BF ₄ ^- , PF ₆ ^- , ClO _{4 ^{-, NO 3 -, AlCl 2}} -, Al 2 Cl 7 -, AsF 6 -, Sb 2 F 11, Fe 2 Cl 7, Zn 2 Cl 5, Zn 3 Cl 7, CuCl 2, SnCl 2, CH 3 COO - ^{_{(OAc), CF 3 COO -}} , CH 3 CH (OH) CO 2 -, RSO 3 - (R = alkyl having 1 to ^{_{3), RSO 4 - (R}} = alkyl having 1 to 3 carbon atoms), trifluoromethyl (CF ₃ SO ₃ ^- , OTf), trifluoromethanesulfonylimide (CF ₃ SO ₂ ) ₂ N ^- , TFSI), fluorosulfonylimide (FSO ₂ ) ₂ N ^- , FSI) , ( ^{_{CF 3 SO 2) 3 C -}} , (C 2 F 3 CF 2 SO 2) 2 N -, C 4 F 9 SO 3 -, C 3 F 7 COO -, (CF 2 SO 2) (CF 3 CO) N ^- can be used.

Here, the ionic liquid is the reaction medium used to improve the conventional dioxydehydration (DODH) reaction conditions, ie, the difficulty of separating the catalyst due to the presence of the catalyst in a uniformly molten state with the reactants and the product and the mixture .

During the dioxydihydration (DODH) reaction, the ionic liquid exists in a state of being uniformly mixed with the solvent so that the reaction product and the catalyst can be efficiently reacted. After the reaction, the organic solvent for layer separation And has a specific solubility under which the layer is separated in a state including the remainder excluding the product. Therefore, the ionic liquid of the present invention should use a certain amount or more of an ionic liquid to sufficiently dissolve the catalysts used in the dioxydihydration (DODH) reaction. In addition to the ionic liquid, the reaction of the above- The solvent must be used together with the reducing agent.

Accordingly, the ratio of the ionic liquid to the reaction solvent used in the step of preparing the reaction solution (S120) can be used in a volume ratio of 1: 1 to 1: 200, and most preferably in a volume ratio of 1:60.

When the mixing ratio of the ionic liquid and the reaction solvent is out of the above range and the amount of the reaction solvent is small, the alcohol used as a reaction solvent is not effective in serving as a reducing agent and the yield of the product muconate is lowered Can occur.

The dioxydihydration (DODH) reaction step (S130) is a step of preparing muconate by reacting the reaction solution prepared in the step (S120) of the reaction solution with a reflux stirring for a predetermined time at a predetermined temperature.

In the dioxidation (DODH) reaction step (S130), the reaction solution containing the mucic acid diester of the formula (2) is reacted at a reaction temperature of 100 to 200 ° C for 12 to 72 hours And the mixture is stirred under reflux for deoxydehydration (DODH).

If the reaction temperature is lower than 100 ° C, there is a problem of decreasing the reaction yield. Conversely, if the reaction temperature is higher than 200 ° C, the byproducts are increased to decrease the separation efficiency of the product and decompose the ionic liquid At high reaction temperatures, it is not suitable for the manufacturing process because it consumes too much energy.

If the reaction time is less than 12 hours, the production yield of muconate is lowered because the deoxydehydration (DODH) reaction is not performed properly. If the reaction time exceeds 72 hours, the yield of muconate production remains unchanged, It is preferable to perform the process within the range of the temperature and the process time.

In this way, a muconate is generated in the reaction solution by the dioxydihydration (DODH) reaction step (S130).

(S140) of removing the solvent used in the reaction product obtained from the dioxidation (DODH) reaction step (S130), separating the organic solvent layer after stirring the organic solvent, and concentrating the recovered organic solvent layer The step of obtaining a muconate by purification (S150) comprises the step of obtaining a muconate contained in the reaction solution from a reaction solution in which deoxydehydration (DODH) reaction is performed in the dioxydihydrate reaction step (S130) to be.

As a specific example, in step S140 of removing the solvent used in the reaction product obtained from the dioxidization reaction step (S130), stirring the organic solvent, and separating the organic solvent layer, a dioxydihydration (DODH) reaction step S130), the solvent may be evaporated by using a rotary evaporator to concentrate, and then the muconate produced as a product may be dissolved in the concentrate. Alternatively, the reaction solution may be mixed with an ionic liquid Add the solvent and stir. After stirring for several minutes, stirring is stopped, and when the mixture is left to stand for a few minutes, an ionic liquid layer containing a catalyst for dioxydihydration reaction and an acid catalyst and an organic solvent layer containing muconate And the organic solvent layer only in the upper layer among the separated layers is selectively recovered. An embodiment of this process is schematically shown in FIG.

Examples of the organic solvent used in step S140 include acetone, dichloromethane, chloroform, ethyl acetate, acetomitrole, diethyl ether, hexane, tetrahydrofuran, benzene, toluene, and xylene. Of these solvents, diethyl ether can be preferably used.

In step S150 of concentrating and purifying the recovered organic solvent layer through step S140 to obtain muconate, the organic solvent layer is separated, the organic solvent is added to the remaining solution, and the organic solvent layer is selectively mixed again, The reaction product in the ionic liquid can be removed by repeating the process of recovering the ionic liquid.

In the step of obtaining muconate (S150), the organic solvent layer selectively recovered through S140 is evaporated by evaporating the organic solvent using a flash evaporation concentrator, and then concentrated to obtain muconate through purification.

In the step of obtaining the muconate (S150), the purification method is a purification process by a chemical purification process through a column chromatography or a distillation method. Preferably, purification by silica gel column chromatography is performed, The eluted fraction is obtained and concentrated to give the muconate.

Here, the purification method is not limited thereto and can be carried out through various purification methods known in the art.

According to the present invention, dibutyl muconate is prepared as a muconate, a step (S111) of producing muconic acid dibutyl ester as shown in FIG. 2 based on the above-described muconate production method, a step In step S121, the produced reaction solution is subjected to a deoxydehydration (DODH) reaction (S131). Diethyl ether is added to the reaction solution, (S141) of recovering the diethyl ether layer among the diethyl ether layer, and step (S151) of concentrating and purifying the recovered diethyl ether layer to obtain dibutyl muconate.

The method for producing dibutyl muconate according to one embodiment of the present invention is a method of producing mucic acid dibutyl ester and dibutyl muconate from mucic acid sequentially as shown in the reaction formula of FIG. .

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

In addition, the ionic liquid and Methyltrioxorhenium (MTO) catalyst used in Examples and Comparative Examples of the present invention were obtained from Sigma-Aldrich product of the United States and rhenium oxide Re ₂ O ₇ ), 3-pentanol and para-toluenesulfonic acid were Alfa Aesar products.

Example 1 was prepared by reacting 0.5 mmol (162 mg) of mucic acid dibutyl ester with the mucic acid diester, 1-butyl-3-methylimidazolium trifluoromethanesulfonate -3-methylimidazolium trifluoromethanesulfonate, [C ₄ mim] OTf (1.0 g), 5 mol% of rhenium oxide (Re ₂ O ₇ ) as a catalyst for dioxydihydration reaction, para- 5 mol% (6 mg) of toluenesulfonic acid, p-TsOH) was added to a 30 cc butanol solution and refluxed at 120 ° C for 12 hours or more in a dean-stark manner.

After the completion of the reaction, all butanol was evaporated using a rotary evaporator, 30 to 50 cc of diethyl ether was added to the residue, and the mixture was stirred. When the ionic liquid layer and the diethyl ether layer were separated after stirring, the diethyl ether layer was recovered. This process was repeated three times to remove the reaction product dibutyl muconate in the ionic liquid layer.

The recovered diethyl ether layer was removed with a rotary evaporator and then purified by column chromatography (hexane: ethyl acetate = 16: 1) to give muconate Muconate (dibutyl muconate) was obtained.

Example 2 shows the change in the length of an alkyl group bonded to the cation of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) used in Example 1 as an ionic liquid Except that 1-octyl-3-methylimidazolium trifluoromethanesulfonate, [C ₈ mim] OTf was used instead of 1-octyl-3-methylimidazolium trifluoromethanesulfonate. Dibutyl muconate was prepared.

Example 3 was prepared by dissolving the trifluoromethanesulfonate (OTf) anion of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) used in Example 1 as an ionic liquid 3-methylimidazolium bis (trifluoromethylsulfonyl) imide, which is obtained by changing 1-butyl-3-methylimidazolium bromide to trifluoromethanesulfonylimide (TFSI) C < ₄ > mim] TFSI) was used as the initiator in the preparation of the dibutyl muconate.

Example 4 was prepared by using 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) modified in the cation of the 1-butyl-3-methylimidazolium trifluoromethanesulfonate used in Example 1 Dibutyl muconate was prepared in the same manner as in Example 1 except that 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate was used instead of methyl pyrrolidinium trifluoromethanesulfonate.

In Example 5, an ionic liquid was prepared by dissolving 0.9 g of 1-butyl-3-methylimidazolium trifluoromethanesulfonate, [C ₄ mim] OTf) The same procedure as in Example 1 was carried out except that 5 mol% (16 mg) of ammonium perrhenate (NH ₄ ReO ₄ ) was used as a catalyst and the mixture was refluxed at 116 ° C. for 24 hours or more in a dean- To prepare dibutyl muconate.

Examples 6 to 8 illustrate the use of 1-butyl-3-methylimidazolium trifluoromethanesulfonate, [C ₄ mim] OTf as an ionic liquid in a modified amount Dibutyl muconate was prepared in the same manner as in Example 5 except that the amount of the ionic liquid was 1.5 g in Example 6, 1.0 g in Example 7, Was used.

In Examples 9 to 12, 30 cc of 3-pentanol was used as a reaction solvent, and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (1-butyl-3-methylimidazolium trifluoromethanesulfonate, Dibutyl muconate was prepared in the same manner as in Example 5 except that the amount of [C ₄ mim] OTf used was changed. Specifically, in Example 9, the amount of the ionic liquid was 0.9 g, 1.5 g in Example 10, 1.0 g in Example 11, and 1.2 g in Example 12 were used.

In Comparative Example 1, 1-ethyl-3-methylimidazolium bromide ([C ₂ mim] Br) was used as the ionic liquid and the rhenium catalyst was replaced with rhenium oxide (Re ₂ O ₇ Dibutyl muconate was prepared in the same manner as in Example 1 except that 7 mg of methyltrioxorhenium (MTO) was used instead of methyltrioxorhenium (MTO).

In Comparative Example 2, the trifluoromethane sulfonate (OTf) anion of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) used in Example 1 was used as an ionic liquid bromine anions (Br ^-) to change a 1-butyl-3-methylimidazolium bromide (1-butyl-3-methylimidazolium bromide, [C 4 mim] Br) , and the use, rhenium catalyst of rhenium oxide (Re ₂ O to ₇₎ was prepared in place of the die-butyl myuko carbonate (dibutyl muconate) in the same manner as example 1, except that 7 mg of methyltriethoxysilane oxo rhenium (Methyltrioxorhenium, MTO).

In Comparative Example 3, the trifluoromethane sulfonate (OTf) anion of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) used in Example 1 was used as an ionic liquid bromine anions (Br ^-) same procedure as in example 1, except that a 1-butyl-3-methyl changed using the imidazolium bromide (1-butyl-3-methylimidazolium bromide, [C 4 mim] Br) To prepare dibutyl muconate.

In Comparative Example 4, a trifluoromethane sulfonate (OTf) anion of 1-butyl-3-methylimidazolium trifluoromethane sulfonate ([C ₄ mim] OTf) used in Example 1 was used as an ionic liquid chlorine (Cl ^-) in the l-butyl-3-methyl imidazolium chloride changed using (1-ethyl-3-methylimidazolium chloride, [C 4 mim] Cl) and rhenium catalysts rhenium oxide (Re ₂ O ₇ Dibutyl muconate was prepared in the same manner as in Example 1 except that 7 mg of methyltrioxorhenium (MTO) was used instead of methyltrioxorhenium (MTO).

In Comparative Example 5, the trifluoromethane sulfonate (OTf) anion of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) used in Example 1 was used as an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate, [C ₄ mim] BF ₄ ) was used instead of tetrafluoroboric acid (BF ₄ ^- Dibutyl muconate was prepared in the same manner as in Example 1 except that 7 mg of methyltrioxorhenium (MTO) was used instead of rhenium oxide (Re ₂ O ₇ ).

In Comparative Example 6, the trifluoromethanesulfonate (OTf) anion of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C ₄ mim] OTf) used in Example 1 was used as an ionic liquid hexafluorophosphate (PF ₆ ^-) use of phosphate (1-butyl-3-methylimidazolium hexafluorophosphate, [C 4 mim] PF 6) as a 1-butyl-3-methylimidazolium hexafluoro-change, and rhenium catalysts Dibutyl muconate was prepared in the same manner as in Example 1 except that 7 mg of methyltrioxorhenium (MTO) was used instead of rhenium oxide (Re ₂ O ₇ ).

In Comparative Example 7, dibutyl muconate was prepared in the same manner as in Example 1 except that 7 mg of methyltrioxorhenium (MTO) was used instead of rhenium oxide (Re ₂ O ₇ ) as a rhenium catalyst. .

Comparative Example 8 was the same as Example 5 except that 1.0 g of 1-ethyl-3-methylimidazolium bromide, [C ₂ MIM] Br as an ionic liquid was used. To prepare dibutyl muconate.

Comparative Example 9 was prepared in the same manner as in Example 5, except that 1.0 g of 1-ethyl-3-methylimidazolium bromide, [C ₄ MIM] Br as an ionic liquid was used. To prepare dibutyl muconate.

Comparative Example 10 was prepared in the same manner as in Example 5, except that 1.0 g of 1-ethyl-3-methylimidazolium bromide, [C ₆ MIM] Br as an ionic liquid was used. To prepare dibutyl muconate.

Comparative Example 11 was the same as Example 5 except that 1.0 g of 3-octyl-1-methylimidazolium bromide, [C ₈ MIM] Br as an ionic liquid was used. To prepare dibutyl muconate.

Hereinafter, in Experimental Example 1, nuclear magnetic resonance (NMR) analysis was performed to confirm the components of the samples prepared in Examples 1 to 12 and Comparative Examples 1 to 11. Nuclear magnetic resonance spectrum was analyzed using a Bruker AVIII 400 instrument and dissolved in CDCl ₃ and dimethyl sulfoxide (DMSO) containing trimethylsilane (TMS) as an internal standard ( ¹ H at 400 MHz, ¹³ C at 100 MHz).

FIG. 5 shows the results of analysis of the product synthesized in the process for producing dibutyl muconate according to Example 1 of the present invention by using a hydrogen atom nuclear magnetic resonance ( ¹ H NMR) spectrum. According to Example 1 The deoxydehydration (DODH) reaction was carried out using 1-butyl-3-methylimidazolium trifluoromethanesulfonate, [C ₄ mim] OTf as the result of 1-butyl-3-methylimidazolium trifluoromethanesulfonate It can be seen that it is produced in dibutyl muconate.

¹ H NMR (CDCl ₃ )? 7.32-7.28 (m, 2H), 6.21-6.17 (m, 2H), 4.18 (t, J = 6.6,4H), 1.68-1.64 m, 4H), 0.95 (t, J = 7.2, 6H)

_{^{13 C NMR (CDCl 3) δ166.0}} , 140.7, 128.4, 64.7, 30.6, 19.1, 13.67

As can be seen from the results of nuclear magnetic resonance analysis data obtained in the analysis of samples of the examples and comparative examples of the present invention, it can be seen that dibutyl muconate is produced from the desired muconate.

In addition, the yield of dibutyl muconate through the dioxidization reaction was {(moles of produced dibutyl muconate) / (moles of consumed mucic acid dibutylester)} x 100% The yields of dibutyl muconate in Examples 1 to 12 and Comparative Examples 1 to 11 were measured, and the results are summarized in Tables 1 and 2 below.

division Yield (%) Example 1 ([C ₄ MIM] OTf, Re ₂ O ₇ ) ≥ 90 Example 2 ([C ₈ MIM] OTf, Re ₂ O ₇ )
(Ionic liquid change condition) ≥ 90 Example 3 ([C ₄ MIM] OTf, Re ₂ O ₇ )
(Ionic liquid change condition) ≥ 90 Example 4 ([1-butyl-1-methyl pyrrolidinium trifluoromethanesulfonate, Re ₂ O ₇ )
(Ionic liquid change condition) ≥ 90 Example 5 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Ammonium perrhenate) ≥ 90 Example 6 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Conditions for changing the amount of catalyst input) ≥ 90 Example 7 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Conditions for changing the amount of catalyst input) ≥ 90 Example 8 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Conditions for changing the amount of catalyst input) ≥ 90 Example 9 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Catalyst input amount, reaction solvent change condition) ≥ 90 Example 10 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Catalyst input amount, reaction solvent change condition) ≥ 90 Example 11 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Catalyst input amount, reaction solvent change condition) ≥ 90 Example 12 ([C ₄ mim] OTf, NH ₄ ReO ₄ )
(Catalyst input amount, reaction solvent change condition) ≥ 90

division Yield (%) Comparative Example 1 ([C ₂ mim] Br, MTO)
(Ionic liquid, rhenium catalyst change condition) No reaction Comparative Example 2 ([C ₄ mim] Br, MTO)
(Ionic liquid, rhenium catalyst change condition) 33 Comparative Example 3 ([C ₄ mim] Br, Re ₂ O ₇ )
(Ionic liquid change condition) No reaction Comparative Example 4 ([C ₄ mim] Cl, MTO)
(Ionic liquid, rhenium catalyst change condition) 20 Comparative Example 5 ([C ₄ mim] BF ₄ , MTO)
(Ionic liquid, rhenium catalyst change condition) 5 Comparative Example 6 ([C ₄ mim] PF ₆ , MTO)
(Ionic liquid, rhenium catalyst change condition) No reaction Comparative Example 7 ([C ₄ mim] OTf, MTO)
(Conditions for changing the rhenium catalyst) 80 Comparative Example 8 ([C ₂ mim] Br, NH ₄ ReO ₄ )
(Ionic liquid change condition) No reaction Comparative Example 9 ([C ₄ mim] Br, NH ₄ ReO ₄ )
(Ionic liquid change condition) 33 Comparative Example 10 ([C ₆ mim] Br, NH ₄ ReO ₄ )
(Ionic liquid change condition) 19 Comparative Example 11 ([C ₈ mim] Br, NH ₄ ReO ₄ )
(Ionic liquid change condition) 10

The results of measuring the yield of dibutyl muconate together with the conditions for carrying out the reaction in Examples 1 to 12 and Comparative Examples 1 to 11 are summarized in Table 3 and Table 4 below.

division Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 Example
9 Example
10 Example
11 Example
12 A (mg) 162 162 162 162 162 162 162 162 162 162 162 162 B-1 (mg) 14 14 14 14 - - - - - - - - B-2 (mg) - - - - 16 16 16 16 16 16 16 16 C-1 (g) 1.0 - - - 0.9 1.5 1.0 1.2 0.9 1.5 1.0 1.2 C-2 (g) - 1.0 - - - - - - - - - - C-3 (g) - - 1.0 - - - - - - - - - C-4 (g) - - - 1.0 - - - - - - - - D (cc) 30 30 30 30 30 30 30 30 E (cc) 30 30 30 30 F (mg) 6 6 6 6 6 6 6 6 6 6 6 6 Reaction temperature
(° C) ≥120 ≥120 ≥120 ≥120 116 116 116 116 116 116 116 116 Dibutyl muconate synthesis yield (%) ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 ≥ 90 A: [diacetic acid dibutyl ester]
B-1: [Re ₂ O ₇ Catalyst] Charge amount
B-2: [Ammonium perrhenate (NH ₄ ReO ₄ ) catalyst]
C-1: [ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate]
C-2: [ionic liquid 3-octyl-1-methylimidazolium trifluoromethanesulfonate]
C-3: [ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonylimide]
C-4: [Ionic liquid 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate] Charge amount
D: [butanol] input amount
E: [3-pentanol]
F: [para-toluenesulfonic acid]

division Comparative Example
One Comparative Example
2 Comparative Example
3 Comparative Example
4 Comparative Example
5 Comparative Example
6 Comparative Example
7 Comparative Example
8 Comparative Example
9 Comparative Example
10 Comparative Example
11 A (mg) 162 162 162 162 162 162 162 162 162 162 162 B-1 (mg) - - 14 - - - - - - - - B-2 (mg) - - - - - - - 16 16 16 16 B-3 (mg) 7 7 - 7 7 7 7 - - - - C-1 (g) - - - - - - 1.0 - - - - C-4 (g) 1.0 - - - - - - 1.0 - - - C-5 (g) - 1.0 1.0 - - - - - 1.0 - - C-6 (g) - - - 1.0 - - - - - - - C-7 (g) - - - - 1.0 - - - - - - C-8 (g) - - - - - 1.0 - - - - - C-9 (g) - - - - - - - - - 1.0 - C-10 (g) - - - - 1.0 - - - - - 1.0 D (cc) 30 30 30 30 30 30 30 30 30 30 30 F (mg) 6 6 6 6 6 6 6 6 6 6 6 Reaction temperature (캜) ≥120 ≥120 ≥120 ≥120 ≥120 ≥120 ≥120 116 117 116 116 Dibutyl muconate
Synthesis yield (%) 0 33 0 20 5 0 80 0 33 19 10 A: [diacetic acid dibutyl ester]
B-1: [Re ₂ O ₇ Catalyst] Charge amount
B-2: [Ammonium perrhenate (NH ₄ ReO ₄ ) catalyst]
B-3: [Methyltrioxorhenium (MTO) catalyst]
C-1: [ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate]
C-4: [Ionic liquid 1-ethyl-3-methylimidazolium bromide] Charge amount
C-5: [Ionic liquid 1-butyl-3-methylimidazolium bromide] Charge amount
C-6: [Ionic liquid 1-butyl-3-methylimidazolium chloride]
C-7: [Ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate]
C-8: [ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate]
C-9: [ionic liquid 1-hexyl-3-methylimidazolium bromide]
C-10: [ionic liquid 1-octyl-3-methylimidazolium bromide]
D: [butanol] input amount
F: [para-toluene sulfonic acid]

According to the results of Tables 1 to 4, the reaction solution of the present invention uses butanol or 3-pentanol as a reaction solvent, and rhenium oxide (Re ₂ O ₇ ) and ammonium perrhenate as a catalyst for dioxydihydration reaction (NH ₄ ReO ₄ ), a solution in which a specific ionic liquid is mixed can be used, and in particular, 1-butyl-3-methylimidazolium trifluoromethane sulfonate ([C ₄ mim] OTf ), It was confirmed that the yield of dibutyl muconate was the highest.

That is, in Example 1 (Comparative Example 1) using an ionic liquid having a trifluoromethanesulfonate anion ( ^- OTf) and a bis (trifluoromethylsulfonyl) imide anion, ^- TFSI, To Example 12, yield of dibutyl muconate was 90 or more, which was superior to the comparative examples shown in Table 4. It was confirmed that even when only the reactant and the solvent were added to the recovered ionic liquid, It was confirmed that the same product was obtained.

The dibutyl muconate thus prepared is hydrolyzed using a noble metal catalyst such as platinum or palladium catalyst and hydrolyzed to produce adipic acid.

Therefore, the yield of the excellent dibutyl muconate in the examples of the present invention is influential on the production of adipic acid thereafter, thereby improving the yield of adipic acid.

Conventionally, in general, there is a problem in that a strong and toxic chemical product is used for the synthesis of mucic acid to adipic acid, or the yield is very low. However, according to the production method of the present invention, biomass such as marine resources To produce adipic acid which is a raw material of nylon 66 and is environmentally friendly and provides a possibility of producing a high yield adipic acid at a low cost through a much simpler process than the conventional production method, It is used as a raw material of nylon 66 which is used as a material for automobile parts using pickles, which has a large ripple effect on the industry.

Claims (12)

(a) preparing a reaction solution by adding a mucic acid diester, a catalyst for dioxydihydration reaction, an acid catalyst, and an ionic liquid represented by the following formula 2 to a reaction solvent;
(b) subjecting the prepared reaction solution to a deoxydehydration (DODH) reaction at a predetermined temperature for a predetermined time;
(c) the reaction solution obtained in the step (b) is concentrated, and the resultant muconate may be dissolved. Alternatively, an organic solvent immiscible with the ionic liquid may be added and mixed, ; And
(d) concentrating and purifying the recovered organic solvent layer to obtain and isolating a muconate represented by the following formula (3)
In the step (a)
Wherein the reaction solvent is 1-butanol or 3-pentanol,
The catalyst for the dioxydihydration reaction is rhenium oxide (Re ₂ O ₇ ) or ammonium perrhenate (NH ₄ ReO ₄ )
The acid catalyst is para-toluene sulfonic acid,
Wherein the ionic liquid is selected from the group consisting of 1-butyl-3-methylimidazolium trifluoromethanesulfonate, [C ₄ mim] OTf), 1-octyl-3-methylimidazolium tri (1-octyl-3-methylimidazolium trifluoromethanesulfonate, [C ₈ mim] OTf) and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate Wherein the mucronate is one selected from the group consisting of mica and mica.

(Wherein R is a linear or branched alkyl having 1 to 20 carbon atoms). The method according to claim 1,
Wherein the step (a) comprises reacting mucic acid with an alcohol having 1 to 10 carbon atoms to prepare a mucic acid diester. delete delete delete delete The method according to claim 1,
Wherein the ionic liquid and the reaction solvent are mixed in a volume ratio of 1: 1 to 1: 200 in the step (a). The method according to claim 1,
Wherein the step (b) is performed at a temperature of 100 ° C to 200 ° C. The method according to claim 1,
Wherein the step (b) is carried out by reflux stirring for 12 hours to 72 hours to perform deoxydehydration (DODH) reaction. The method according to claim 1,
In the step (c), an organic solvent which can dissolve the muconate in the reaction solution containing the muconate and is immiscible with the ionic liquid is added to the mixture, and the mixture is mixed with a catalyst for the dioxydihydration reaction And separating into an ionic liquid layer containing an acid catalyst and an organic solvent layer containing muconate on the upper part of the mixture. 11. The method of claim 10,
The organic solvent may be selected from the group consisting of acetone, dichloromethane, chloroform, ethyl acetate, acetomitrole, diethyl ether, hexane, tetrahydrofuran, Wherein the catalyst is at least one selected from the group consisting of tetrahydrofuran, benzene, toluene and xylene. The method according to claim 1,
Wherein the step (d) comprises purifying the organic solvent layer separated through the step (c) through a column chromatography or a distillation method.

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