Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

Definitions

• the present invention provides a 3-hydroxyadipic acid-3,6-lactone composition containing 3-hydroxyadipic acid-3,6-lactone as a raw material of adipic acid as a main component, and the 3-hydroxyadipic acid-3,
• the present invention relates to a method for producing adipic acid from a 6-lactone composition and a method for producing polyamide and polyester using the adipic acid.
• Adipic acid is a raw material monomer for polyamides and polyesters.
• Adipic acid can be industrially produced by nitric acid oxidation of a mixture of cyclohexanone and cyclohexanol (KA oil).
• KA oil a mixture of cyclohexanone and cyclohexanol
• Patent Document 1 describes a process of reacting 3-hydroxyadipic acid-3,6-lactone with hydrogen in the presence of a hydrogenation catalyst to produce adipic acid without by-producing dinitrogen monoxide.
• 3-hydroxyadipic acid-3,6-lactone is known to be a raw material for adipic acid.
• Non-Patent Document 1 describes that when ⁇ -hydromuconic acid was reacted with hydrogen in the presence of a hydrogenation catalyst, adipic acid was produced without dinitrogen monoxide as a by-product.
• Acid is known to be a raw material for adipic acid.
• Patent Document 2 describes that a mixture of 3-hydroxyadipic acid-3,6-lactone and ⁇ -hydromuconic acid may be used as a raw material for ⁇ -caprolactam. and the appropriate composition of the mixture as a source of adipic acid are not suggested.
• Non-Patent Document 2 discloses the relationship between fatty acid metabolism and urinary 3-hydroxyadipate-3,6-lactone concentration.
• a reference sample of 3-hydroxyadipate-3,6-lactone is chemically synthesized for the purpose of quantifying 3-hydroxyadipate-3,6-lactone in urine.
• the synthesized 3-hydroxyadipic acid-3,6-lactone contains 2 parts by weight of ⁇ -hydromuconic acid per 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone.
• a 3,6-lactone composition is described, but the utility of such mixture as a source of adipic acid is neither described nor suggested.
• 3-hydroxyadipic acid-3,6-lactone or ⁇ -hydromuconic acid is known to be a raw material for adipic acid. It was newly found that when ,6-lactone or ⁇ -hydromuconic acid is reacted with hydrogen in the presence of a hydrogenation catalyst to produce adipic acid, the adipic acid selectivity is insufficient.
• the present inventors have made intensive studies to solve the above-mentioned problems in producing adipic acid using 3-hydroxyadipic acid-3,6-lactone as a starting material, and as a result, have found that 3-hydroxyadipic acid-3,6- A 3-hydroxyadipic acid-3,6-lactone composition containing a lactone containing a specific amount of ⁇ -hydromuconic acid as an auxiliary component is a good adipic acid raw material capable of suppressing the production of by-products. and completed the present invention.
• the present invention consists of the following (1) to (11).
• a 3-hydroxyadipic acid-3,6-lactone composition containing 3 to 30 parts by weight of ⁇ -hydromuconic acid per 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone.
• 3-hydroxyadipic acid-3,6-lactone comprising the step of heating 3-hydroxyadipic acid-3,6-lactone to obtain the 3-hydroxyadipic acid-3,6-lactone composition according to (1);
• a method for producing a 3,6-lactone composition A method for producing adipic acid, comprising a step of reacting the 3-hydroxyadipic acid-3,6-lactone composition according to (1) with hydrogen in the presence of a hydrogenation catalyst (hydrogenation step).
• a method for producing adipic acid according to (3) comprising a step of obtaining the 3-hydroxyadipic acid-3,6-lactone composition according to (1) by the method according to (2).
• a method for producing a polyamide comprising a step of producing adipic acid by the method described in (3) or (4), and a step of polycondensing the adipic acid and the diamine.
• the method for producing a polyamide according to (5) or (6), wherein the polyamide is polyamide 46, polyamide 56 or polyamide 66.
• a method for producing a polyester comprising a step of producing adipic acid by the method described in (3) or (4), and a step of polycondensing adipic acid and glycols or adipic acid, glycols and dicarboxylic acid. .
• (11) The method for producing a polyester according to any one of (8) to (10), wherein the polyester is polybutylene adipate terephthalate or polybutylene succinate adipate.
• the present invention it is possible to increase the adipic acid selectivity when producing adipic acid using 3-hydroxyadipic acid-3,6-lactone as a raw material.
• 3-hydroxyadipic acid-3,6-lactone is an organic compound represented by the following chemical formula (1). It can be chemically synthesized by the method shown.
• 3-hydroxyadipic acid-3,6-lactone can be synthesized by using 3-oxoadipic acid that can be synthesized from biomass resources as a raw material, for example, by the reaction shown in Scheme 1 below.
• the 3-hydroxyadipic acid-3,6-lactone may be a carboxylic acid, a carboxylic acid salt, a carboxylic acid ester, or even a mixture thereof can be used as a starting material in the present invention, and these are collectively referred to as "3-hydroxyadipic acid-3,6-lactone".
• the carboxylate of 3-hydroxyadipic acid-3,6-lactone includes, for example, alkali metal salts, alkaline earth metal salts or ammonium salts, specifically lithium salts, sodium salts, potassium salts, ammonium salts and the like.
• carboxylic acid esters of 3-hydroxyadipic acid-3,6-lactone include alkyl esters, and specific alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n- butyl group, isobutyl group, tert-butyl group and the like.
• 3-hydroxyadipic acid represented by the following chemical formula (2) is dissolved in water and the pH is adjusted to 4 or less to prepare 3-hydroxyadipic acid-3,6-lactone. can do.
• the acid added to adjust the pH to 4 or less is not particularly limited, but mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and boric acid, and organic acids such as formic acid, acetic acid and propionic acid are preferably used. can.
• ⁇ -hydromuconic acid is an organic compound represented by the following chemical formula (3), and can be chemically synthesized, for example, by the method shown in Reference Example 2 of Examples below.
• ⁇ -hydromuconic acid can also be obtained by converting a carbon source derivable from biomass by microbial fermentation, as described in WO 2019/107516. Since ⁇ -hydromuconic acid has one double bond in the molecule, there are cis and trans geometric isomers. and trans isomer mixtures can be used as starting materials.
• ⁇ -hydromuconic acid may be a carboxylic acid, a carboxylate salt, a carboxylic acid ester, or even a mixture thereof can be used as a starting material in the present invention, and are collectively referred to herein as " ⁇ - called hydromuconic acid.
• the carboxylic acid salt of ⁇ -hydromuconic acid includes, for example, alkali metal salts, alkaline earth metal salts and ammonium salts. Potassium salt, dipotassium salt, magnesium salt, calcium salt, monoammonium salt, diammonium salt and the like.
• Carboxylic acid esters of ⁇ -hydromuconic acid include, for example, monoalkyl esters and dialkyl esters, and specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl group, tert-butyl group and the like.
• the 3-hydroxyadipic acid-3,6-lactone composition of the present invention is characterized by containing 3-hydroxyadipic acid-3,6-lactone as a main component and ⁇ -hydromuconic acid as a secondary component.
• adipic acid can be synthesized with high selectivity.
• mainly composed 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 60% by weight. % or more, more preferably 70% by weight or more.
• the content of ⁇ -hydromuconic acid is preferably 3 to 30 parts by weight per 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone. is 4 to 28 parts by weight, and more preferably 5 to 25 parts by weight. Selectivity can be increased.
• the method for producing the 3-hydroxyadipic acid-3,6-lactone composition of the present invention is not particularly limited. It may be prepared by mixing.
• 3-hydroxyadipic acid-3 of the present invention can be obtained by appropriately adjusting the amount of impurities.
• ,6-lactone compositions may be prepared. Specifically, ⁇ -hydromuconic acid may be generated by heating during the production process of 3-hydroxyadipic acid-3,6-lactone or the like. content can be adjusted. The higher the heating temperature, the more easily ⁇ -hydromuconic acid is produced. However, if the heating temperature is too high, the 3-hydroxyadipic acid-3,6-lactone composition is likely to be thermally decomposed. From such a viewpoint, the heating temperature is preferably 100 to 300°C, more preferably 120 to 250°C, still more preferably 150 to 200°C.
• the 3-hydroxyadipic acid-3,6-lactone and ⁇ -hydromuconic acid contained in the 3-hydroxyadipic acid-3,6-lactone composition of the present invention can be dissolved in water to obtain an aqueous solution. It can be quantified by analysis by high performance liquid chromatography (HPLC). Conductivity detector (CDD) and UV-Vis detector (measurement wavelength: 210 nm) are used for HPLC analysis of 3-hydroxyadipic acid-3,6-lactone and ⁇ -hydromuconic acid, respectively.
• the concentration of the present composition in the aqueous solution of the 3-hydroxyadipic acid-3,6-lactone composition prepared for HPLC analysis is suitably 1 to 10 g/L from the viewpoint of detection sensitivity.
• the 3-hydroxyadipic acid-3,6-lactone composition contains water, alcohol, carboxylic acid, ether, ester, It may contain ions.
• alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and the like.
• 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, ⁇ -ketoglutarate.
• ethers include dimethyl ether, diethyl ether, 1,2-dimethoxyethane, diglyme, tetrahydrofuran, dioxane and the like.
• esters include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, ⁇ -butyrolactone and the like.
• ions include H + , Li + , Na + , K + , NH 4 + , Mg 2+ , Ca 2+ , Fe 2+ , Fe 3+ , Zn 2+ , Ni 2+ , Mn 2+ , OH ⁇ , Cl ⁇ , NO 3 ⁇ , SO 4 2 ⁇ , PO 4 3 ⁇ , CO 3 2 ⁇ and the like.
• the 3-hydroxyadipic acid-3,6-lactone composition of the present invention the sum of the contents of 3-hydroxyadipic acid-3,6-lactone (main component) and ⁇ -hydromuconic acid (secondary component) and 100 weight
• the % difference is understood to be made up of the third component above.
• 75% by weight of 3-hydroxyadipic acid-3,6-lactone and 10% by weight of ⁇ -hydromuconic acid 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone and 13% by weight of ⁇ -hydromuconic acid.
• 3 parts by weight) and 15% by weight of water is included in the 3-hydroxyadipic acid-3,6-lactone composition of the present invention.
• the third component may be of one type or a plurality of types, but when it is included, water is preferable.
• water is included as the third component of the 3-hydroxyadipic acid-3,6-lactone composition
• the water content in the composition is specifically It is preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably 25% by weight or less, and particularly preferably 20% by weight or less, based on 100% by weight.
• Adipic acid can be produced by reacting (hydrogenating) the 3-hydroxyadipic acid-3,6-lactone composition of the present invention with hydrogen in the presence of a hydrogenation catalyst.
• the hydrogenation catalyst preferably contains a transition metal element, specifically selected from the group consisting of palladium, platinum, ruthenium, rhodium, rhenium, nickel, cobalt, iron, iridium, osmium, copper and chromium. It preferably contains one or more, more preferably one or more selected from the group consisting of palladium, platinum, nickel, cobalt, iron, copper and chromium.
• the hydrogenation catalyst is preferably supported on a carrier from the viewpoints of saving the amount of metal used and increasing the active surface of the catalyst.
• Supporting of the hydrogenation catalyst on the carrier can be carried out by known methods such as an impregnation method, a deposition precipitation method, and a vapor phase support method.
• carriers include carbon, polymers, metal oxides, metal sulfides, zeolites, clays, heteropolyacids, solid phosphoric acid, hydroxyapatite, and the like.
• the hydrogen to be reacted with the 3-hydroxyadipic acid-3,6-lactone composition may be added all at once or sequentially to the reactor.
• the partial pressure of hydrogen is not particularly limited, but if it is too low, the reaction time will be long, and if the partial pressure of hydrogen is too high, it is undesirable from the standpoint of equipment safety. More preferably 0.3 MPa or more and 5 MPa or less (gauge pressure), more preferably 0.5 MPa or more and 3 MPa or less (gauge pressure).
• the reaction format may be a reaction format using any of a batch type tank reactor, a semi-batch type tank reactor, a continuous tank reactor, a continuous tubular reactor, and a trickle bed tubular reactor.
• a solid hydrogenation catalyst When a solid hydrogenation catalyst is used, the reaction can be carried out in any of suspended bed, fixed bed, moving bed and fluidized bed systems.
• the reaction temperature for hydrogenation is not particularly limited, but if it is too low, the reaction rate will slow down, and if the reaction temperature is too high, energy consumption will increase, which is not preferable. From such a viewpoint, the reaction temperature is preferably 100 to 350°C, more preferably 120 to 300°C, even more preferably 130 to 280°C, and further preferably 140 to 250°C. It is preferably 150 to 230°C, more preferably 160 to 220°C.
• an inert gas such as nitrogen, helium, or argon may coexist. It is preferably vol% or less.
• the amount of ammonia with respect to the 3-hydroxyadipic acid-3,6-lactone composition should be 5% by weight or less. It is preferably 3% by weight or less, more preferably 0% by weight (that is, reaction in the absence of ammonia).
• the hydrogenation of the 3-hydroxyadipic acid-3,6-lactone composition is preferably carried out in the presence of a solvent.
• Solvents for hydrogenation include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentane, hexane, cyclohexane, heptane, octane, decane, dimethyl ether, diethyl ether, 1,2-dimethoxy Ethane, diglyme, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, ⁇ -butyrolactone, N-methylpyrrolidone, dimethylsulfoxide, aqueous solvents and the like can be used, and two or more of these can be used.
• a mixed solvent may be used, but it is preferable to use an aqueous solvent from the viewpoint of economy and environment.
• aqueous solvent means water or a mixed solvent in which a water-miscible organic solvent is mixed with water as the main component.
• Constaining mainly water means that the ratio of water in the mixed solvent is more than 50% by volume, preferably 70% by volume or more, more preferably 90% by volume or more.
• Water-miscible organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1,2-dimethoxyethane, diglyme, tetrahydrofuran, dioxane, ⁇ -butyrolactone, N-methylpyrrolidone. , dimethylsulfoxide, dimethylformamide, dimethylacetamide, acetone and the like.
• the pH of the aqueous solvent is not particularly limited, it is preferably pH 2 to 13, more preferably pH 3 to 11, considering the suppression of catalyst deterioration, the suppression of by-product formation, the corrosiveness to the reactor, etc.
• a pH of 4 to 10 is more preferred.
• the amount of the 3-hydroxyadipic acid-3,6-lactone composition to be charged to the solvent is not particularly limited, a small amount to be charged is not industrially preferable. From this point of view, the amount of the 3-hydroxyadipic acid-3,6-lactone composition to be charged with respect to 100 parts by weight of the solvent is 0.1 part by weight or more as an equivalent amount of 3-hydroxyadipic acid-3,6-lactone. It is preferably 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.
• adipic acid When a solvent other than a primary alcohol and a secondary alcohol is used as a hydrogenation solvent, the corresponding adipic acid is obtained from the carboxylic acid, carboxylic acid salt, and carboxylic acid ester of the 3-hydroxyadipic acid-3,6-lactone composition. , adipate, and adipate are produced.
• a solvent containing a primary or secondary alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, or isobutanol is used as the hydrogenation solvent
• adipic acid, adipic acid salt, adipic acid A mixture of monoesters and adipic acid diesters is obtained.
• carboxylic acids, carboxylates, carboxylic acid esters and mixtures thereof of adipic acid are collectively referred to as "adipic acid".
• the carboxylic acid of adipic acid obtained in the present invention can be further converted to an adipic acid ester by subjecting it to an esterification reaction.
• the method of esterification is not particularly limited, and examples thereof include dehydration condensation of carboxylic acid and alcohol using an acid catalyst or condensing agent, and methods using alkylating reagents such as diazomethane and alkyl halides.
• the adipic acid obtained in the present invention can be separated and purified by ordinary unit operations such as centrifugation, filtration, membrane filtration, distillation, extraction, crystallization and drying.
• Adiponitrile can be produced from the adipic acid obtained in the present invention by a known method (eg, JP-B-61-24555). Hexamethylenediamine can be produced by hydrogenating the obtained adiponitrile by a known method (for example, JP-T-2000-508305).
• Adipic acid obtained in the present invention is polycondensed with diamine by a known method (see, for example, Osamu Fukumoto, "Polyamide Resin Handbook” Nikkan Kogyo Publishing Co., Ltd. (January 1998)) to produce a polyamide.
• a known method see, for example, Osamu Fukumoto, "Polyamide Resin Handbook” Nikkan Kogyo Publishing Co., Ltd. (January 1998)
• polyamide 46, polyamide 56, and polyamide 66 can be produced, respectively.
• a polyamide fiber can be produced by processing polyamide by a known method (eg, International Publication No. 2019/208427).
• the polyamide fiber thus obtained can be used for clothing such as innerwear, sportswear and casual wear, and for industrial materials such as airbags and tire cords.
• a polyamide molded article can be produced by molding a polyamide by a known method (for example, International Publication No. 2021/006257).
• the polyamide molded article thus obtained can be used for automobile parts, electric parts, electronic parts, construction members, various containers, daily necessities, household goods, sanitary goods and the like.
• Adipic acid obtained in the present invention is polycondensed with glycols by a known method (see, for example, "Paint Research, vol.151, p2-8" Kansai Paint Co., Ltd. (November 2009)).
• polyester can be produced.
• glycols ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2- Methyl-1,3-propanediol and the like can be used.
• any dicarboxylic acid may be copolymerized.
• dicarboxylic acids to be copolymerized include oxalic acid, malonic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 2, 5-Furandicarboxylic acid and the like can be exemplified.
• Polybutylene adipate terephthalate (PBAT) and polybutylene succinate adipate (PBSA) can be obtained by using 1,4-butanediol as the diol and terephthalic acid or succinic acid as the dicarboxylic acid. is biodegradable, it is preferable from an environmental point of view.
• Polybutylene adipate terephthalate (PBAT) and polybutylene succinate adipate (PBSA) are prepared by known methods (for example, Journal of Polymer Science: Part A: Polymer Chemistry, vol.40, p4141-4157 (2002) and International Publication 1996/ 019521).
• the term "biodegradability" refers to the property of being decomposed down to the molecular level by the action of microorganisms, and finally becoming carbon dioxide and water, which circulates in the natural world.
• a polyester fiber can be produced by processing polyester by a known method (eg, International Publication No. 2007/037174).
• the polyester fibers thus obtained can be made into textile products such as woven fabrics, knitted fabrics and non-woven fabrics, as well as clothing, fiber brushes, rugs and the like using them.
• a polyester molded product can be produced by molding polyester by a known method (eg, International Publication No. 2015/072216).
• the polyester molded article thus obtained can be used for automobile parts, electric parts, electronic parts, mechanical parts, construction parts, various containers, daily necessities, household goods, sanitary goods and the like.
• a polyester film can be produced by stretching polyester by a known method (for example, International Publication No. 2010/038655).
• the polyester film thus obtained can be used in a wide variety of applications such as electronic equipment, semiconductor products, electric products, automobile parts, packaging applications and building materials.
• Product selectivity (%) product production amount (mol)/reacted starting material (mol) x 100.
• HPLC analysis condition 1 HPLC device: "Prominence” (manufactured by Shimadzu Corporation) Column: “Synergi Polar-RP” (manufactured by Phenomenex), length 250 mm, inner diameter 4.60 mm, particle size 4 ⁇ m + “Synergi hydro-RP” (manufactured by Phenomenex), length 250 mm, inner diameter 4.60 mm, particle size 4 ⁇ m
• Reaction solution: 5 mM formic acid + 20 mM Bis-Tris + 0.1 mM EDTA/2Na aqueous solution/acetonitrile 98/2 (volume ratio)
• pH analysis method A Horiba pH meter F-52 (manufactured by Horiba, Ltd.) was used. pH calibration is pH 4.01 standard solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), pH 6.86 standard solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), pH 9.18 standard solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used.
• Example 1 By physically mixing 0.92 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.08 g of ⁇ -hydromuconic acid (carboxylic acid) prepared in Reference Example 2, 3 A 3-hydroxyadipic acid-3,6-lactone composition containing 8.7 parts by weight of ⁇ -hydromuconic acid per 100 parts by weight of 3,6-hydroxyadipic acid-lactone was obtained.
• Example 2 By physically mixing 0.8 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.2 g of ⁇ -hydromuconic acid (carboxylic acid) prepared in Reference Example 2, 3 - A 3-hydroxyadipic acid-3,6-lactone composition containing 25 parts by weight of ⁇ -hydromuconic acid per 100 parts by weight of hydroxyadipic acid-3,6-lactone was obtained and reacted in the same manner as in Example 1. did Table 1 shows the results.
• Example 3 3 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was added to an eggplant flask, heated to 165°C in an oil bath, maintained at 165°C for 30 minutes, and allowed to cool to room temperature. chilled. An aqueous solution obtained by adding 300 mL of water into an eggplant flask was analyzed by HPLC. The content of ⁇ -hydromuconic acid in the aqueous solution was 5.9 parts by weight with respect to 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone. A reaction was carried out in the same manner as in Example 1 using 1 g of the 3-hydroxyadipic acid-3,6-lactone composition obtained by removing water with a rotary evaporator. Table 1 shows the results.
• Example 4 3 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was added to an eggplant flask, heated to 190°C in an oil bath, maintained at 190°C for 30 minutes, and allowed to cool to room temperature. chilled. An aqueous solution obtained by adding 300 mL of water into an eggplant flask was analyzed by HPLC. The content of ⁇ -hydromuconic acid in the aqueous solution was 11 parts by weight with respect to 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone. A reaction was carried out in the same manner as in Example 1 using 1 g of the 3-hydroxyadipic acid-3,6-lactone composition obtained by removing water with a rotary evaporator. Table 2 shows the results.
• Example 5 By physically mixing 0.9 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 and 0.1 g of ⁇ -hydromuconic acid (carboxylic acid) prepared in Reference Example 2, 3 A 3-hydroxyadipic acid-3,6-lactone composition containing 11.1 parts by weight of ⁇ -hydromuconic acid per 100 parts by weight of hydroxyadipic acid-3,6-lactone was obtained, and 5% palladium was used as a catalyst.
• the reaction was carried out in the same manner as in Example 1 except that 0.005 g of /carbon (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used and the reaction temperature was changed to 160°C. Table 2 shows the results.
• Example 6 A reaction was carried out in the same manner as in Example 1, except that tetrahydrofuran (THF) was used as the solvent instead of water. Table 2 shows the results.
• Example 7 A reaction was carried out in the same manner as in Example 1, except that a mixed solvent of water and tetrahydrofuran (water/THF 6/4 v/v) was used instead of water. Table 2 shows the results.
• Example 8 20 g of 3-hydroxyadipic acid-3,6-lactone (carboxylic acid) prepared in Reference Example 1 was added to an eggplant flask, heated to 200°C in an oil bath, maintained at 200°C for 30 minutes, and allowed to cool to room temperature. After cooling, a 3-hydroxyadipic acid-3,6-lactone composition containing 8.6 parts by weight of ⁇ -hydromuconic acid per 100 parts by weight of 3-hydroxyadipic acid-3,6-lactone was obtained.
• Example 9 The reaction was carried out in the same manner as in Example 1, except that 0.05 g of Raney nickel (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as a catalyst. Table 2 shows the results.

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