3-Hydroxyadipic acid-3,6-lactone composition

Abstract

This invention utilizes a composition containing 3-30 parts by weight of α-hydrogenated adipate relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone as a raw material to produce adipic acid with high selectivity without nitrous oxide emissions. The resulting adipic acid can be used as a polyamide or polyester raw material.

Description

Technical Field

[0001] This invention relates to a 3-hydroxyadipic acid-3,6-lactone composition with 3-hydroxyadipic acid-3,6-lactone as the main component, a method for manufacturing adipic acid from the 3-hydroxyadipic acid-3,6-lactone composition, and a method for manufacturing polyamides and polyesters using the adipic acid. Background Technology

[0002] Adipic acid is a raw material monomer for polyamides and polyesters. Industrially, adipic acid can be produced by nitric acid oxidation of a mixture of cyclohexanone and cyclohexanol (KA oil), but this process produces a large amount of nitrous oxide (N2O) gas, which has a high greenhouse effect. Therefore, a method for producing adipic acid without producing nitrous oxide as a byproduct is desired.

[0003] Patent Document 1 describes a process for producing adipic acid by reacting 3-hydroxyadipate-3,6-lactone with hydrogen in the presence of a hydrogenation catalyst without producing nitrous oxide as a byproduct. 3-hydroxyadipate-3,6-lactone is known as a raw material for adipic acid. Non-Patent Document 1 describes a process for producing adipic acid by reacting α-hydrogenated adipate with hydrogen in the presence of a hydrogenation catalyst without producing nitrous oxide. α-Hydrated adipate is known as a raw material for adipic acid. Furthermore, Patent Document 2 describes the use of a mixture of 3-hydroxyadipate-3,6-lactone and α-hydrogenated adipate as a raw material for ε-caprolactam, but does not suggest the possibility of using this mixture as a raw material for adipic acid, or the suitable composition of such a mixture.

[0004] Non-Patent Literature 2 discloses the correlation between fatty acid metabolism and the concentration of 3-hydroxyadipate-3,6-lactone in urine. In this literature, a standard sample of 3-hydroxyadipate-3,6-lactone was chemically synthesized for the purpose of quantifying 3-hydroxyadipate-3,6-lactone in urine. Regarding the synthesized 3-hydroxyadipate-3,6-lactone, a composition containing 2 parts by weight of α-hydrogenated adipate relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone is described, but the possibility of using this mixture as a raw material for adipic acid is neither described nor suggested.

[0005] Existing technical documents

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2015 / 086821

[0008] Patent Document 2: International Publication No. 2016 / 068108

[0009] Non-patent literature

[0010] Non-patent literature 1: Angewandte Chemie International Edition, vol.53, pp.7785-7788 (2014).

[0011] Non-patent literature 2: Metabolism, vol.38, No.7, pp.655-661 (1989). Summary of the Invention

[0012] Problems to be solved by the invention

[0013] As mentioned above, 3-hydroxyadipic acid-3,6-lactone or α-hydrogenated adipate is known as a raw material for adipic acid. However, the inventors have discovered that when pure 3-hydroxyadipic acid-3,6-lactone or α-hydrogenated adipate reacts with hydrogen in the presence of a hydrogenation catalyst to generate adipic acid, there is a problem of insufficient adipic acid selectivity.

[0014] Problem-solving methods

[0015] In order to solve the above-mentioned problems when using 3-hydroxyadipate-3,6-lactone as a raw material to manufacture adipic acid, the inventors conducted in-depth research and found that a 3-hydroxyadipate-3,6-lactone composition containing a specific amount of α-hydrogenated adipate as a by-product is a good adipic acid raw material that can suppress the generation of by-products, thus completing the present invention.

[0016] That is, the present invention is composed of the following (1) to (11).

[0017] (1) A 3-hydroxyadipic acid-3,6-lactone composition, wherein, relative to 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone, it contains 3 to 30 parts by weight of α-hydrogenated hexadienoic acid.

[0018] (2) A method for manufacturing a 3-hydroxyadipic acid-3,6-lactone composition, comprising the step of heating 3-hydroxyadipic acid-3,6-lactone to obtain the 3-hydroxyadipic acid-3,6-lactone composition of (1).

[0019] (3) A method for manufacturing adipic acid, comprising a step of reacting the 3-hydroxyadipic acid-3,6-lactone composition of (1) with hydrogen in the presence of a hydrogenation catalyst (hydrogenation step).

[0020] (4) The method for manufacturing adipic acid according to (3) includes the step of obtaining the 3-hydroxyadipic acid-3,6-lactone composition of (1) by the method of (2).

[0021] (5) A method for manufacturing a polyamide, comprising a step of manufacturing adipic acid by the method of (3) or (4), and a step of polycondensing adipic acid and diamine.

[0022] (6) According to the method for manufacturing polyamide described in (5), the diamine is a diamine containing 1,4-butanediamine, 1,5-pentanediamine or hexamethylenediamine.

[0023] (7) The polyamide is polyamide 46, polyamide 56 or polyamide 66 according to the method of manufacturing polyamide according to (5) or (6).

[0024] (8) A method for manufacturing a polyester, comprising a step of manufacturing adipic acid by the method of (3) or (4), and a step of polycondensing adipic acid and diols or adipic acid, diols and dicarboxylic acids.

[0025] (9) In the method of manufacturing polyester according to (8), the diol is a diol containing 1,4-butanediol.

[0026] (10) In the method of manufacturing polyester according to (8) or (9), the dicarboxylic acid is a dicarboxylic acid containing terephthalic acid or succinic acid.

[0027] (11) The method for manufacturing a polyester according to any one of (8) to (10), wherein the polyester is polybutylene adipate or polybutylene adipate succinate.

[0028] Invention Effects

[0029] According to the present invention, the adipic acid selectivity can be improved when using 3-hydroxyadipic acid-3,6-lactone as a raw material to manufacture adipic acid. Detailed Implementation

[0030] The present invention will now be described in more detail.

[0031] [3-Hydroxyadipic acid-3,6-lactone]

[0032] 3-hydroxyadipic acid-3,6-lactone is an organic compound represented by the following chemical formula (1), which can be chemically synthesized, for example, by the method shown in Reference Example 1 of the examples described later.

[0033]

[0034] Alternatively, 3-hydroxyadipic acid-3,6-lactone can be synthesized using 3-oxoadipic acid, which can be synthesized from biomass resources, as a starting material via a reaction as shown in, for example, route 1 below.

[0035]

[0036] The 3-hydroxyadipic acid-3,6-lactone can be a carboxylic acid, a carboxyl salt, a carboxyl ester, or a mixture thereof, and is used as the starting material of this invention. In this specification, they are collectively referred to as "3-hydroxyadipic acid-3,6-lactone".

[0037] Examples of carboxylates that are 3-hydroxyadipic acid-3,6-lactones include, for example, alkali metal salts, alkaline earth metal salts, or ammonium salts; specifically, lithium salts, sodium salts, potassium salts, ammonium salts, etc.

[0038] Carboxylic acid esters that are 3-hydroxyadipic acid-3,6-lactones can be exemplified by alkyl esters, and specific alkyl groups can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.

[0039] In addition, 3-hydroxyadipic acid (represented by the following chemical formula (2)) can be prepared by dissolving it in water and adjusting the pH to below 4.

[0040]

[0041] There are no particular restrictions on the type of acid added to adjust the pH to below 4; inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and boric acid, as well as organic acids such as formic acid, acetic acid, and propionic acid, are preferred.

[0042] [α-Hydroxyhexadienoic acid]

[0043] α-hydromuconic acid is an organic compound represented by the following chemical formula (3), which can be chemically synthesized, for example, by the method shown in Reference Example 2 of the examples described later.

[0044]

[0045] α-Hydroxyhexadienoic acid can also be obtained by converting a carbon source capable of being derived from biomass through microbial fermentation, as described in International Publication No. 2019 / 107516. α-Hydroxyhexadienoic acid contains one double bond within its molecule, thus exhibiting geometric isomers of cis and trans. However, in the manufacturing method of this invention, the cis, trans, or a mixture of cis and trans can all be used as raw materials.

[0046] α-Hydroxyhexadienoic acid can be a carboxylic acid, a carboxylate, a carboxylic acid ester, or a mixture thereof, and is thus used as a starting material for the present invention. In this specification, they are collectively referred to as "α-Hydroxyhexadienoic acid".

[0047] As carboxylates of α-hydrogenated hexadienediaic acid, examples include alkali metal salts, alkaline earth metal salts, and ammonium salts. Specifically, examples include monolithium salts, dilithium salts, monosodium salts, disodium salts, monopotassium salts, dipotassium salts, magnesium salts, calcium salts, monoammonium salts, and diammonium salts.

[0048] As carboxylic acid esters of α-hydrogenated hexadienedioic acid, examples include monoalkyl esters and dialkyl esters. As specific alkyl groups, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.

[0049] [3-Hydroxyadipic acid-3,6-lactone composition]

[0050] The 3-hydroxyadipate-3,6-lactone composition of the present invention is characterized by having 3-hydroxyadipate-3,6-lactone as the main component and containing α-hydrogenated adipate as a secondary component. By using the 3-hydroxyadipate-3,6-lactone composition of the present invention, adipic acid can be synthesized with high selectivity.

[0051] Here, "as a main component" means that the content of 3-hydroxyadipic acid-3,6-lactone in the 3-hydroxyadipic acid-3,6-lactone composition is more than 50% by weight, preferably more than 60% by weight, and more preferably more than 70% by weight.

[0052] In the 3-hydroxyadipic acid-3,6-lactone composition of the present invention, the content of α-hydrogenated adipate is 3 to 30 parts by weight, preferably 4 to 28 parts by weight, and more preferably 5 to 25 parts by weight, relative to 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone. With this composition, the by-product yield of valeric acid is reduced, thereby improving the adipic acid selectivity during the production of adipic acid.

[0053] There are no particular limitations on the method for manufacturing the 3-hydroxyadipic acid-3,6-lactone composition of the present invention. It can be prepared by mixing separately prepared pure 3-hydroxyadipic acid-3,6-lactone with α-hydrogenated adipate.

[0054] Furthermore, when α-hydrogenated adipate is present as an impurity during the manufacture of 3-hydroxyadipate-3,6-lactone, the 3-hydroxyadipate-3,6-lactone composition of the present invention can be prepared by appropriately adjusting the amount of impurity. Specifically, α-hydrogenated adipate is sometimes generated due to heating during the manufacturing process of 3-hydroxyadipate-3,6-lactone. In this case, the content of α-hydrogenated adipate can be adjusted by appropriately adjusting the heating temperature. There is a tendency that higher heating temperatures make it easier to generate α-hydrogenated adipate, but if the heating temperature is too high, the 3-hydroxyadipate-3,6-lactone composition is prone to thermal decomposition. From this perspective, the heating temperature is preferably 100–300°C, more preferably 120–250°C, and even more preferably 150–200°C.

[0055] The 3-hydroxyadipate-3,6-lactone and α-hydrogenated adipate contained in the 3-hydroxyadipate-3,6-lactone composition of the present invention can be quantified by analyzing the aqueous solution obtained by dissolving the composition in water using high-performance liquid chromatography (HPLC). The HPLC analysis of 3-hydroxyadipate-3,6-lactone and α-hydrogenated adipate was performed using a conductivity detector (CDD) and a UV-Vis detector (measurement wavelength 210 nm), respectively. From the perspective of detection sensitivity, a concentration of 1 to 10 g / L of the composition in the aqueous solution of the 3-hydroxyadipate-3,6-lactone composition prepared for HPLC analysis is appropriate.

[0056] In a 3-hydroxyadipate-3,6-lactone composition, the third component, besides 3-hydroxyadipate-3,6-lactone and α-hydrogenated adipate, may include water, alcohol, carboxylic acid, ether, ester, or ion. Specific examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, etc. Specific examples of carboxylic acids include oxalic acid, acetic acid, lactic acid, formic acid, pyruvic acid, propionic acid, malonic acid, succinic acid, citric acid, glycolic acid, malic acid, n-butyric acid, isobutyric acid, hydroxybutyric acid, α-ketoglutaric acid, maleic acid, tartaric acid, glyoxylic acid, citralic acid, pyroglutaric acid, ascorbic acid, 3-hydroxyadipate, etc. Specific examples of ethers include dimethyl ether, diethyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc. Specific examples of esters include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and γ-butyrolactone. Specific examples of ions include H+. + Li + Na + K + NH4 + Mg 2+ Ca 2+ Fe 2+ Fe3+ Zn 2+ Ni 2+ 、Mn 2+ OH - Cl - NO3 - SO4 2- PO4 3- CO3 2- wait.

[0057] In the 3-hydroxyadipate-3,6-lactone composition of the present invention, the difference between the sum of the contents of 3-hydroxyadipate-3,6-lactone (main component) and α-hydrogenated adipate (secondary component) and 100% by weight can be understood as constituting the aforementioned third component. Therefore, for example, a mixture consisting of 75% by weight of 3-hydroxyadipate-3,6-lactone, 10% by weight of α-hydrogenated adipate (equivalent to 13.3 parts by weight of α-hydrogenated adipate relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone), and 15% by weight of water is included in the 3-hydroxyadipate-3,6-lactone composition of the present invention.

[0058] The aforementioned third component can be one or more, and when present, water is preferred. Specifically, regarding the water content in the composition when water is included as the third component of the 3-hydroxyadipic acid-3,6-lactone composition, it is preferably 40% by weight or less, more preferably 30% by weight or less, further preferably 25% by weight or less, and particularly preferably 20% by weight or less, in 100% by weight of the 3-hydroxyadipic acid-3,6-lactone composition.

[0059] [The manufacture of adipic acid]

[0060] Adipic acid can be produced by reacting the 3-hydroxyadipic acid-3,6-lactone composition of the present invention with hydrogen in the presence of a hydrogenation catalyst (hydrogenation).

[0061] The hydrogenation catalyst preferably contains a transition metal element, specifically, preferably one or more selected from palladium, platinum, ruthenium, rhodium, rhenium, nickel, cobalt, iron, iridium, osmium, copper and chromium, more preferably one or more selected from palladium, platinum, nickel, cobalt, iron, copper and chromium.

[0062] Considering the savings in metal usage and the increase in the active surface area of ​​the catalyst, hydrogenation catalysts are preferably used supported on a carrier. The loading of hydrogenation catalysts onto a carrier can be carried out using known methods such as impregnation, precipitation, and gas-phase loading. Examples of suitable carriers include carbon, polymers, metal oxides, metal sulfides, zeolites, clays, heteropoly acids, solid phosphoric acid, and hydroxyapatite.

[0063] The hydrogen reacting with the 3-hydroxyadipic acid-3,6-lactone composition can be added to the reactor all at once or gradually. There is no particular limitation on the partial pressure of hydrogen; however, if it is too low, the reaction time will be longer. On the other hand, if the partial pressure of hydrogen is too high, it is not preferable from an equipment safety perspective. Therefore, at room temperature, a pressure of 0.1 MPa or higher and 10 MPa or lower (gauge pressure) is preferred, more preferably 0.3 MPa or higher and 5 MPa or lower (gauge pressure), and even more preferably 0.5 MPa or higher and 3 MPa or lower (gauge pressure).

[0064] The reaction can be carried out using any of the following reactor types: batch tank reactor, semi-batch tank reactor, continuous tank reactor, continuous tubular reactor, or trickle bed tubular reactor. When using a solid hydrogenation catalyst, the reaction can be carried out using any of the following methods: suspended bed, fixed bed, moving bed, or fluidized bed.

[0065] There is no particular limitation on the reaction temperature for hydrogenation. If the temperature is too low, the reaction rate will slow down; if the temperature is too high, the energy consumption will increase, which is not preferable. Considering this, the preferred reaction temperature is 100–350°C, more preferably 120–300°C, even more preferably 130–280°C, even more preferably 140–250°C, even more preferably 150–230°C, and even more preferably 160–220°C.

[0066] In addition to hydrogen, inert gases such as nitrogen, helium, and argon can coexist in the reactor atmosphere. However, since this can lead to the deterioration of the hydrogenation catalyst and the generation of detonating gases, the oxygen concentration is preferably 5% by volume or less. Furthermore, considering the stability of the 3-hydroxyadipate-3,6-lactone composition and adipic acid, the amount of ammonia relative to the 3-hydroxyadipate-3,6-lactone composition is preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 0% by weight (i.e., the reaction in the absence of ammonia).

[0067] The hydrogenation of the 3-hydroxyadipic acid-3,6-lactone composition is preferably carried out in the presence of a solvent.

[0068] As solvents for hydrogenation, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentane, hexane, cyclohexane, heptane, octane, decane, dimethyl ether, diethyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, and aqueous solvents can be used. Mixed solvents of two or more of these can be used. Considering economic and environmental factors, aqueous solvents are preferred.

[0069] In this invention, aqueous solvents refer to water or a mixed solvent consisting mainly of water and a water-soluble organic solvent. "Mainly water" means that the proportion of water in the mixed solvent is more than 50% by volume, preferably more than 70% by volume, and more preferably more than 90% by volume.

[0070] Examples of water-soluble organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and acetone.

[0071] There are no particular restrictions on the pH of aqueous solvents. However, if factors such as inhibiting catalyst degradation, inhibiting the formation of byproducts, and the corrosiveness to the reaction apparatus are taken into account, a pH of 2 to 13 is preferred, a pH of 3 to 11 is more preferred, and a pH of 4 to 10 is even more preferred.

[0072] There is no particular limitation on the amount of the 3-hydroxyadipate-3,6-lactone composition relative to the solvent, but low amounts are not preferred industrially. From this perspective, for the amount of the 3-hydroxyadipate-3,6-lactone composition relative to 100 parts by weight of the solvent, it is preferably 0.1 parts by weight or more and 900 parts by weight or less, more preferably 0.2 parts by weight or more and 800 parts by weight or less, and even more preferably 1.0 parts by weight or more and 700 parts by weight or less, in terms of the amount of 3-hydroxyadipate-3,6-lactone.

[0073] When a solvent other than primary and secondary alcohols is used as the hydrogenation solvent, the carboxylic acid, carboxylate, and carboxyl ester of the 3-hydroxyadipic acid-3,6-lactone composition are converted into the corresponding adipic acid, adipic acid salt, and adipic acid ester, respectively. When a solvent containing primary or secondary alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol is used as the hydrogenation solvent, a mixture of adipic acid, adipic acid salt, adipic acid monoester, and adipic acid diester is obtained after the reaction. It should be noted that in this specification, the carboxylic acid, carboxylate, carboxyl ester, and mixtures thereof are collectively referred to as "adipic acid".

[0074] The adipic acid carboxylic acid obtained in this invention can be further converted into adipate ester by esterification. There are no particular limitations on the esterification method; examples include the dehydration condensation of the carboxylic acid and alcohol using an acid catalyst or condensing agent, and methods using alkylating agents such as diazomethane or haloalkyl groups.

[0075] The adipic acid obtained in this invention can be separated and purified by conventional unit operations such as centrifugation, filtration, membrane filtration, distillation, extraction, crystallization, and drying.

[0076] [Manufacturing of various chemicals using adipic acid as a raw material]

[0077] Adiponitrile can be produced from the adipic acid obtained in this invention using known methods (e.g., Japanese Patent Publication No. 61-24555). Hexamethylenediamine can be produced by hydrogenating the obtained adiponitrile using known methods (e.g., Japanese Patent Publication No. 2000-508305).

[0078] Polyamides can be manufactured by polycondensing adipic acid obtained in this invention with a diamine using known methods (for example, see Fukumoto Osamu, "Polyamide Resin Handbook," Nikkan Kogyo Publishing (January 1998)). Specifically, polyamide 46, polyamide 56, and polyamide 66 can be manufactured by using 1,4-diaminobutane, 1,5-pentanediamine, and hexamethylenediamine as diamines.

[0079] Polyamide fibers can be manufactured by processing polyamides using well-known methods (e.g., International Publication No. 2019 / 208427). The resulting polyamide fibers can be used in clothing applications such as underwear, sportswear, and casual wear, as well as in industrial materials such as airbags and tire cords.

[0080] Alternatively, polyamide can be molded using known methods (e.g., International Publication No. 2021 / 006257) to manufacture polyamide molded articles. The resulting polyamide molded articles can be used in automotive parts, electrical components, electronic components, building components, various containers, daily necessities, household goods, and hygiene products, etc.

[0081] Polyesters can be manufactured by polycondensing adipic acid obtained in this invention with diols using known methods (for example, see "Research on Coatings, vol. 151, pp. 2-8," Kansai Paint Co., Ltd. (November 2009)). Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, etc., can be used as diols. In this case, in addition to the adipic acid obtained in this invention, it can also be copolymerized with any dicarboxylic acid. Specifically, examples of dicarboxylic acids that can be copolymerized include oxalic acid, malonic acid, succinic acid, glutaric acid, octanoic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 2,5-furandicarboxylic acid, etc. Here, by using 1,4-butanediol as the diol and terephthalic acid or succinic acid as the dicarboxylic acid, polybutylene terephthalate adipate (PBAT) and polybutylene adipate adipate (PBSA) can be obtained, respectively. These polyesters are biodegradable and therefore preferred from an environmental perspective. PBAT and PBSA can be manufactured by known methods (e.g., Journal of Polymer Science: Part A: Polymer Chemistry, vol. 40, pp. 4141-4157 (2002), International Publication No. 1996 / 019521). "Biodegradability" refers to the property of being broken down to the molecular level by microorganisms, ultimately becoming carbon dioxide and water and cycling back into nature.

[0082] Polyester fibers can be manufactured by processing polyester using known methods (e.g., International Publication No. 2007 / 037174). The resulting polyester fibers can be used to make woven fabrics, knitted fabrics, nonwoven fabrics, and other fiber products, as well as clothing, fiber brushes, blankets, and other items that use them.

[0083] Polyester can be molded using known methods (e.g., International Publication No. 2015 / 072216) to manufacture polyester molded articles. These polyester molded articles can be used in automotive parts, electrical components, electronic components, mechanical parts, building components, various containers, daily necessities, household goods, and hygiene products, etc.

[0084] Polyester film can be manufactured by stretching polyester using well-known methods (e.g., International Publication No. 2010 / 038655). The resulting polyester film can be used in a variety of applications, including electronic devices, semiconductor products, electrical appliances, automotive parts, packaging, and building materials.

[0085] Example

[0086] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples. It should be noted that the reaction results in the examples and comparative examples are defined by the following formula.

[0087] Product selectivity (%) = Product yield (mol) / Raw material yield (mol) × 100.

[0088] The analysis and quantification of 3-hydroxyadipic acid-3,6-lactone and adipic acid were performed under HPLC analysis conditions 1 shown below. The analysis and quantification of α-hydrogenated adipate and n-valeric acid were performed under HPLC analysis conditions 2 shown below. Quantification of raw materials and products was performed using absolute standard curves prepared with reference standards.

[0089] [HPLC Analysis Conditions 1]

[0090] HPLC apparatus: Prominence (manufactured by Shimadzu Corporation)

[0091] Columns: "Synergi Polar-RP" (manufactured by Phenomenex), 250 mm in length, 4.60 mm in inner diameter, and 4 μm in particle size; + "Synergi hydro-RP" (manufactured by Phenomenex), 250 mm in length, 4.60 mm in inner diameter, and 4 μm in particle size.

[0092] Mobile phase: 5 mM formic acid aqueous solution / acetonitrile = 98 / 2 (volume ratio)

[0093] Reaction solution: 5mM formic acid + 20mM Bis-Tris + 0.1mM EDTA·2Na aqueous solution / acetonitrile = 98 / 2 (volume ratio)

[0094] Flow rate: 1.0 mL / min

[0095] Detector: Conductivity Detector (CDD)

[0096] Column temperature: 45℃.

[0097] [HPLC Analysis Conditions 2]

[0098] HPLC apparatus: Prominence (manufactured by Shimadzu Corporation)

[0099] Column: "Synergi hydro-RP" (manufactured by Phenomenex), 250 mm in length, 4.60 mm in inner diameter, and 4 μm in particle size.

[0100] Mobile phase: 0.1 wt% aqueous phosphoric acid / acetonitrile = 95 / 5 (volume ratio)

[0101] Flow rate: 1.0 mL / min

[0102] Detector: UV-Vis detector (measurement wavelength 210nm)

[0103] Column temperature: 40℃.

[0104] [pH Analysis Method]

[0105] A Horiba pH meter F-52 (manufactured by Horiba Corporation) was used. pH calibration was performed using pH 4.01 standard solution (manufactured by Fuji Film & Wako Pure Chemical Co., Ltd.), pH 6.86 standard solution (manufactured by Fuji Film & Wako Pure Chemical Co., Ltd.), and pH 9.18 standard solution (manufactured by Fuji Film & Wako Pure Chemical Co., Ltd.).

[0106] (Refer to Example 1) Chemical Synthesis of 3-Hydroxyadipic Acid-3,6-Lactone

[0107] The 3-hydroxyadipic acid-3,6-lactone used in this invention is prepared by chemical synthesis. First, 13.2 g (0.1 mol) of monomethyl succinate (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.) was added to 1.5 L of superhydrohydrofuran (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.), while stirring. Simultaneously, 16.2 g (0.1 mol) of carbonyl diimidazole (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. Then, 15.6 g (0.1 mol) of potassium monomethyl malonate and 9.5 g (0.1 mol) of magnesium chloride were added to the suspension, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere, followed by stirring at 40°C for 12 hours. After the reaction was completed, 0.05 L of 1 mol / L hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The mixture was then separated and purified by silica gel column chromatography (hexane:ethyl acetate = 1:5) to obtain 13.1 g of pure dimethyl 3-oxohexanedicarboxylic acid.

[0108] 10 g (0.05 mol) of the obtained dimethyl 3-oxohexanedicarboxylate was added to 0.1 L of methanol (manufactured by a domestic chemical company), and 0.02 L of 5 mol / L sodium hydroxide aqueous solution was added while stirring. The mixture was stirred at room temperature for 2 hours. After the reaction was completed, the pH was adjusted to 1 with 5 mol / L hydrochloric acid. Then, 2.0 g (0.05 mol) of sodium borohydride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. After concentration using a rotary evaporator, 0.1 L of ultrapure water was added, and 0.01 L of 1 mol / L sulfuric acid was added while stirring. The mixture was stirred at 100 °C for 2 hours. The solution was concentrated using a rotary evaporator and purified by silica gel column chromatography (chloroform:methanol = 10:1) to obtain 5.8 g of pure 3-hydroxyadipic acid-3,6-lactone (carboxylic acid).

[0109] 1 H-NMR (400MHz, D2O): δ2.03 (m, 1H), δ2.04-2.90 (m, 5H), δ5.00 (m, 1H).

[0110] (Refer to Example 2) Chemical Synthesis of α-Hydroxyhexadienoic Acid

[0111] The α-hydrogenated hexadienoic acid used in this invention was prepared by chemical synthesis. 0.1 L of methanol (manufactured by a domestic chemical company) was added to 10 g (0.05 mol) of dimethyl 3-oxohexanedicarboxylate obtained in the same manner as in Reference Example 1. While stirring, 2.0 g (0.05 mol) of sodium borohydride (manufactured by Fuji Film Wako Pure Chemical Industries Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour. Next, 0.02 L of a 5 mol / L aqueous solution of sodium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the pH was adjusted to 1 with 5 mol / L hydrochloric acid, concentrated using a rotary evaporator, and recrystallized with water to obtain 7.2 g of pure α-hydrogenated hexadienoic acid (carboxylic acid).

[0112] 1 H-NMR (400MHz, CD3OD): δ2.48(m,4H), δ5.84(d,1H), δ6.96(m,1H).

[0113] (Refer to Example 3) Chemical Synthesis of 3-Hydroxyhexanoic Acid

[0114] The 3-hydroxyadipic acid used in this invention was prepared by chemical synthesis. 0.1 L of methanol (manufactured by a domestic chemical company) was added to 10 g (0.05 mol) of dimethyl 3-oxohexanedicarboxylate obtained in the same manner as in Reference Example 1. While stirring, 0.02 L of a 5 mol / L aqueous solution of sodium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the pH was adjusted to 1 with 5 mol / L hydrochloric acid. Then, 2.0 g (0.05 mol) of sodium borohydride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated using a rotary evaporator, and then recrystallized with water to obtain 7.2 g of pure 3-hydroxyadipic acid (carboxylic acid).

[0115] 1 H-NMR (400MHz, CD3OD): δ1.70(m,1H), δ1.83(m,1H), δ2.42(m,4H), δ4.01(m,1H).

[0116] (Example 1)

[0117] By physically mixing 0.92 g of 3-hydroxyadipate-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.08 g of α-hydrogenated hexadienediaic acid (carboxylic acid) prepared in Reference Example 2, a 3-hydroxyadipate-3,6-lactone composition containing 8.7 parts by weight of α-hydrogenated hexadienediaic acid relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone was obtained.

[0118] In a 0.1L stainless steel autoclave (manufactured by Pressure Glass Industry Co., Ltd.), 1.0g of the above-mentioned 3-hydroxyadipic acid-3,6-lactone composition, 20g of water, and 0.025g of palladium (5% on gamma alumina powder, reduced) (manufactured by Alfa Aesar) were added. After purging the autoclave with nitrogen, hydrogen was added to adjust the hydrogen partial pressure to 0.9MPa (gauge pressure). The temperature inside the autoclave was raised to 200°C and maintained at 200°C for 3 hours. Then, it was allowed to cool naturally to room temperature, the gas inside the autoclave was released, and the pressure was restored to atmospheric pressure. The reaction solution was recovered. The filtrate after removing the catalyst was analyzed by HPLC, and the product selectivity was calculated. The results are shown in Table 1.

[0119] (Example 2)

[0120] By physically mixing 0.8 g of 3-hydroxyadipate-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.2 g of α-hydrogenated hexadienediaic acid (carboxylic acid) prepared in Reference Example 2, a 3-hydroxyadipate-3,6-lactone composition containing 25 parts by weight of α-hydrogenated hexadienediaic acid relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone was obtained, and the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0121] (Comparative Example 1)

[0122] The reaction was carried out in the same manner as in Example 1, except that 1 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was used instead of the 3-hydroxyadipic acid-3,6-lactone composition. The results are shown in Table 1.

[0123] (Comparative Example 2)

[0124] The reaction was carried out in the same manner as in Example 1, except that 1 g of α-hydrogenated adipate (carboxylic acid) prepared in Reference Example 2 was used instead of the 3-hydroxyadipate-3,6-lactone composition. The results are shown in Table 1.

[0125] (Example 3)

[0126] 3 g of the 3-hydroxyadipate-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was added to a round-bottom flask, heated to 165°C in an oil bath, maintained at 165°C for 30 minutes, and then allowed to cool naturally to room temperature. The aqueous solution obtained by adding 300 mL of water to the round-bottom flask was analyzed by HPLC. The content of α-hydrogenated adipate was 5.9 parts by weight relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone in the aqueous solution. 1 g of the 3-hydroxyadipate-3,6-lactone composition obtained by removing water using a rotary evaporator was reacted in the same manner as in Example 1. The results are shown in Table 1.

[0127] Table 1 Dicarboxylic Acids

[0128]

[0129] 3HA macroesters

[0130] C-HMA: α-Hydroxyhexadienoic acid

[0131] Examples 1-3 and Comparative Examples 1-2 demonstrate that, compared to using pure 3-hydroxyadipate-3,6-lactone or pure α-hydrogenated adipate as raw materials, by using a 3-hydroxyadipate-3,6-lactone composition containing 3-30 parts by weight of α-hydrogenated adipate relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone as raw material, the formation of valeric acid as a byproduct is suppressed, and adipic acid can be produced with high selectivity.

[0132] (Comparative Example 3)

[0133] By physically mixing 0.98 g of 3-hydroxyadipate-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.02 g of α-hydrogenated hexadienediaic acid (carboxylic acid) prepared in Reference Example 2, a 3-hydroxyadipate-3,6-lactone composition containing 2 parts by weight of α-hydrogenated hexadienediaic acid per 100 parts by weight of 3-hydroxyadipate-3,6-lactone was obtained, and the reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

[0134] (Example 4)

[0135] 3 g of the 3-hydroxyadipate-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was added to a round-bottom flask, heated to 190°C in an oil bath, maintained at 190°C for 30 minutes, and then allowed to cool naturally to room temperature. The aqueous solution obtained by adding 300 mL of water to the round-bottom flask was analyzed by HPLC. The content of α-hydrogenated adipate was 11 parts by weight relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone in the aqueous solution. 1 g of the 3-hydroxyadipate-3,6-lactone composition obtained by removing water using a rotary evaporator was reacted in the same manner as in Example 1. The results are shown in Table 2.

[0136] (Example 5)

[0137] 0.9 g of 3-hydroxyadipate-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.1 g of α-hydrogenated hexadienediaic acid (carboxylic acid) prepared in Reference Example 2 were physically mixed to obtain a 3-hydroxyadipate-3,6-lactone composition containing 11.1 parts by weight of α-hydrogenated hexadienediaic acid relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone. The catalyst was 0.005 g of 5% palladium / carbon (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and the reaction temperature was 160°C. Otherwise, the reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

[0138] (Example 6)

[0139] The reaction was carried out in the same manner as in Example 1, except that tetrahydrofuran (THF) was used instead of water as the solvent. The results are shown in Table 2.

[0140] (Example 7)

[0141] The reaction was carried out in the same manner as in Example 1, except that a mixed solvent of water and tetrahydrofuran (water / THF ratio of 6 / 4 v / v) was used instead of water. The results are shown in Table 2.

[0142] (Example 8)

[0143] 20 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was added to a round-bottom flask, heated to 200°C in an oil bath, and maintained at 200°C for 30 minutes. After cooling naturally to room temperature, a 3-hydroxyadipic acid-3,6-lactone composition containing 8.6 parts by weight of α-hydrogenated hexadienediaic acid was obtained relative to 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone.

[0144] In a 0.1L stainless steel autoclave (manufactured by Pressure Glass Industry Co., Ltd.), 10g of the above-mentioned 3-hydroxyadipic acid-3,6-lactone composition, 20g of water, and 0.02g of 5% palladium on carbon (Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added. The autoclave was purged with nitrogen and then pressurized with hydrogen to maintain the pressure inside the autoclave at 0.9MPa (gauge pressure) during hydrogenation. The temperature was raised to 150°C and maintained at 150°C for 15 hours. The autoclave was then allowed to cool naturally to room temperature, releasing the gas inside and restoring the pressure to atmospheric pressure. The reaction solution was recovered. The filtrate after removing the catalyst was analyzed by HPLC, and the product selectivity was calculated. The results are shown in Table 2.

[0145] (Example 9)

[0146] Except for using 0.05 g of Raney nickel (manufactured by Fuji Film Wako Pure Chemical Industries Co., Ltd.) as a catalyst, the reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

[0147] Table 2

[0148] Adipic acid is manufactured from a composition of 3-hydroxyadipic acid-3,6-lactone.

[0149]

[0150] 3HAL: 3-Hydroxyadipic acid-3,6-lactone

[0151] α-HMA: α-Hydroxyhexadienoic acid

[0152] THF: Tetrahydrofuran

[0153] Comparative Examples 3 and Examples 4-9 demonstrate that, regardless of the solvent, reaction temperature, or catalyst, by using a 3-hydroxyadipate-3,6-lactone composition containing 3 to 30 parts by weight of α-hydrogenated hexadienediaic acid relative to 100 parts by weight of 3-hydroxyadipate-3,6-lactone as a starting material, the formation of valeric acid as a byproduct is suppressed, and adipic acid can be produced with high selectivity.

Claims

1. A 3-hydroxyadipic acid-3,6-lactone composition, wherein, relative to 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone, it contains 3 to 30 parts by weight of α-hydrogenated hexadienoic acid.

2. A method for manufacturing a 3-hydroxyadipic acid-3,6-lactone composition, comprising the step of heating 3-hydroxyadipic acid-3,6-lactone to obtain the 3-hydroxyadipic acid-3,6-lactone composition of claim 1.

3. A method for producing adipic acid, comprising a hydrogenation step of reacting the 3-hydroxyadipic acid-3,6-lactone composition of claim 1 with hydrogen in the presence of a hydrogenation catalyst.

4. The method for manufacturing adipic acid according to claim 3, comprising the step of obtaining the 3-hydroxyadipic acid-3,6-lactone composition of claim 1 by the method of claim 2.

5. A method for manufacturing a polyamide, comprising a step of manufacturing adipic acid by the method of claim 3 or 4, and a step of polycondensing adipic acid and a diamine.

6. The method for manufacturing polyamide according to claim 5, wherein the diamine is a diamine containing 1,4-butanediamine, 1,5-pentanediamine or hexamethylenediamine.

7. The method for manufacturing polyamide according to claim 5 or 6, wherein the polyamide is polyamide 46, polyamide 56 or polyamide 66.

8. A method for manufacturing a polyester, comprising a step of manufacturing adipic acid by the method of claim 3 or 4, and a step of polycondensing adipic acid and a diol or adipic acid, a diol and a dicarboxylic acid.

9. The method for manufacturing polyester according to claim 8, wherein the diol is a diol containing 1,4-butanediol.

10. The method for manufacturing polyester according to claim 8 or 9, wherein the dicarboxylic acid is a dicarboxylic acid containing terephthalic acid or succinic acid.

11. The method for manufacturing polyester according to claim 8 or 9, wherein the polyester is polybutylene adipate or polybutylene adipate succinate.

12. The method for manufacturing polyester according to claim 10, wherein the polyester is polybutylene adipate or polybutylene adipate succinate.

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