Method for producing 1, 6-hexanediol composition, 1, 6-hexanediol composition, and polymer

Abstract

The purpose of the present invention is to provide an environmentally-friendly production method for a biomass resource-derived 1, 6-hexanediol composition having excellent reactivity, a 1, 6-hexanediol composition having excellent reactivity obtained by the production method, and a polymer having excellent reactivity obtained by reacting the 1, 6-hexanediol composition. A method for producing a 1, 6-hexanediol composition according to the present invention comprises: a step (1) for producing a 1, 6-hexanediol composition from 6-hydroxyhexanoic acid and / or a derivative thereof obtained from a raw material derived from a biomass resource; and a step (2) for purifying the 1, 6-hexanediol composition obtained in step (1) by ion exchange and / or distillation.

Description

Technical Field

[0001] The present invention relates to a method for producing a 1,6-hexanediol composition, a 1,6-hexanediol composition, and a polymer. Background Art

[0002] 1,6-Hexanediol (1,6-HD) compositions are useful intermediates for the production of polymers such as polyesters and polyurethanes. Conventionally, 1,6-Hexanediol compositions are produced by esterifying a carboxylic acid mixture containing adipic acid, 6-hydroxycaproic acid, and glutaric acid, generated by oxidizing cyclohexane, a petrochemical, followed by hydrogenation and purification by distillation.

[0003] Meanwhile, with increasing environmental awareness in recent years, there is a desire for raw materials derived from biomass resources, rather than petroleum-derived raw materials that contribute to global warming. Regarding 1,6-hexanediol, attempts have been made to produce biomass-derived 1,6-hexanediol compositions from biomass-derived raw materials using microorganisms, but no commercially available products exist. For example, Patent Documents 1 and 2 disclose methods for producing 1,6-hexanediol compositions using enzymes, including information on enzyme genes and a production method based on metabolic pathway purification.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-114227

[0007] Patent Document 2: Japanese Patent No. 6680671 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, while Patent Documents 1 and 2 disclose environmentally friendly methods for producing 1,6-hexanediol compositions derived from biomass resources, they do not disclose impurities contained in the 1,6-hexanediol compositions, nor do they address the reactivity of polymers such as polyesters and polyurethanes obtained using the 1,6-hexanediol. The present inventors produced a 1,6-hexanediol composition according to Japanese Patent No. 6680671 and then purified it using known methods. When this 1,6-hexanediol composition was used to produce polyesters and polyurethanes, they observed a decrease in reactivity and a reduction in physical properties such as tensile strength and elongation, which were not observed in conventional petroleum-derived 1,6-hexanediol compositions. Detailed research by the present inventors has revealed that this phenomenon is observed when the raw materials for the biomass-derived 1,6-hexanediol composition, such as glucose, contain high levels of compounds having two or more secondary hydroxyl groups per molecule, as well as 6-hydroxyhexanal and / or its derivatives.

[0010] The present invention aims to solve the above-mentioned problems and provide an environmentally friendly method for producing a highly reactive 1,6-hexanediol composition derived from biomass resources, a highly reactive 1,6-hexanediol composition obtained by the production method, and a highly reactive polymer such as a polyester or polyurethane obtained by reacting the 1,6-hexanediol composition.

[0011] Means for solving problems

[0012] The present inventors conducted intensive research and found that the reactivity of a 1,6-hexanediol composition derived from biomass resources can be improved by controlling the content of a compound having two or more secondary hydroxyl groups per molecule, 6-hydroxyhexanal, and / or its derivatives to a specific amount or less. This led to the completion of the present invention.

[0013] That is, the present invention provides the following inventions.

[0014] [1] A method for producing a 1,6-hexanediol composition, comprising: a step (1) of producing the 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from a biomass resource; and a step (2) of purifying the 1,6-hexanediol composition obtained in the step (1) by ion exchange and / or distillation, wherein the 1,6-hexanediol composition contains: one or both of 1,6-hexanediol and a 1,6-hexanediol derivative, a compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and / or its derivatives (B), wherein the content of the compound (A) having two or more secondary hydroxyl groups in one molecule is 100 ppm by mass or less relative to the total amount of the 1,6-hexanediol composition, and the total content of 6-hydroxyhexanal and / or its derivatives (B) is 1500 ppm by mass or less relative to the total amount of the 1,6-hexanediol composition.

[0015] [2] The method for producing a 1,6-hexanediol composition according to [1], wherein the step (1) is a step of producing the 1,6-hexanediol composition at 70° C. or lower.

[0016] [3] The method for producing a 1,6-hexanediol composition according to [1], wherein the step (1) is a step of producing the 1,6-hexanediol composition at 50° C. or lower.

[0017] [4] The method for producing a 1,6-hexanediol composition according to any one of [1] to [3], wherein the step (1) is a step of producing the 1,6-hexanediol composition using a microorganism.

[0018] [5] A 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition according to any one of [1] to [4], comprising: one or both of 1,6-hexanediol and a 1,6-hexanediol derivative; a compound (A) having two or more secondary hydroxyl groups in one molecule; and 6-hydroxyhexanal and / or its derivative (B), wherein the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule is 100 ppm by mass or less relative to the total amount of the 1,6-hexanediol composition, and the total content of 6-hydroxyhexanal and / or its derivative (B) is 1500 ppm by mass or less relative to the total amount of the 1,6-hexanediol composition.

[0019] [6] A polymer comprising the 1,6-hexanediol composition of [5] as a reaction raw material.

[0020] [7] The polymer according to [6], wherein the polymer is polyester or polyurethane.

[0021] Effects of the Invention

[0022] The method for producing a 1,6-hexanediol composition of the present invention is environmentally friendly, as it produces the 1,6-hexanediol composition from raw materials derived from biomass resources. This method can reduce carbon dioxide emissions and other environmentally friendly measures. Furthermore, the 1,6-hexanediol composition of the present invention has excellent reactivity because the total content of compounds (A) having two or more secondary hydroxyl groups per molecule is 100 ppm by mass or less, and the total content of 6-hydroxyhexanal and / or its derivatives (B) is 1500 ppm by mass or less. Therefore, the method for producing a 1,6-hexanediol composition of the present invention can produce a 1,6-hexanediol composition with excellent reactivity while being environmentally friendly.

[0023] The polymer (polyester, etc.) of the present invention obtained by reacting the 1,6-hexanediol composition of the present invention also has excellent reactivity. Furthermore, the polyurethane of the present invention has excellent tensile strength and elongation. DETAILED DESCRIPTION

[0024] First, the 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition of the present invention (also referred to as the 1,6-hexanediol composition of the present invention) will be described.

[0025] <1,6-Hexanediol Composition>

[0026] The 1,6-hexanediol composition of the present invention (sometimes simply referred to as the "composition") comprises one or both of 1,6-hexanediol and a 1,6-hexanediol derivative; a compound (A) having two or more secondary hydroxyl groups per molecule; and 6-hydroxyhexanal and / or its derivative (B). In this specification, a secondary hydroxyl group refers to a hydroxyl group whose carbon atom to which the hydroxyl group is bonded is a secondary carbon atom.

[0027] In this specification, the compound (A) having two or more secondary hydroxyl groups in one molecule may be simply referred to as "component (A)", and the same applies to component (B).

[0028] <<1,6-Hexanediol, 1,6-Hexanediol derivatives>>

[0029] The 1,6-hexanediol contained in the composition of the present invention is preferably unmodified 1,6-hexanediol, but may be a 1,6-hexanediol derivative. That is, the composition of the present invention contains at least one of 1,6-hexanediol and a 1,6-hexanediol derivative.

[0030] The 1,6-hexanediol derivative contained in the composition of the present invention is a compound obtained by modifying one or both of the two hydroxyl groups present in the 1,6-hexanediol contained in the 1,6-hexanediol composition of the present invention. The hydroxyl groups present in 1,6-hexanediol can be modified by any known method, such as etherification, esterification, and modification with (meth)acrylic acid.

[0031] Examples of the 1,6-hexanediol derivatives include epoxy group-containing 1,6-hexanediol derivatives such as 1,6-hexanediol diglycidyl ether and 6-hydroxyhexyl glycidyl ether; (meth)acryloyl group-containing 1,6-hexanediol derivatives such as 1,6-hexanediol di(meth)acrylate, 6-hydroxyhexyl acrylate, and 1,6-hexanediol monoacrylate monomethacrylate; vinyl ether group-containing 1,6-hexanediol derivatives such as 1,6-hexanediol divinyl ether and 1,6-hexanediol monovinyl ether; aliphatic alkyl ether group-containing 1,6-hexanediol derivatives such as 6-propoxy-1-hexanol, 1,6-dipropoxy-hexane, 1,6-hexanediol methyl ether, and 1,6-dimethoxyhexane; and fatty acid ester group-containing 1,6-hexanediol derivatives such as 6-hydroxyhexanoate, di-n-propyl adipate, 6-hydroxyhexanoate methyl, and dimethyl adipate. These may be used alone or in combination of two or more.

[0032] In this specification, a (meth)acryloyl group refers to one or both of an acryloyl group and a methacryloyl group, and a (meth)acrylate group refers to one or both of an acrylate group and a methacrylate group.

[0033] In the composition of the present invention, the total content of one or both of 1,6-hexanediol and the 1,6-hexanediol derivative is preferably 96.00 to 99.99% by mass, more preferably 98.00 to 99.99% by mass, and even more preferably 99.50 to 99.99% by mass, relative to the total amount of the composition. By setting the total content of component (A) and the total content of component (B) within the above ranges and the purity of the 1,6-hexanediol composition within the above ranges, the effects of the present invention tend to be more preferably achieved.

[0034] In this specification, the total content of one or both of 1,6-hexanediol and a 1,6-hexanediol derivative is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0035] <<(A) Ingredient>>

[0036] Component (A) is not particularly limited as long as it is a compound having two or more secondary hydroxyl groups per molecule. Examples include aliphatic polyols represented by 2,3-butanediol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, and heptyl alcohol; alicyclic polyols represented by 1,2-cyclohexanediol, 1,4-cyclohexanediol, glucose, fructose, inositol, and quercetin; and oligomers formed by dehydration condensation of any combination of these compounds. These compounds may be present singly or in combination. Of these, 1,4-cyclohexanediol and glucose are preferred because they have a significant impact on the reactivity of the 1,6-hexanediol composition and the reactivity of polymers such as polyesters obtained by reacting the 1,6-hexanediol composition.

[0037] The total content of the compound (A) having two or more secondary hydroxyl groups per molecule (preferably the total content of either or both 1,4-cyclohexanediol and glucose) relative to the total amount of the 1,6-hexanediol composition of the present invention is 100 ppm by mass or less, preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, and particularly preferably 0 ppm by mass (not included). This tends to result in good reactivity of the composition of the present invention, good reactivity of polymers (such as polyesters) using the composition of the present invention as a reaction raw material, and good film properties (tensile strength and elongation) of the polyurethane.

[0038] In this specification, the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0039] <<(B)Ingredient>>

[0040] The component (B) is not particularly limited as long as it is one or both of 6-hydroxyhexanal and a derivative of 6-hydroxyhexanal.

[0041] The derivatives of 6-hydroxyhexanal are not particularly limited as long as they are derivatives of 6-hydroxyhexanal (a compound represented by the following formula (1)). Examples thereof include cyclized products, aldol condensation products, glycerol reaction products, and hexanediol (HDO) reaction products. Specific examples include compounds represented by the following formulas (2) to (7). These may be used alone or in combination of two or more.

[0042] [Chemical Formula 1]

[0043]

[0044] The component (B) may be 6-hydroxyhexanal, since it has a significant influence on the reactivity of the 1,6-hexanediol composition and the reactivity of a polymer such as a polyester obtained by reacting the 1,6-hexanediol composition.

[0045] The total content of 6-hydroxyhexanal and / or its derivatives (B) (preferably the content of 6-hydroxyhexanal) relative to the total amount of the 1,6-hexanediol composition of the present invention is 1500 mass ppm or less, preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, even more preferably 200 mass ppm or less, and particularly preferably 0 mass ppm (not included). This tends to result in good reactivity of the composition of the present invention, good reactivity of polymers (such as polyesters) using the composition as a reaction raw material, and good tensile strength and elongation of polyurethanes. Furthermore, coloration and odor of the composition and polymers using the composition as a reaction raw material can be reduced.

[0046] In this specification, the total content of 6-hydroxyhexanal and / or its derivative (B) is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0047] As described above, by keeping the contents of components (A) and (B) within the above ranges, the composition of the present invention exhibits excellent reactivity. Furthermore, polymers such as polyesters, which are produced using the composition of the present invention as a reaction raw material, also exhibit excellent reactivity. The reason for these effects is not yet clear, but is presumed as follows.

[0048] Secondary hydroxyl groups have low reactivity. Therefore, if the composition of the present invention contains a large amount of component (A), polymers such as polyesters produced using the composition of the present invention as a reaction raw material often have secondary hydroxyl groups at their terminals, thereby reducing the reactivity of the polyesters. Furthermore, if the composition of the present invention contains a large amount of component (B), chain interruption or branching may occur during a polymerization reaction using the composition of the present invention as a reaction raw material.

[0049] Therefore, it is presumed that by setting the total content of the (A) component to a specific amount or less and the total content of the (B) component to a specific amount or less, the reactivity of the 1,6-hexanediol composition and the reactivity of a polymer such as polyester obtained by reacting the 1,6-hexanediol composition are excellent.

[0050] Furthermore, polyurethanes produced using the composition of the present invention as a reaction raw material exhibit excellent tensile strength and elongation. This is because the production of polyols with secondary hydroxyl groups at the end is suppressed to a low level during the synthesis of polyols (a reaction raw material for polyurethanes) from the composition of the present invention. Therefore, it is speculated that this is because the molecular weight does not decrease during polyurethane formation, and the number of hydroxyl groups at the polyester ends increases, causing branching during polyurethane formation and reducing the cohesive strength of the polyurethane.

[0051] <<Alkali Metal Elements>>

[0052] The 1,6-hexanediol composition of the present invention preferably further contains an alkali metal element.

[0053] Generally, when polyester is heated in the presence of water, the catalyst residue from the dehydration condensation reaction coordinates and bonds with the ester bonds of the polyester, causing ester hydrolysis. However, the alkali metal element inhibits the coordination of the catalyst residue with the ester bonds of the polyester. This effectively suppresses the hydrolysis of the polyester and the polyurethane having ester bonds, resulting in excellent hydrolysis resistance.

[0054] On the other hand, if the composition contains a large amount of alkali metal elements, there is a risk that the alkali metal elements may coordinate with the catalyst during the synthesis of polymers such as polyesters, thereby reducing the catalyst's original function, namely, its function of increasing the polymerization reaction rate. Therefore, by containing only a specific amount of alkali metal elements in the 1,6-hexanediol composition of the present invention, it is possible to suppress excessive reduction in the catalyst's original function due to the alkali metal, thereby preventing adverse effects during the synthesis of polymers such as polyesters and polyurethanes.

[0055] Therefore, the 1,6-hexanediol composition of the present invention further contains an alkali metal element. If the alkali metal element is present in a specific amount, it can impart excellent hydrolysis resistance to the polymer. Furthermore, when the 1,6-hexanediol composition of the present invention is used as a reaction raw material to synthesize polymers such as polyesters and polyurethanes, there is no adverse effect, and the polymers (e.g., polyesters and polyurethanes having ester bonds) obtained by reacting the 1,6-hexanediol composition have excellent hydrolysis resistance.

[0056] Therefore, specifically, the total content of the alkali metal elements is preferably 0.1 to 1000 ppm by mass relative to the total amount of the 1,6-hexanediol composition of the present invention.

[0057] The alkali metal element is not particularly limited, and examples thereof include lithium, sodium, potassium, rubidium, and cesium. These may be used alone or in combination of two or more. Among these, sodium and potassium are preferred.

[0058] The presence state of the alkali metal element contained in the composition of the present invention is not particularly limited, and may be a simple alkali metal, an alkali metal compound, an alkali metal ion, or the like.

[0059] Specific examples of the alkali metal compound include metal salts of the above-mentioned alkali metal elements with acids such as acetic acid, phosphoric acid, and nitric acid.

[0060] The total content of alkali metal elements (preferably the total content of either or both sodium and potassium metal elements) relative to the total amount of the 1,6-hexanediol composition of the present invention is 0.1 to 1000 ppm by mass, preferably 0.1 to 800 ppm by mass, and more preferably 0.1 to 600 ppm by mass. A total alkali metal content of 0.1 ppm by mass or greater can achieve improved reactivity, hydrolysis resistance, and tensile strength and elongation. A total alkali metal content of 1000 ppm by mass or less tends to achieve improved reactivity when synthesizing polymers, such as polyesters or polyurethanes, using the 1,6-hexanediol composition as a raw material.

[0061] In this specification, the total content of alkali metals is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0062] <<Glycerin>>

[0063] The 1,6-hexanediol composition of the present invention may further contain glycerol. The glycerol content relative to the total amount of the composition is preferably 2000 ppm by mass or less, more preferably 1500 ppm by mass or less, even more preferably 1000 ppm by mass or less, particularly preferably 500 ppm by mass or less, and most preferably 0 ppm by mass (not included). When the glycerol content is 2000 ppm by mass or less, when the 1,6-hexanediol composition is reacted to synthesize a polymer such as polyester, excessive incorporation of glycerol into the polymer can be suppressed. Consequently, the formation of branching and gelation of the polyester can be more effectively suppressed, and better reactivity tends to be achieved.

[0064] In this specification, the glycerol content is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0065] The 1,6-hexanediol composition of the present invention may be produced so that the total content of the component (A) and the total content of the component (B) fall within the above-mentioned range.

[0066] When the alkali metal content of the 1,6-hexanediol composition of the present invention is low, for example, an acid such as acetic acid, phosphoric acid, or nitric acid and an alkali metal salt may be added to adjust the total alkali metal content to be within the above range.

[0067] <Method for producing 1,6-hexanediol composition>

[0068] Specifically, the 1,6-hexanediol composition of the present invention (1,6-hexanediol composition derived from biomass resources) obtained by the following environmentally friendly production method (production method of the 1,6-hexanediol composition of the present invention) can be preferably used.

[0069] The method for producing the 1,6-hexanediol composition of the present invention will be described.

[0070] The method for producing a 1,6-hexanediol composition of the present invention comprises: a step (1) of producing the 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from a biomass resource; and a step (2) of purifying the 1,6-hexanediol composition obtained in the step (1) by ion exchange and / or distillation.

[0071] <<Process (1)>>

[0072] Step (1) is a step of producing a 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from a biomass resource. Here, the production of a 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from a biomass resource means that the 1,6-hexanediol composition is produced from the raw material derived from a biomass resource via 6-hydroxyhexanoic acid and / or its derivatives. The term "via 6-hydroxyhexanoic acid and / or its derivatives" may refer to any process that involves converting the raw material derived from a biomass resource via 6-hydroxyhexanoic acid and / or its derivatives into a 1,6-hexanediol composition within the cells of a microorganism. Alternatively, the process may be a process in which 6-hydroxyhexanoic acid and / or its derivatives are produced from a raw material derived from a biomass resource using a microorganism, and a culture solution containing the compound is directly used to convert the compound into a 1,6-hexanediol composition using the microorganism. Alternatively, the process may be a process in which the culture solution is purified and the compound is converted into a 1,6-hexanediol composition using the microorganism in a different reaction tank.

[0073] Derivatives of 6-hydroxyhexanoic acid are not particularly limited as long as they are derivatives of 6-hydroxyhexanoic acid. Examples thereof include ester compounds such as 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxyhexanoic acid, cyclized products of 6-hydroxyhexanoic acid, condensates of 6-hydroxyhexanoic acids, and condensates of 6-hydroxyhexanoic acid and 1,6-hexanediol. These may be used alone or in combination of two or more. Among them, 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxyhexanoic acid, is preferred.

[0074] In this specification, CoA means coenzyme A.

[0075] Among the above-mentioned 6-hydroxyhexanoic acid and / or its derivatives, 6-hydroxyhexanoic acid and 6-hydroxy-hexanoyl-CoA are preferred, and 6-hydroxyhexanoic acid is more preferred.

[0076] The above-mentioned step (1) is preferably a step of producing a 1,6-hexanediol composition at a temperature of 70°C or lower, and more preferably a step of producing a 1,6-hexanediol composition at a temperature of 50°C or lower. The lower limit of the temperature is not particularly limited, but is preferably 20°C or higher. By carrying out production at a lower temperature, the amount of carbon dioxide emitted during production can be reduced, and side reactions such as cyclization associated with dehydration can be reduced, thereby suppressing the formation of by-products such as cyclic oligomers. As a result, fogging, which is a problem in automotive interior materials, can also be suppressed. In addition, the stacking hindrance factor of the polymer chain is reduced, which can improve the physical properties of the film.

[0077] The above step (1) can be carried out, for example, using a microorganism capable of producing (biosynthesizing) 1,6-hexanediol. Examples of microorganisms capable of producing 1,6-hexanediol include those described in Japanese Patent Application Publication No. 2020-114227 and Japanese Patent Publication No. 6680671. These can be used alone or in combination of two or more. A person skilled in the art can easily produce or obtain a microorganism capable of producing 1,6-hexanediol based on known techniques such as those in the above publications.

[0078] Through the metabolic pathway within the microorganism, 3-oxopropionate and 3-hydroxypropionaldehyde are produced.

[0079] An example of 3-hydroxypropionaldehyde production in microorganisms will be described. As described in Figure 1 of Japanese Patent No. 6680671 and other publications, 3-phosphoglyceraldehyde is produced from sugars (pentoses and hexoses) via metabolic pathways of the glycolytic system, such as the pentose phosphate pathway (PP pathway), within microorganisms. Similarly, 3-phosphoglyceraldehyde is produced from glycerol via metabolic pathways within microorganisms. Subsequently, 3-hydroxypropionaldehyde is produced from 3-phosphoglyceraldehyde via reactions catalyzed by various enzymes possessed by the microorganisms. Alternatively, 3-hydroxypropionaldehyde is produced from glycerol via a single reaction using diol dehydratase and / or glycerol dehydratase.

[0080] An example of 3-oxopropionate production in microorganisms will be described. As described in Figure 1 of Japanese Patent No. 6680671, 3-phosphoglycerate and 2-phosphoglycerate are produced from sugars (pentoses and hexoses) in microorganisms via metabolic pathways of the glycolytic system, such as the Emden-Mayerhof pathway (EM pathway). Glycerate is produced from 3-phosphoglycerate and 2-phosphoglycerate using enzymes described in Table 1 of Japanese Patent No. 6680671, or by the reverse reaction of glycerate kinase. 3-oxopropionate is produced from glycerate using diol dehydratase and / or glycerol dehydratase. Furthermore, 3-oxopropionate can be produced from oxaloacetate, a metabolic intermediate in the TCA cycle, in a single reaction using ketoacid decarboxylase. Oxaloacetate can also be produced from sugars without going through the TCA cycle using phosphoenolpyruvate carboxylase or pyruvate carboxylase.

[0081] For example, 1,6-hexanediol is produced from 3-oxopropionic acid ester and 3-hydroxypropionaldehyde produced by metabolic pathways in microorganisms using various pathways shown in Figures 2 to 5 of Japanese Patent No. 6680671.

[0082] Preferable examples of microorganisms capable of producing 1,6-hexanediol from 3-oxopropionic acid ester and 3-hydroxypropionaldehyde, that is, microorganisms capable of producing 1,6-hexanediol include the following microorganisms.

[0083] A microorganism having genes encoding 10 enzymes of the 1,6-hexanediol pathway, the 10 enzymes comprising 4,6-dihydroxy-2-oxohexanoic acid aldolase (2A in the diagram of Japanese Patent No. 6680671), 4,6-dihydroxy-2-oxohexanoic acid 4-dehydratase (2B in the diagram of Japanese Patent No. 6680671), 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase (2C in the diagram of Japanese Patent No. 6680671), 6-hydroxy-2-oxohexanoic acid 2-reductase (2D in the diagram of Japanese Patent No. 6680671), 2,6-dihydroxy-hexanoic acid CoA-transferase ( 6,680,671), 2,6-dihydroxyhexanoyl-CoA2-dehydratase (2F in the figure of Japanese Patent No. 6,680,671), 6-hydroxy-2,3-dehydrohexanoyl-CoA2,3-reductase (2G in the figure of Japanese Patent No. 6,680,671), 6-hydroxyhexanoyl-CoA-transferase (4F3 in the figure of Japanese Patent No. 6,680,671), 6-hydroxyhexanoate 1-reductase (5R in the figure of Japanese Patent No. 6,680,671), and 6-hydroxyhexanal 1-reductase (5S in the figure of Japanese Patent No. 6,680,671).

[0084] The microorganism having genes encoding the 10 enzymes in the 1,6-hexanediol pathway is not particularly limited as long as it has genes encoding the 10 enzymes in the 1,6-hexanediol pathway, and examples thereof include prokaryotes and eukaryotes.

[0085] Furthermore, the microorganisms harboring genes encoding the ten enzymes of the 1,6-hexanediol pathway may be genetically modified microorganisms into which all and / or a portion of the ten genes (enzymes) encoding the ten enzymes of the 1,6-hexanediol pathway have been introduced. For example, if the microorganism to be used only possesses eight of the ten enzymes, genes encoding the remaining two enzymes can be introduced into the microorganism. Furthermore, if the microorganism to be used only possesses a portion of the ten enzymes, a single or multiple microorganisms harboring genes encoding the remaining enzymes may be used in combination.

[0086] Furthermore, the above-mentioned microorganism preferably has a gene encoding a diol dehydratase and / or a glycerol dehydratase.

[0087] Here, gene introduction can be performed by known methods.

[0088] Examples of prokaryotes include bacteria.

[0089] Examples of eukaryotic organisms include yeast and filamentous fungi.

[0090] Examples of the bacteria include bacteria belonging to the Enterobacteriaceae family, Corynebacterium-type bacteria, Bacillus bacteria, acetic acid bacteria, actinomycetes, and lactic acid bacteria.

[0091] Examples of bacteria belonging to the Enterobacteriaceae family include bacteria belonging to the genera Escherichia, Enterobacter, Pantoea, Klebsiella, Serratia, Erwinia, Photorhabdus, Providencia, Salmonella, and Morganella. Specifically, bacteria classified as Enterobacteriaceae according to the classification system used in the NCBI (National Center for Biotechnology Information) database (http: / / www.ncbi.nlm.nih.gov / Taxonomy / Browser / wwwtax.cgi?id=91347) can be used.

[0092] Escherichia bacteria are not particularly limited, and examples include bacteria classified as Escherichia according to the classification known to microbiologists. Examples of Escherichia bacteria include those described in Neidhardt et al. (Backmann, BJ 1996. Derivations and Genotypes of some mutant derivatives of Escherichia coli K-12, pp. 2460-2488. Table 1. In FD Neidhardt (ed.), Escherichia coli and Salmonella Cellular and Molecular Biology / Second Edition, American Society for Microbiology Press, Washington, DC). Examples of Escherichia bacteria include Escherichia coli. Examples of Escherichia coli include Escherichia coli K-12 strains such as W3110 strain (ATCC 27325) and MG1655 strain (ATCC 47076); Escherichia coli K5 strain (ATCC 23506); Escherichia coli B strains such as BL21 (DE3) strain; and derivative strains thereof.

[0093] Examples of Enterobacter bacteria include Enterobacter agglomerans and Enterobacter aerogenes. Examples of Pantoea bacteria include Pantoea ananatis, Pantoea stewartii, Pantoea agglomerans, and Pantoea citrea. Examples of Erwinia bacteria include Erwinia amylovora and Erwinia carotovora. Examples of Klebsiella bacteria include Klebsiella planticola.

[0094] Examples of the coryneform bacteria include bacteria belonging to the genus Corynebacterium, Brevibacterium, and Microbacterium.

[0095] Specific examples of coryneform bacteria include the following.

[0096] Corynebacterium acetoacidophilum

[0097] Corynebacterium acetoglutamicum

[0098] Corynebacterium alkanolyticum

[0099] Corynebacterium callunae

[0100] Corynebacterium crenatum

[0101] Corynebacterium glutamicum

[0102] Corynebacterium lilium

[0103] Corynebacterium melassecola

[0104] Corynebacterium thermoaminogenes (Corynebacterium efficiens)

[0105] Corynebacterium herculis

[0106] Brevibacterium divaricatum (Corynebacterium glutamicum)

[0107] Brevibacterium flavum (Corynebacterium glutamicum)

[0108] Brevibacterium immariophilum

[0109] Brevibacterium lactofermentum (Corynebacterium glutamicum)

[0110] Brevibacterium roseum

[0111] Brevibacterium saccharolyticum

[0112] Brevibacterium thiogenitalis

[0113] Corynebacterium ammoniagenes (Corynebacterium stationis)

[0114] Brevibacterium album

[0115] Brevibacterium cerinum

[0116] Microbacterium ammoniaphilum

[0117] Specific examples of coryneform bacteria include the following strains.

[0118] Corynebacterium acetoaceticum ATCC 13870

[0119] Corynebacterium acetoglutamicum ATCC 15806

[0120] Corynebacterium ATCC 21511

[0121] Corynebacterium sclerotiorum ATCC 15991

[0122] Corynebacterium scutellariae AS1.542

[0123] Corynebacterium glutamicum ATCC 13020, ATCC 13032, ATCC 13060, ATCC 13869, FERM BP-734

[0124] Corynebacterium lilii ATCC 15990

[0125] Corynebacterium molasses ATCC 17965

[0126] Effective Corynebacterium (Corynebacterium thermoammoniagenes) AJ12340 (FERM BP-1539)

[0127] Corynebacterium ligusticum ATCC 13868

[0128] Brevibacterium bifidum (Corynebacterium glutamicum) ATCC 14020

[0129] Brevibacterium flavum (Corynebacterium glutamicum) ATCC 13826, ATCC 14067, AJ12418 (FERM BP-2205)

[0130] Immature Brevibacterium ATCC 14068

[0131] Brevibacterium lactofermentum (Corynebacterium glutamicum) ATCC 13869

[0132] Brevibacterium roseum ATCC 13825

[0133] Brevibacterium saccharolyticum ATCC 14066

[0134] Brevibacterium thiogenes ATCC 19240

[0135] Corynebacterium ammoniagenes (Corynebacterium stagnantum) ATCC 6871, ATCC 6872

[0136] Brevibacterium albus ATCC 15111

[0137] Brevibacterium cereus ATCC 15112

[0138] Microbacterium ammoniaphilum ATCC 15354

[0139] It should be noted that bacteria in the genus Corynebacterium also include bacteria that were previously classified as Brevibacterium but are now collectively classified as Corynebacterium (Int. J. Syst. Bacteriol., 41, 255 (1991)). Furthermore, bacteria in the genus Corynebacterium also include bacteria that were previously classified as Corynebacterium ammoniagenes but were reclassified as Corynebacterium based on 16S rRNA base sequence analysis, etc. (Int. J. Syst. Evol. Microbiol., 60, 874-879 (2010)).

[0140] Examples of Bacillus bacteria include Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, Bacillus licheniformis, Bacillus megaterium, Bacillus brevis, Bacillus polymixa, and Bacillus stearothermophilus. Specific examples of Bacillus subtilis include Bacillus subtilis 168 Marburg strain (ATCC 6051) and Bacillus subtilis PY79 strain (Plasmid, 1984, 12, 1-9). Specific examples of Bacillus amyloliquefaciens include Bacillus amyloliquefaciens T strain (ATCC 23842) and Bacillus amyloliquefaciens N strain (ATCC 23845).

[0141] Examples of acetic acid bacteria include those belonging to the genera Gluconobacter, Acetobacter, Gluconacetobacter, Acidicaldus, Acidiphilium, Acidisphaera, Acidocella, Acidomonas, Asaia, Belnapia, Craurococcus, Granulibacter, and Kozakia. ), Leahibacter, Muricoccus, Neoasaia, Oleomonas, Paracraurococcus, Rhodopila, Roseococcus, Rubritepida, Saccharibacter, Stella, Swaminathania, Teicococcus, and Zavarzinia.

[0142] Specific examples of acetic acid bacteria include Gluconobacter oxydans, Acetobacter xylinum, Asidomonas methanolicus, Asaia bogorensis, Asaia krungthepensis, Belnapia moabensis, Gluconacetobacter xylinus, Granulibacter bethesdensis, Kozakia baliensis, and Oleomonas sagaranensis.

[0143] Examples of actinomycetes include bacteria belonging to the genera Actinomyces, Mycobacterium, Nocardia, Streptomyces, Actinoplanes, and Rhodococcus.

[0144] Specific examples of actinomycetes include Streptomyces coelicolor, Streptomyces griseus, Streptomyces avermitilis, and Rhodococcus zopfii.

[0145] Examples of lactic acid bacteria include bacteria belonging to the genera Lacticaseibacillus, Lactobacillus, Ligilactobacillus, Limosilactobacillus, Liquorilactobacillus, Lactiplantibacillus, Streptococcus, Lactococcus, and Enterococcus.

[0146] Specific examples of lactic acid bacteria include Lactobacillus casei, Lactobacillus gasseri, Lactobacillus acidophilus, Lactobacillus helveticus, Lactobacillus delbrueckii subsp. bulgaricus, Lactobacillus delbrueckii subsp. delbrueckii, Lactobacillus johnsonii, Ligilactobacillus salivarius, Limosilactobacillus fermentum, Liquorilactobacillus mali, Lactiplantibacillus plantarum, Streptococcus thermophilus, and Lactococcus lactis. subsp. lactis), Lactococcus lactissubsp. cremoris, Lactococcus plantarum, Lactococcus raffinolactis, Lactococcus cremoris, Enterococcus faecalis, Enterococcus faecium, etc.

[0147] Examples of bacteria other than the above bacteria include bacteria belonging to the genus Pseudomonas, the genus Agrobacterium, the genus Alicyclobacillus, the genus Arthrobacter, the genus Azotobacter, the genus Chromatium, the genus Methylobacterium, the genus Rhodobacter, the genus Rhodopseudomonas, the genus Rhodospirillum, the genus Zymomonas, the genus Achromobacter, and the genus Achromobacter. Bacteria of the genera romobacter, Aerobacter, Alcaligenes, Arthrobacter, Erwinia, Microbacterium, Micrococcus, Protaminobacter, Proteus, Sartina, Xanthomonas, Aeromonas, Flavobacterium, and Rhizobium.

[0148] Examples of yeast include yeast belonging to the genera Saccharomyces, Candida, Phichia, Schizosaccharomyces, Kluyveromyces, Rhodotorula, Crytpococcus, Torulopsis, Hansenula, Issatchenkia, Kluyveromyces, and Yarrowia.

[0149] Specific examples of yeast include Saccharomyces cerevisiae, Candida utilis, Pichia pastoris, Hansenula polymorpha, and Schizosaccharomyces pombe.

[0150] Examples of filamentous fungi (molds) include bacteria belonging to the genera Aspergillus, Paecilomyces, Penicillium, Neurospora, Trichoderma, Fusarium, and Chrysosporium.

[0151] Specific examples of filamentous fungi (molds) include Aspergillus oryzae, Paecilomyces saturatus, Paecilomyces divaricatus, and Penicillium camemberti.

[0152] These strains can be obtained, for example, from the American Type Culture Collection (12301 Parklawn Drive, Rockville, Maryland 20852, PO Box 1549, Manassas, VA 20108, United States of America). Each strain is assigned an accession number, which can be used to distribute the strain (see http: / / www.atcc.org / ). The accession number corresponding to each strain is listed in the American Type Culture Collection catalog. Alternatively, these strains can be obtained, for example, from the depository institution that holds the strain.

[0153] The above-mentioned microorganisms may be used alone or in combination of two or more. Among them, prokaryotes are preferred, bacteria are more preferred, microorganisms belonging to the Enterobacteriaceae family are even more preferred, microorganisms belonging to the genus Escherichia are particularly preferred, and Escherichia coli is most preferred. Specifically, prokaryotes having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are preferred, bacteria having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are more preferred, microorganisms belonging to the Enterobacteriaceae family having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are even more preferred, microorganisms belonging to the genus Escherichia having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are particularly preferred, and Escherichia coli having genes encoding the 10 enzymes of the 1,6-hexanediol pathway is most preferred.

[0154] When the above genes (enzymes) are exogenously introduced into a microorganism and expressed, it is preferred that the above 4,6-dihydroxy-2-oxo-hexanoic acid aldolase is 2,4-dihydroxyhept-2-ene-1,7-dioic acid aldolase encoded by the HpaI gene of Escherichia coli, the above 4,6-dihydroxy-2-oxo-hexanoic acid 4-dehydratase is 2-oxo-hept-4-ene-1,7-dioic acid hydratase encoded by the HpcG / HpaH gene of Escherichia coli, and the above 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase is Arabidopsis thaliana with the NADP-dependent enal reductase (Japanese: アルケナールレダクターゼ) P1 of GenBank accession number CAC01710.1, the above-mentioned 6-hydroxy-2-oxohexanoic acid 2-reductase is a D-2-hydroxy acid dehydrogenase encoded by the panE gene of Lactococcus lactis, the above-mentioned 2,6-dihydroxy-hexanoic acid CoA-transferase and the above-mentioned 6-hydroxyhexanoyl-CoA-transferase are glutaconate-CoA-transferases encoded by the HadA gene of Clostridium difficile, and the above-mentioned 2,6-dihydroxy-hexanoyl-CoA2-dehydratase is a D-2-hydroxy acid dehydrogenase encoded by the panE gene of Clostridium difficile. The 2-hydroxyisocaproyl-CoA dehydratase expressed by the bacterium, the above-mentioned 6-hydroxy-2,3-dehydrohexanoyl-CoA2,3-reductase is the trans-2-enoyl-CoA reductase of GenBank Accession No. AE017248 of Treponema denticola, the above-mentioned 6-hydroxyhexanoate 1-reductase is the ATP / NADPH-CAR of GenBank Accession No. AAR91681.1 of Nocardia iovanni, and / or the above-mentioned 6-hydroxyhexanal 1-reductase is the 6-hydroxyhexanoate dehydrogenase of GenBank Accession No. AAN37489.1 of Rhodococcus.

[0155] By using the above-described microorganism, it is possible to perform (a) the step of converting a C3 aldehyde and pyruvate into a C6 β-hydroxyketone intermediate via aldol addition, and then (b) the step of converting the C6 β-hydroxyketone intermediate into 1,6-hexanediol or a solvate thereof via an enzymatic step. Preferably, the conversion includes reduction of an enoyl group or an enolate, reduction of a ketone, reduction of an aldehyde, dehydration, formation of a thioester, reduction of a thioester, or a combination thereof.

[0156] In addition, it is preferred to further include a step of producing C3 aldehyde and pyruvate from a source selected from glycerol, pentose, hexose, phosphoglyceride, other carbon sources, intermediates in the glycolysis pathway, intermediates in propionate metabolism, or a combination thereof.

[0157] Alternatively, the C3 aldehyde is obtained via a series of enzymatic steps, wherein the enzymatic steps preferably include dehydration of the diol.

[0158] More specifically, using the above-mentioned microorganism, 1,6-hexanediol is produced from 3-oxopropionate and 3-hydroxypropionaldehyde produced through a metabolic pathway within the microorganism, and through the pathways 2A, 2B, 2C, 2D, 2E, 2F, 2G, 4F3, 5R, and 5S shown in Figures 2 and 5 of Japanese Patent No. 6680671. In this biosynthetic pathway, 6-hydroxyhexanoyl-CoA is produced by the enzymatic reactions up to the pathway 2G, followed by the enzymatic reaction of 4F3 to produce 6-hydroxyhexanoic acid, followed by the enzymatic reaction of 5R to produce 6-hydroxyhexanal, and finally, 1,6-hexanediol is produced by the enzymatic reaction of 5S.

[0159] Therefore, the above-mentioned step (1) can be carried out by culturing the above-mentioned microorganism in a culture medium containing a raw material derived from a biomass resource. That is, by culturing the above-mentioned microorganism in a culture medium containing a raw material derived from a biomass resource, a 1,6-hexanediol composition can be produced from 6-hydroxyhexanoic acid and / or its derivatives obtained from the raw material derived from a biomass resource.

[0160] The raw materials derived from biomass resources are not particularly limited, but include pentoses such as xylose, xylulose, ribulose, arabinose, lyxose, and ribose; hexoses such as allose, altrose, glucose, mannose, gulose, idose, talose, galactose, fructose, psicose, sorbose, and tagatose; monosaccharides such as lactose, cellobiose, sucrose, and maltose; polysaccharides such as starch, cellulose, agarose, and dextran; alcohols such as sorbitol, ethanol, and glycerol; carbon sources used in culture medium components such as peptone, tryptone, and casamino acids; and nitrogen sources used in culture medium components such as organic nitrogen compounds such as peptone, tryptone, casamino acids, yeast extract, meat extract, and corn steep liquor. These can be used alone or in combination of two or more. Among these, carbon sources used in culture medium components are preferred, and monosaccharides and alcohols are more preferred.

[0161] Among monosaccharides, hexose is more preferred, and glucose is particularly preferred.

[0162] Among the alcohols, glycerol is further preferred.

[0163] Therefore, glucose and glycerol are most preferred as raw materials derived from biomass resources.

[0164] The culture medium is not particularly limited as long as it contains the above-mentioned raw materials derived from biomass resources. It can be a conventional culture medium containing a carbon source, a nitrogen source, inorganic ions, and, if necessary, an organic nutrient source, and can be appropriately prepared according to the microorganisms used. Among them, the raw materials derived from biomass resources preferably contain the above-mentioned carbon source.

[0165] Carbon sources other than the above components are not particularly limited as long as they can be utilized by microorganisms, and examples thereof include organic acids such as fumaric acid, citric acid, acetic acid, propionic acid, and their salts, carbohydrates such as paraffin, etc. These may be used alone or in combination of two or more.

[0166] Examples of nitrogen sources other than the above components include ammonium salts of inorganic salts such as ammonium sulfate and ammonium chloride, ammonium salts of organic acids such as ammonium fumarate and ammonium citrate, and nitrates such as sodium nitrate and potassium nitrate. These may be used alone or in combination of two or more.

[0167] The above-mentioned culture medium can use the nutrient source used in common culture medium such as trace metal salts, vitamins, hormones. These can be used alone or in combination of two or more. Wherein, with regard to trace metal salts, preferably sodium and / or potassium are contained.

[0168] The culture conditions are also not particularly limited. For example, the culture can be carried out for approximately 4 to 140 hours while appropriately controlling the pH and temperature within the range of pH 3 to 11 and the temperature of 20 to 70°C (more preferably 20 to 50°C). The culture can be carried out under either aerobic or anaerobic conditions, which can be appropriately selected depending on the microorganisms used, but aerobic conditions are preferred.

[0169] As described above, a 1,6-hexanediol composition can be produced by culturing the aforementioned microorganisms in a culture medium containing raw materials derived from biomass resources. Since the 1,6-hexanediol composition exists in the culture medium along with the microorganisms, the microorganisms can be removed from the culture medium as needed. The method for removing the microorganisms is not particularly limited, and for example, centrifugation and / or membrane separation can be used.

[0170] Centrifugal separation is not particularly limited, and for example, continuous centrifugal separation using a continuous centrifuge can be used. Examples of continuous centrifugal separators include cage centrifuges, disc centrifuges, and nozzle centrifuges. These can be used alone or in combination of two or more.

[0171] The membrane used in membrane separation is not particularly limited, for example, a membrane with a pore size of less than 10.0 μm can be enumerated, specifically, for example, a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, etc. can be enumerated. They can be used alone or in combination with two or more. In addition, the shape of the membrane is not particularly limited, and can be any shape such as a flat membrane, a hollow fiber membrane, a spiral membrane, a tubular membrane, a pleated membrane. The form of filtration is also not particularly limited, and any of the terminal mode and the tangential flow mode can be applied, preferably the tangential flow mode.

[0172] <<Process (2)>>

[0173] Step (2) is a step of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and / or distillation. Step (2) is not particularly limited as long as it is a step for appropriately removing impurities contained in the 1,6-hexanediol composition obtained in step (1), for example, in a culture medium containing the 1,6-hexanediol composition after removal of microorganisms, by ion exchange and / or distillation. However, step (2) is preferably a step of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and distillation. Furthermore, the ion exchange is preferably cation exchange and anion exchange, and more preferably cation exchange and anion exchange are performed in this order. Furthermore, the distillation is preferably performed to remove water, components with a boiling point lower than 1,6-hexanediol, and components with a boiling point higher than 1,6-hexanediol, and more preferably water, components with a boiling point lower than 1,6-hexanediol, and components with a boiling point higher than 1,6-hexanediol are removed in this order.

[0174] The 1,6-hexanediol composition obtained in step (1) to be supplied to step (2) is not particularly limited as long as it is the 1,6-hexanediol composition obtained in step (1). However, it is preferably a liquid obtained by removing microorganisms from a culture medium containing the 1,6-hexanediol composition obtained in step (1). More preferably, it is a liquid obtained by removing microorganisms from the culture medium containing the 1,6-hexanediol composition obtained in step (1) by subjecting the culture medium containing the 1,6-hexanediol composition obtained in step (1) to centrifugation and membrane separation.

[0175] Hereinafter, an example of step (2) will be described in detail.

[0176] [Ion exchange process]

[0177] In the ion exchange step, a 1,6-hexanediol composition is obtained through the following steps (a) and (b) in this order.

[0178] Step (a): a step of contacting the 1,6-hexanediol composition obtained in step (1) with a cation exchange resin to obtain a 1,6-hexanediol composition A.

[0179] Step (b): a step of contacting the 1,6-hexanediol composition A obtained in step (a) with an anion exchange resin to obtain a 1,6-hexanediol composition B.

[0180] Examples of the component removed by contact with the cation exchange resin in the step (a) include metal cations and ammonium ions.

[0181] Examples of components removed by contact with the anion exchange resin in step (b) include chloride ions, sulfate ions, phosphate ions, organic acids, etc. The organic acids listed here include compounds (A) having an acid group and two or more secondary hydroxyl groups in one molecule.

[0182] The treatment with the ion exchange resin is not particularly limited, but is preferably performed by a batch method or a column method.

[0183] <Step (a): Step of Removing Cations Contained in 1,6-Hexanediol Composition>

[0184] In step (a), the 1,6-hexanediol composition is brought into contact with a cation exchange resin to remove cations.

[0185] Examples of the cation exchange resins used include strongly acidic and weakly acidic resins, without particular limitation. Examples include styrene-based, acrylic-based, and hydrogel-based resins, without particular limitation. Examples include gel-based, porous, and highly porous resins, without particular limitation. Examples of the resin form include powdery, spherical, fibrous, and film-like resins, without particular limitation.

[0186] <Step (b): Step of Removing Anions Contained in 1,6-Hexanediol Composition>

[0187] In step (b), the 1,6-hexanediol composition is brought into contact with an anion exchange resin to remove anions.

[0188] Examples of the anion exchange resin to be used include strongly basic and weakly basic anions, without particular limitation. Examples include styrene-based, acrylic-based, and hydrogel-based anions, without particular limitation. Examples include gel-based, porous, and highly porous anions, without particular limitation. Examples of the resin's form include powdered, spherical, fibrous, and film-like anions, without particular limitation.

[0189] It should be noted that, while the above description describes a method in which the steps (a) and (b) are performed sequentially, the steps (b) and (a) may also be performed sequentially. Specifically, the 1,6-hexanediol composition obtained in step (1) may be contacted with an anion exchange resin and then with a cation exchange resin.

[0190] Alternatively, the above steps (a) and (b) may be performed simultaneously. That is, the 1,6-hexanediol composition obtained in step (1) may be brought into contact with a cation exchange resin and an anion exchange resin simultaneously.

[0191] [Distillation process]

[0192] The distillation is sequentially carried out through the following steps (c), (d), and (e) to obtain a 1,6-hexanediol composition E. When it is desired to further increase the purity, purification may be performed through the step (f).

[0193] Step (c): a step of removing water contained in the liquid containing the 1,6-hexanediol composition from the 1,6-hexanediol composition (eg, 1,6-hexanediol composition B) obtained in the above-mentioned ion exchange step to obtain a 1,6-hexanediol composition C.

[0194] Step (d): a step of removing components having a boiling point lower than that of 1,6-hexanediol from the 1,6-hexanediol composition C obtained in step (c) to obtain a 1,6-hexanediol composition D.

[0195] Step (e): a step of removing components having a boiling point higher than that of 1,6-hexanediol from the 1,6-hexanediol composition D obtained in the step (d) to obtain a 1,6-hexanediol composition E.

[0196] Step (f): a step of distilling the 1,6-hexanediol composition E obtained in step (e) to obtain 1,6-hexanediol of higher purity.

[0197] Examples of the component having a boiling point lower than that of 1,6-hexanediol in the step (d) include 1,3-propylene glycol, a compound (A) having two or more secondary hydroxyl groups in one molecule, 6-hydroxyhexanal and / or its derivative (B).

[0198] Examples of the component having a boiling point higher than 1,6-hexanediol in the step (e) include glycerol, a compound (A) having two or more secondary hydroxyl groups in one molecule, 6-hydroxyhexanal and / or its derivative (B), and the like.

[0199] The distillation method is not particularly limited, but removal by continuous or batch distillation is preferred.

[0200] <Step (c): Removal of Water Contained in 1,6-Hexanediol Composition>

[0201] In step (c), the 1,6-hexanediol composition obtained in the ion exchange step (eg, 1,6-hexanediol composition B) is heated to a temperature at which water evaporates, and the pressure is reduced as needed to remove water from the 1,6-hexanediol composition B.

[0202] Examples of the apparatus used include, but are not particularly limited to, a continuous distillation column, a multi-effect tank, a thin-film evaporator, an evaporator, a batch still, and an atomizing separator.

[0203] <Step (d): Removal of components having a boiling point lower than that of 1,6-hexanediol>

[0204] In step (d), components having a boiling point lower than that of 1,6-hexanediol are removed from the 1,6-hexanediol composition C.

[0205] Step (d) is performed for the dual purpose of fully removing low-boiling-point components and removing trace amounts of coloring components to obtain high-purity 1,6-hexanediol. In particular, this operation removes or reduces the boiling point of components with lower boiling points than 1,6-hexanediol, such as the coloring components themselves and their hydrides.

[0206] The distillation in step (d) can be performed using known methods and apparatuses, such as atmospheric distillation, reduced pressure distillation, and pressurized distillation. Examples of the apparatus for removal include, but are not particularly limited to, continuous distillation columns, multi-effect tanks, thin-film evaporators, evaporators, batch stills, and atomizing separation devices. The operating conditions used in step (d) can be appropriately set, taking into account the composition of the 1,6-hexanediol composition C and the desired final purity, and are not particularly limited.

[0207] <Step (e): Removal of components having a boiling point higher than 1,6-hexanediol>

[0208] In the step (e), components having a boiling point higher than that of 1,6-hexanediol are removed from the 1,6-hexanediol composition D obtained in the step (d).

[0209] In the step (e), in particular, components having a boiling point higher than 1,6-hexanediol, which are specific to fermentation methods, such as nitrogen-containing components derived from amino acids and proteins, sugars and their decomposition products, are removed.

[0210] Examples of the apparatus for removal include continuous distillation columns, multi-effect tanks, thin-film evaporators, evaporators, batch stills, and atomizing separation devices, but are not particularly limited. The operating conditions used in step (e) can be appropriately set taking into account the composition of the 1,6-hexanediol composition D, the desired final purity, and the like, and are not particularly limited.

[0211] <Step (f): Step of Obtaining a Higher-Purity 1,6-Hexanediol Composition>

[0212] In step (f), the 1,6-hexanediol composition E obtained through steps (c), (d), and (e) is purified to obtain a 1,6-hexanediol composition of higher purity.

[0213] Examples of the apparatus for obtaining a higher-purity 1,6-hexanediol composition include, but are not particularly limited to, a continuous distillation column, a multi-effect tank, a thin-film evaporator, an evaporator, a batch still, and an atomizing separator.

[0214] The operating conditions used in the step (f) may be appropriately set in consideration of the composition of the liquid to be purified, the purity to be finally obtained, and the like, and are not particularly limited.

[0215] By carrying out the above step (e) and, if necessary, the above step (f), the 1,6-hexanediol composition of the present invention can be obtained.

[0216] In addition, in the above description, a method of performing the above steps (c), (d), and (e) in sequence has been described, but they may be performed in a different order.

[0217] The method for producing a 1,6-hexanediol composition of the present invention only needs to include step (1) and step (2), and may include other steps besides step (1) and step (2).

[0218] By performing the above-mentioned step (2), the total content of the compound (A) having two or more secondary hydroxyl groups per molecule and the total content of 6-hydroxyhexanal and / or its derivatives (B) are within the above-mentioned ranges. Alternatively, the step (2) may be repeated so that the total content of the compound (A) having two or more secondary hydroxyl groups per molecule and the total content of 6-hydroxyhexanal and / or its derivatives (B) are more preferably within the above-mentioned ranges. By repeating the step (2), the total content of the compound (A) having two or more secondary hydroxyl groups per molecule and the total content of 6-hydroxyhexanal and / or its derivatives (B) can be further reduced.

[0219] Polymers

[0220] The polymer of the present invention is a polymer obtained by reacting the 1,6-hexanediol composition of the present invention. The polymer is not particularly limited as long as it has structural units derived from the 1,6-hexanediol composition of the present invention, and also includes oligomers. Examples of the polymer of the present invention include polyesters, polyurethanes, polycarbonates, polyethers, epoxy polymers using the above-mentioned epoxy-containing 1,6-hexanediol derivatives as raw materials, and acrylic polymers using the above-mentioned (meth)acryloyl-containing 1,6-hexanediol derivatives as raw materials. These can be used alone or in combination of two or more. Among them, polyesters, polyurethanes, polycarbonates, and polyethers are preferred, polyesters, polyurethanes, and polyethers are more preferred, and polyesters and polyurethanes are even more preferred.

[0221] The polymer of the present invention has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, and may contain a structural unit derived from glycerol contained in the 1,6-hexanediol composition.

[0222] The content of the structural units derived from the 1,6-hexanediol composition of the present invention in 100% by mass of the polymer of the present invention is preferably 10 to 100% by mass, more preferably 20 to 100% by mass. This tends to provide more suitable effects.

[0223] In this specification, the content of each structural unit in a polymer is measured by NMR.

[0224] The total content of the structural units derived from the component (A) in one molecule of 100% by mass of the polymer of the present invention is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, further preferably 5 ppm by mass or less, and particularly preferably 0 ppm by mass (not included).

[0225] This tends to result in more favorable effects.

[0226] The total content of the structural units derived from the component (B) in 100% by mass of the polymer of the present invention is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, further preferably 200 ppm by mass or less, and particularly preferably 0 ppm by mass (not included).

[0227] This tends to result in more favorable effects.

[0228] In the polymer of the present invention, the total alkali metal content (preferably the total content of either or both sodium and potassium metals) is preferably 0.05 to 500 mass ppm, more preferably 0.05 to 400 mass ppm, and even more preferably 0.05 to 300 mass ppm. This tends to achieve more favorable effects. When the total alkali metal content is 0.05 mass ppm or greater, better reactivity, hydrolysis resistance, and tensile strength and elongation are achieved. When it is 500 mass ppm or less, reactivity tends to be further improved during polymer synthesis.

[0229] The content of the structural unit derived from glycerol in 100% by mass of the polymer of the present invention is preferably 1500 ppm by mass or less, more preferably 1000 ppm by mass or less, further preferably 500 ppm by mass or less, and particularly preferably 0 ppm by mass (not included).

[0230] This tends to result in more favorable effects.

[0231] The polymer may be modified. The modification is not particularly limited, and examples thereof include the modifications described for 1,6-hexanediol derivatives. Among these, modification with (meth)acrylic acid is preferred. In particular, when the polymer is a polyester, modification with (meth)acrylic acid is preferred.

[0232] The number average molecular weight (Mn) of the polymer of the present invention is preferably 500 to 1,000,000, more preferably 3,000 to 500,000. In this specification, the number average molecular weight (Mn) of the polymer is a value measured by gel permeation chromatography (GPC).

[0233] Hereinafter, polyester and polyurethane among the above-mentioned polymers will be described in detail, but the above-mentioned polymer is not limited to polyester and polyurethane.

[0234] <<Polyester>>

[0235] The polyester of the present invention is obtained by reacting the 1,6-hexanediol composition of the present invention. Specifically, the polyester of the present invention is a polycondensate synthesized by forming ester bonds through dehydration condensation of a carboxylic acid and an alcohol. As the alcohol, at least the 1,6-hexanediol composition of the present invention is used. Therefore, the polyester of the present invention is a reaction product (polycondensate) obtained through the polycondensation reaction of a carboxylic acid and an alcohol. The polyester of the present invention has at least structural units derived from the 1,6-hexanediol composition of the present invention and may also contain structural units derived from glycerol contained in the 1,6-hexanediol composition.

[0236] The polyester of the present invention may be a polyester polyol.

[0237] Examples of polyester polyols include condensation polyester polyols and lactone polyester polyols. Examples of condensation polyester polyols include low molecular weight polyols (ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-) butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerol, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, 1,4-cyclohexanedimethanol, etc.) Reaction products of polycarboxylic acids (e.g., sugars such as sorbitol) with polycarboxylic acids (e.g., glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, oligomeric acids (e.g., hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid). Lactone polyester polyols are, for example, polycaprolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone, α-methyl-ε-caprolactone, and ε-methyl-ε-caprolactone.

[0238] As the above carboxylic acids, for example, aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, etc.; alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid (Japanese: 1,4-シクロヘクサンジカルボン酸), etc.; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, trimellitic acid, etc.; aliphatic monocarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid, acrylic acid, methacrylic acid, etc.; aromatic monocarboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid, etc.; fatty acids derived from various animal and vegetable oils such as soybean oil fatty acid, tall oil fatty acid, linoleic acid, eicosapentaenoic acid, etc.; and their acid anhydrides, etc. They can be used alone or in combination of two or more. Among them, aliphatic carboxylic acids are preferred, and adipic acid is more preferred.

[0239] The alcohol that can be used other than the 1,6-hexanediol composition of the present invention is not particularly limited as long as it is a compound having a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group). As the above alcohol, aliphatic monohydric alcohols such as ethanol, butanol, 2-ethylhexanol, etc.; aliphatic polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, etc.; aromatic mono / polyhydric phenols such as phenol, cresol, bisphenol-A, etc.; and their ethylene oxide adducts (Japanese: 伸長物), hydrogenated alicyclics, etc. They can be used alone or in combination of two or more.

[0240] The content of the 1,6-hexanediol composition of the present invention in 100% by mass of the alcohol as a reaction raw material for the polyester is preferably 10 to 100% by mass, more preferably 50 to 100% by mass. Thereby, there is a tendency to more suitably obtain the effects.

[0241] The polyester (polyester polyol as the case may be) of the present invention can be obtained by a known method for producing a polyester. Specifically, it can be synthesized by a production method in which water generated is removed from the system while reacting the above carboxylic acid and the above alcohol at a reaction temperature of 150 to 280°C. In addition, a reaction catalyst, an antioxidant, etc. can also be used in combination during the synthesis.

[0242] The content of the structural unit derived from the 1,6-hexanediol composition of the present invention in 100% by mass of the polyester of the present invention is preferably 10 to 70% by mass, more preferably 2 to 70% by mass. Thereby, there is a tendency to more suitably obtain the effects.

[0243] In this specification, the content of each structural unit in the polyester is measured by NMR.

[0244] The total content of the structural units derived from the compound (A) having two or more secondary hydroxyl groups in one molecule in 100% by mass of the polyester of the present invention is preferably 70 ppm by mass or less, more preferably 35 ppm by mass or less, further preferably 7 ppm by mass or less, and particularly preferably 0 ppm by mass (excluding the compound).

[0245] This tends to result in more favorable effects.

[0246] The total content of structural units derived from 6-hydroxyhexanal and / or its derivative (B) in 100% by mass of the polyester of the present invention is preferably 700 ppm by mass or less, more preferably 350 ppm by mass or less, further preferably 140 ppm by mass or less, and particularly preferably 0 ppm by mass (excluding 6-hydroxyhexanal).

[0247] This tends to result in more favorable effects.

[0248] In the polyester of the present invention, the total alkali metal content (preferably the total content of either or both sodium and potassium metals) is preferably 0.05 to 500 mass ppm, more preferably 0.05 to 400 mass ppm, and even more preferably 0.05 to 300 mass ppm. When the total alkali metal content is 0.05 mass ppm or greater, better reactivity, hydrolysis resistance, and tensile strength and elongation are achieved. When the total alkali metal content is 500 mass ppm or less, the reactivity tends to be further improved when synthesizing urethane using the polyester of the present invention as a raw material.

[0249] The content of the structural unit derived from glycerol in 100% by mass of the polyester of the present invention is preferably 1400 ppm by mass or less, more preferably 1050 ppm by mass or less, further preferably 700 ppm by mass or less, and particularly preferably 0 ppm by mass (not included).

[0250] This tends to result in more favorable effects.

[0251] The number average molecular weight (Mn) of the polyester of the present invention is preferably 500 to 120,000, more preferably 3,000 to 50,000. In this specification, the number average molecular weight (Mn) of the polyester is a value measured by gel permeation chromatography (GPC).

[0252] <<Polyurethane>>

[0253] The polyurethane of the present invention is a reaction product obtained by reacting a polyol using the 1,6-hexanediol composition of the present invention as a reaction raw material with a polyisocyanate. Furthermore, polyols other than the 1,6-hexanediol composition as a reaction raw material, chain extenders, chain terminators, crosslinking agents, and the like may be used in combination as reaction raw materials for the polyurethane of the present invention, as needed.

[0254] Therefore, the polyurethane of the present invention has structural units derived from polyols and structural units derived from polyisocyanates, has at least structural units derived from the 1,6-hexanediol composition of the present invention, and optionally contains structural units derived from glycerol contained in the 1,6-hexanediol composition of the present invention.

[0255] Examples of the polyol include polycarbonate polyols, polyether polyols, polyester polyols, and the like. These polyols may or may not use a 1,6-hexanediol composition as a reaction raw material. The polyurethane of the present invention only requires that a polyol using a 1,6-hexanediol composition as a reaction raw material be used as a reaction raw material.

[0256] Polycarbonate polyols are polyols obtained by the reaction of a diol with a carbonate. Examples of the diol include various saturated or unsaturated diols such as the 1,6-hexanediol composition of the present invention, diethylene glycol, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, tripropylene glycol, polytetramethylene ether glycol, 2-methyl-1,3-propanediol, and 2-ethyl-2-butyl-1,3-propanediol, and alicyclic diols such as 1,4-cyclohexanediglycol and 1,4-cyclohexanedimethanol.

[0257] Examples of carbonates include dialkyl carbonates (such as dimethyl carbonate and diethyl carbonate), ethylene carbonate, and diphenyl carbonate.

[0258] Polyether polyols are, for example, polyether polyols produced by addition polymerization of alkylene oxides using various diols as initiators. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Examples of various diols include the same diols as those used in the polycarbonate diols described above.

[0259] As the polyols, in addition to the above polyols, polycaprolactone polyol, polyacrylic polyol, dimer diol, polybutadiene polyol, hydrogenated polybutadiene polyol, etc. can be used. These polyols can be used alone or in combination of two or more.

[0260] As the chain extender, for example, aliphatic polyol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, sucrose, methylene glycol, glycerol, sorbitol, and neopentyl glycol; aromatic polyol compounds such as bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; and water can be used. Amine compounds such as ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, isophoronediamine, and 4,4'-methylenebis(2-chloroaniline). These chain extenders can also be used, derived from biomass resources. These chain extenders can be used alone or in combination of two or more. Among these, neopentyl glycol, 1,4-butanediol, trimethylolpropane, isophoronediamine, and 4,4'-methylenebis(2-chloroaniline) are more preferred.

[0261] As the polyol, polyester polyols made from the composition of the present invention are particularly preferably used. The content of the polyester polyols made from the composition of the present invention in 100% by mass of the polyol is preferably 10 to 100% by mass, more preferably 50 to 100% by mass.

[0262] As the polyisocyanate, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-Dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, 1-methyl-3,5-diethylphenylene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate Aromatic polyisocyanates such as esters, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate, toluene diisocyanate; aliphatic polyisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate Isocyanates: alicyclic polyisocyanates such as 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate. These polyisocyanates may also be used, derived from biomass resources. These may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred, with 4,4'-diphenylmethane diisocyanate and toluene diisocyanate being more preferred.

[0263] To control the molecular weight of the resulting polyurethane, a chain terminator having one active hydrogen group may be used as needed. Examples of these chain terminators include aliphatic monohydroxy compounds having a hydroxyl group, such as methanol, ethanol, propanol, butanol, and hexanol, and aliphatic monoamines having an amino group, such as morpholine, diethylamine, dibutylamine, monoethanolamine, and diethanolamine. These may be used alone or in combination of two or more.

[0264] In order to improve the heat resistance and strength of the obtained polyurethane, a cross-linking agent having three or more active hydrogen groups or an isocyanate group may be used as needed.

[0265] The polyurethane of the present invention can be obtained by a known polyurethane production method. Specifically, for example, a method of producing the polyurethane by adding the aforementioned polyol, the aforementioned polyisocyanate, and the aforementioned chain extender and reacting them can be used. These reactions are preferably carried out at a temperature of 50 to 100°C for 3 to 10 hours. Furthermore, the reaction can be carried out in an organic solvent.

[0266] Examples of organic solvents include ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl n-propyl ketone, acetone, and methyl isobutyl ketone; ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, and sec-butyl acetate; and alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol. Furthermore, organic solvents derived from biomass resources may be used. These organic solvents may be used alone or in combination of two or more.

[0267] When a polyurethane is prepared using a polyester polyol derived from the 1,6-hexanediol composition of the present invention as a raw material, the content of structural units derived from the polyester polyol of the present invention in 100% by mass of the polyurethane is preferably 10 to 90% by mass, more preferably 20 to 90% by mass. This tends to provide more favorable effects.

[0268] The content of the structural units derived from the 1,6-hexanediol composition of the present invention in 100% by mass of the polyurethane of the present invention is preferably 1 to 63% by mass, more preferably 2 to 63% by mass. This tends to provide more suitable effects.

[0269] In this specification, the content of each structural unit in polyurethane is measured by NMR.

[0270] The total content of the structural units derived from the compound (A) having two or more secondary hydroxyl groups in one molecule in 100% by mass of the polyurethane of the present invention is preferably 63 ppm by mass or less, more preferably 32 ppm by mass or less, further preferably 6 ppm by mass or less, and particularly preferably 0 ppm by mass (not included).

[0271] This tends to result in more favorable effects.

[0272] The total content of structural units derived from 6-hydroxyhexanal and / or its derivative (B) in 100% by mass of the polyurethane of the present invention is preferably 945 ppm by mass or less, more preferably 630 ppm by mass or less, even more preferably 315 ppm by mass or less, and particularly preferably 0 ppm by mass (excluding 6-hydroxyhexanal). This tends to achieve more favorable effects.

[0273] In the polyurethane of the present invention, the total content of alkali metal elements (preferably the total content of either or both sodium and potassium metal elements) is preferably 0.05 to 500 mass ppm, more preferably 0.05 to 400 mass ppm, and even more preferably 0.05 to 300 mass ppm. When the total content of alkali metals is 0.05 mass ppm or greater, better reactivity, hydrolysis resistance, and tensile strength and elongation tend to be achieved.

[0274] The content of the structural unit derived from glycerol in 100% by mass of the polyurethane of the present invention is preferably 1260 ppm by mass or less, more preferably 945 ppm by mass or less, further preferably 630 ppm by mass or less, and particularly preferably 0 ppm by mass (not included).

[0275] This tends to allow more suitable tensile strength and elongation to be obtained.

[0276] The number average molecular weight (Mn) of the polyurethane of the present invention is preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000. This tends to provide more favorable effects. It should be noted that in this specification, the number average molecular weight (Mn) of the polyurethane is the value measured by gel permeation chromatography (GPC).

[0277] The polymers of the present invention can be used in a variety of applications. Specifically, they can be used in a wide range of applications, including artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, coatings, laminating adhesives, elastic fibers, urethane raw materials, automotive parts, sporting goods, vibration-proofing materials, vibration-damping materials, fiber treatment agents, and adhesives.

[0278] The polyester of the present invention can be used in a variety of applications. Specifically, it can be used in solvent-based, water-based, powder-based coatings for metals, automobiles, woodworking, and plastics; as a modifier for packaging materials, containers, optical films, and molded products; as the surface layer, intermediate layer, foam layer, and adhesive layer of artificial and synthetic leather; as adhesives such as laminating adhesives; and in a wide range of applications, including footwear, thermoplastic resins, foamed resins, thermosetting resins, elastic fibers, polyurethane raw materials, automotive parts, and sporting goods.

[0279] The polyurethane of the present invention can be used in a variety of applications. Specifically, it can be used in the surface layer, intermediate layer, foam layer, and adhesive layer of artificial and synthetic leather; various coating agents such as paints, metal surface treatment agents, and film primers; binders for inkjet printing, inks, printing and dyeing, and glass fiber sizing agents; adhesives such as shoes, thermoplastic resins, foamed resins, thermosetting resins, and laminating adhesives; vibration-proofing materials, vibration-damping materials, automotive parts, sporting goods, and fiber treatment agents, among other applications.

[0280] Epoxy polymers made from the epoxy-containing 1,6-hexanediol derivatives described above can be used in a variety of applications. Specifically, they can be used in a wide range of applications, including coatings, metal surface treatment agents, and molded articles such as windmill base resins.

[0281] Acrylic polymers made from these (meth)acryloyl-containing 1,6-hexanediol derivatives can be used in a variety of applications. Specifically, they can be used in a wide range of applications, including coatings, metal surface treatment agents, film coatings, and adhesives for inks and UV inkjet applications.

[0282] Furthermore, the 1,6-hexanediol composition of the present invention can also be added to modify PBS resin, PET resin, PTT resin, PBT resin, and the like.

[0283] It should be noted that, in this specification, the expression “~” means more than the value before the description such as “~” and less than the value after the description such as “~”. In addition, in this specification, with respect to a certain characteristic, when multiple numerical ranges are disclosed by the expression “~”, the upper limit and lower limit of each numerical range can be used in any combination. For example, with respect to the content of a certain compound, when two numerical ranges of 0.001 to 500 mass ppm and 0.05 to 250 mass ppm are disclosed, it means that in addition to 0.001 to 500 mass ppm and 0.05 to 250 mass ppm, the numerical ranges of 0.001 to 250 mass ppm and 0.05 to 500 mass ppm are also disclosed.

[0284] [Example]

[0285] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0286] (Production Example 1) (Production of Recombinant Escherichia coli)

[0287] Plasmid A was prepared by introducing the glycerol dehydrogenase α, β, and γ subunit genes and the dehydrogenase reactivation factor gene from Citrobacter freundii into pACYC184 (Nippon Gene) between the BamHI and HindIII restriction enzyme cleavage sites.

[0288] The Escherichia coli HpaI gene for 4,6-dihydroxy-2-oxohexanoic acid aldolase, the Escherichia coli HpcG gene for 4,6-dihydroxy-2-oxohexanoic acid 4-dehydrogenase, the Arabidopsis thaliana NADPH-dependent oxidoreductase 2-alkenal reductase (GenBank: CAC01710.1) gene for 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase, the Lactococcus lactis PanE gene for 6-hydroxy-2-oxohexanoic acid 2-reductase, and the Clostridium difficile HadA gene for 2,6-dihydroxyhexanoic acid CoA-transferase and 6-hydroxyhexanoyl-CoA-transferase were introduced into the multiple cloning site (MCS) of pUC19 (Nippon Gene) between the BamHI and EcoRI restriction enzyme cleavage sites to construct plasmid B.

[0289] The HadB and HadC genes of Clostridium difficile as the α and β subunit genes of 2-hydroxyisocaproyl-CoA dehydrogenase, the HadI gene of Clostridium difficile as the 2-hydroxyisocaproyl-CoA dehydrogenase activating enzyme, the trans-2-enoyl-CoA reductase gene of Treponema denticola (GenBank: AE017248) as the 6-hydroxy-2,3-dehydrohexanoyl-CoA2,3-reductase, and the trans-2-enoyl-CoA reductase gene of 6-hydroxyhexanoate 1-reductase were cloned. The carboxylic acid reductase gene (GenBank: AAR91681.1) derived from Nocardia iocardii and the 6-hydroxyhexanal 1-reductase gene (GenBank: AAN37489.1) derived from Rhodococcus sp. were introduced into pCOLADuet-1 (Novagen). The HadB, HadC, and HadI genes were introduced into MCS1, and the remaining genes were introduced into MCS2 to create plasmid C.

[0290] The genes referred to in this section refer to translatable frames including stop codons encoding the respective enzymes. Each gene is introduced into a plasmid with a sequence containing a T7 promoter and ribosome binding site upstream and a sequence containing a T7 terminator downstream. Each gene can be expressed in large quantities in a host strain such as Escherichia coli, where T7 RNA polymerase is expressed through appropriate induction.

[0291] Plasmids A, B, and C were sequentially transformed into chemically competent BL21 Star (DE3) cells (Invitrogen) using the heat shock method and selected on LB plates containing the appropriate antibiotics. As a result, BL21 Star (DE3) strains harboring all plasmids A, B, and C were obtained.

[0292] Thus, Escherichia coli was prepared that has genes encoding 10 enzymes of the 1,6-hexanediol pathway, namely 4,6-dihydroxy-2-oxo-hexanoic acid aldolase (2A in the figure of Japanese Patent No. 6680671), 4,6-dihydroxy-2-oxo-hexanoic acid 4-dehydrogenase (2B in the figure of Japanese Patent No. 6680671), 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase (2C in the figure of Japanese Patent No. 6680671), 6-hydroxy-2-oxohexanoic acid 2-reductase (2D in the figure of Japanese Patent No. 6680671), 2,6-dihydroxy-hexanoic acid CoA-transferase (2A in the figure of Japanese Patent No. 6680671), and 1,6-dihydroxy-2-oxohexanoic acid CoA-transferase (2B in the figure of Japanese Patent No. 6680671). Transferase (2E in the figure of Japanese Patent No. 6680671), 2,6-dihydroxy-hexanoyl-CoA2-dehydrogenase (2F in the figure of Japanese Patent No. 6680671), 6-hydroxy-2,3-dehydro-hexanoyl-CoA2,3-reductase (2G in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoyl-CoA-transferase (4F3 in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoate 1-reductase (5R in the figure of Japanese Patent No. 6680671) and 6-hydroxyhexanal 1-reductase (5S in the figure of Japanese Patent No. 6680671).

[0293] (Example 1: Preparation of 1,6-Hexanediol Composition 1 (1,6-HD Composition 1))

[0294] The above-mentioned E. coli is inoculated into a culture medium (carbon source: glucose, glycerol, nitrogen source: enzyme extract, inorganic salts: potassium phosphate, potassium hydroxide, vitamin B12, antibiotics: carbenicillin, kanamycin, chloramphenicol, pH: 7.0, wherein glucose and glycerol are raw materials derived from biomass resources) sterilized by autoclaving and cultured at 30°C under aerobic conditions for 2 to 3 hours. Then, when the optical density of the E. coli at 600 nm reaches 0.3 to 0.6, isopropyl-β-thiogalactoside is added to a final concentration of 0.5 mM and iron (II) sulfate is added to a final concentration of 10 μM, and the culture is further cultured at 30°C for 3 hours to express the enzyme of the 1,6-HD pathway. After expression, an appropriate amount of carbon source (glucose, glycerol) is added, and the culture vessel is placed under a nitrogen atmosphere to establish anaerobic conditions. Under these conditions, culture is carried out at 30°C for 48 hours to produce 1,6-hexanediol (step (1)). The culture solution was centrifuged at 4°C for 20 minutes, and the supernatant was recovered and filtered using an appropriate membrane filter with a pore size of 0.2 to 0.4 μm to obtain a 1,6-hexanediol composition as a filtrate.

[0295] [Purification of 1,6-hexanediol composition]

[0296] <Step (a): Ion Exchange to Remove Cations>

[0297] Cations contained in the 1,6-hexanediol composition were removed. In step (a), cation exchange was performed batchwise. The contact temperature with the cation exchange resin was set at 40°C. DIAION SK1BH, manufactured by Mitsubishi Chemical Co., Ltd., was added to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, the mixture was filtered to obtain a 1,6-hexanediol composition A as a filtrate.

[0298] <Step (b): Ion Exchange to Remove Anions>

[0299] Anions contained in 1,6-hexanediol composition A were removed. In step (b), anion exchange was performed batchwise. The temperature for contact with the anion exchange resin was set at 40°C. DIAION SA10AOH (manufactured by Mitsubishi Chemical Co.) was added to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, the mixture was filtered to obtain 1,6-hexanediol composition B as a filtrate.

[0300] <Step (c): Water Removal Step>

[0301] Water contained in the 1,6-hexanediol composition was removed. A thin-film distiller was used as the apparatus for step (c). The jacket temperature was set at 70°C, and the 1,6-hexanediol-containing composition was continuously introduced, allowing water to be distilled from the top. Simultaneously with the water distillation, the dehydrated 1,6-hexanediol composition C was continuously withdrawn from the bottom as a bottoms liquid. The water concentration in this 1,6-hexanediol composition C was 0.020% by mass (200 ppm by mass).

[0302] <Step (d): Distillation Separation of Low-Boiling-Point Components>

[0303] Components with a boiling point lower than 1,6-hexanediol contained in the 1,6-hexanediol composition C were removed using a continuous distillation column. An Oldershaw distillation column was used as the distillation column in step (d). The 1,6-hexanediol composition C obtained in step (c) was continuously supplied to the distillation column, and the column top temperature was controlled to a constant 240°C. Continuous distillation was performed from the column top and extraction was performed from the column bottom to remove low-boiling-point components from the 1,6-hexanediol composition C. The 1,6-hexanediol composition D, from which components with a boiling point lower than 1,6-hexanediol were removed, was withdrawn from the column bottom.

[0304] <Step (e): Distillation Separation of High-Boiling-Point Components>

[0305] Components with a boiling point higher than 1,6-hexanediol contained in 1,6-hexanediol composition D were removed using a continuous distillation column. An Oldershaw distillation column was used as the distillation column in step (e). The 1,6-hexanediol composition D obtained in step (d) was continuously supplied to the distillation column, and the column bottom temperature was controlled to maintain a constant 260°C. High-boiling-point components in 1,6-hexanediol composition D were removed by continuous extraction from the column bottom. From the column top, 1,6-hexanediol composition E (1,6-HD composition 1), from which components with a boiling point higher than 1,6-hexanediol were removed, was obtained (overhead distillate).

[0306] The analysis results of the resulting 1,6-HD composition 1 are shown below. In the analysis of the 1,6-HD composition, the detection limits for glycerol, glucose, 1,4-cyclohexanediol, 6-hydroxyhexanal, potassium metal, and sodium metal were 5.0 mass ppm, 5.0 mass ppm, 0.3 mass ppm, 10.0 mass ppm, 3.0 mass ppb, and 3.0 mass ppb, respectively. Quantification of potassium metal and sodium metal was performed by ICP-MS analysis, while other analyses were performed by HPLC and GC analysis.

[0307] Glycerol: 800 mass ppm

[0308] Glucose: below the detection limit

[0309] 1,4-Cyclohexanediol: below the detection limit

[0310] 6-Hydroxyhexanal: 500 ppm by mass

[0311] Potassium metal element: 2 mass ppm

[0312] Sodium metal element: 2 mass ppm

[0313] HPLC analysis details

[0314] Apparatus: HPLC apparatus manufactured by Shimadzu Corporation (system controller: SCL-10A, liquid delivery unit: LC-10AD, column oven: CTO-10A, autosampler: SIL-10AD, low pressure gradient unit: FCV-10AL, online degasser: DGU-14A)

[0315] Column: TSKgel OApak-A

[0316] Guard column: TSKgel OApak-P

[0317] Column temperature: 40°C

[0318] Eluent (ISO): 0.75 mM sulfuric acid

[0319] Flow rate: 0.8 mL / min

[0320] Injection volume: 10.0 μL

[0321] Detector: RI (RID-10A)

[0322] GC analysis details

[0323] Equipment: Agilent GC-MS (GC7890B / MSD5977B)

[0324] ·Column: Agilent J&W GC Column-DB-1

[0325] Carrier gas: He

[0326] Flow rate: 0.966 mL / min

[0327] Linear speed: 99.5cm / sec

[0328] Injection volume: 1 μL

[0329] Split ratio: 50

[0330] Column temperature: 75°C (hold: 2 min) - 10°C / min (heating rate, 22.5 min) - 300°C (hold: 5.5 min)

[0331] Detector: FID

[0332] (Synthesis of polyester resin)

[0333] In a reaction vessel equipped with a stirring rod, temperature sensor, and distillation tube, 1546.0 g (4.62 mol) of the 1,6-HD composition and 602.3 g (4.12 mol) of adipic acid were placed under a nitrogen atmosphere. After adding 0.05 g of tetraisopropyl titanate as a catalyst, dry nitrogen was flowed through the flask and the mixture was heated to 210-230°C while stirring to allow a dehydration condensation reaction to proceed. The reaction was continued until the acid value reached 0.2, yielding a polyester polyol with a hydroxyl value of 55.9 and a number average molecular weight of 2000.

[0334] The obtained polyester was evaluated by the following method, and the analysis results are shown below.

[0335] Reaction time: Reaction time until the acid value reaches 0.2 (3-level evaluation)

[0336] Less than 6 hours: 0,

[0337] More than 6 hours and less than 8 hours: △,

[0338] More than 8 hours: ×.

[0339] Color number: The color number is evaluated using the Gardner color scale (JIS K0071; 1998) until the polyester resin melted at 100°C is solidified (smaller numbers indicate less coloration).

[0340] Odor: 1000 g of polyester polyol was added to a 1 kg metal can and placed in a dryer at 100°C for 3 hours to completely dissolve. The intensity of the odor upon opening the can was then sensory evaluated as follows:

[0341] ◎: Almost odorless,

[0342] ○: Slightly smelly,

[0343] △: strong odor,

[0344] ×: Quite strong odor.

[0345] (Evaluation results)

[0346] Reaction time: 0 Color number: 1 Odor: △

[0347] (Synthesis of polyurethane resin)

[0348] In a four-necked flask equipped with a thermometer, a stirrer, and an inert gas inlet, 400 g (0.200 mol) of the aforementioned polyester polyol and 40.0 g (0.384 mol) of neopentyl glycol were dissolved in 542 g of DMF solvent. Next, 101.7 g (0.584 mol) of toluene diisocyanate and 101.7 g (0.584 mol) of Coronate T-80 were added at 40°C, and the mixture was reacted at 90°C until the NCO% reached 0.1% or less, yielding a carbamate solution with a nonvolatile content of 50%.

[0349] The obtained polyurethane was evaluated by the following method, and the analysis results are shown below.

[0350] Reaction time: the time from the addition of TDI until NCO% reaches below 0.1%

[0351] Less than 6 hours: ◎,

[0352] More than 6 hours and less than 8 hours: ○,

[0353] More than 8 hours and less than 10 hours: △,

[0354] More than 10 hours: ×.

[0355] Film Properties: After adding a polyisocyanate crosslinker to the resulting urethane resin (urethane resin solids / crosslinker solids = 10 / 1 by mass), the film was immediately pre-dried using a Werner Mathis at 70°C for 1 minute and then dried at 120°C for 2 minutes to produce a urethane resin film. After aging the film at 40°C for 2 days, the film properties (initial strength and elongation at break) were measured using an Autograph (Shimadzu Corporation) at 23°C and 65% RH. Furthermore, for hydrolysis resistance testing, the urethane film was stored at 70°C and 95% RH for 1 week. After further drying at room temperature for 1 day, the film properties were measured to determine the degree of film degradation.

[0356] Breaking Strength (Initial):

[0357] ◎:Above 50Mpa,

[0358] ○: 40 MPa or more and less than 50 MPa,

[0359] △: 30 MPa or more and less than 40 MPa,

[0360] ×: less than 30 MPa.

[0361] Elongation at break (initial):

[0362] ◎:More than 500%,

[0363] ○: 400% or more and less than 500%,

[0364] △: 300% or more and less than 400%,

[0365] ×: Less than 300%.

[0366] Hydrolysis resistance (evaluated by the retention of breaking strength based on the initial value and the elongation at break after the hydrolysis resistance test):

[0367] ◎: The retention rate of breaking strength is 80% or more, and the elongation at break is 100% or more;

[0368] ○: The retention rate of breaking strength is 70% or more and less than 80%, and the elongation at break is 100% or more;

[0369] △: The retention rate of breaking strength is 50% or more and less than 70%, and the elongation at break is 100% or more;

[0370] ×: The retention rate of breaking strength is less than 50%, or the elongation at break is less than 100%.

[0371] (Evaluation results)

[0372] Reaction time: 0 Breaking strength of film: 0

[0373] Elongation at break of film: △ Hydrolysis resistance: ◎

[0374] (Example 2: Preparation of 1,6-hexanediol composition 2 (1,6-HD composition 2))

[0375] In Example 1, the purification of the 1,6-hexanediol composition obtained by the biological method was repeated to obtain a 1,6-hexanediol composition 2 having a glycerol content of 150 mass ppm and a 6-hydroxyhexanal content of 100 mass ppm.

[0376] The analysis results of the obtained 1,6-HD composition 2 are shown below.

[0377] Glycerol: 150 ppm by mass

[0378] Glucose: below the detection limit

[0379] 1,4-Cyclohexanediol: below the detection limit

[0380] 6-Hydroxyhexanal: 100 ppm by mass

[0381] Potassium metal element: 1 mass ppm

[0382] Sodium metal element: 1 mass ppm

[0383] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0384] (Evaluation results)

[0385] Polyester evaluation reaction time: 0 Color number: <1 Odor: 0

[0386] Polyurethane evaluation reaction time: 0 Film breaking strength: 0

[0387] Elongation at break of film: ○ Hydrolysis resistance: ○

[0388] (Example 3: Preparation of 1,6-Hexanediol Composition 3 (1,6-HD Composition 3))

[0389] In Example 1, the purification of the 1,6-hexanediol composition obtained by the biological method was repeated to obtain a 1,6-hexanediol composition 3 having a glycerol content of 5 mass ppm and a 6-hydroxyhexanal content of 10 mass ppm.

[0390] The analysis results of the obtained 1,6-HD composition 3 are shown below.

[0391] Glycerin: 5 ppm by mass

[0392] Glucose: below the detection limit

[0393] 1,4-Cyclohexanediol: below the detection limit

[0394] 6-Hydroxyhexanal: 10 ppm by mass

[0395] Potassium metal element: below the detection limit

[0396] Sodium metal element: below the detection limit

[0397] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0398] (Evaluation results)

[0399] Polyester evaluation reaction time: 0 Color number: <1 Odor: 0

[0400] Polyurethane evaluation reaction time: 0 Film breaking strength: ◎

[0401] Elongation at break of film: ◎ Hydrolysis resistance: ○

[0402] (Example 4: Preparation of 1,6-Hexanediol Composition 4 (1,6-HD Composition 4))

[0403] Potassium acetate was added to 1,6-HD composition 3 obtained in Example 3 to give a potassium metal element concentration of 300 mass ppm, and sodium acetate was added to give a sodium metal element concentration of 200 mass ppm to prepare 1,6-hexanediol composition 4 (1,6-HD composition 4).

[0404] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0405] (Evaluation results)

[0406] Polyester evaluation reaction time: 0 Color number: <1 Odor: 0

[0407] Polyurethane evaluation reaction time: ◎ Film breaking strength: ◎

[0408] Elongation at break of film: ◎ Hydrolysis resistance: ◎

[0409] (Example 5: Preparation of 1,6-Hexanediol Composition 5 (1,6-HD Composition 5))

[0410] To the 1,6-HD composition 3 obtained in Example 3, glycerin was added so as to be 150 ppm by mass of glycerin, thereby preparing a 1,6-hexanediol composition 5 (1,6-HD composition 5).

[0411] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0412] (Evaluation results)

[0413] Polyester evaluation reaction time: 0 Color number: <1 Odor: 0

[0414] Polyurethane evaluation reaction time: 0 Film breaking strength: ◎

[0415] Elongation at break of film: ◎ Hydrolysis resistance: ◎

[0416] (Example 6: Preparation of 1,6-hexanediol composition 6 (1,6-HD composition 6))

[0417] To the 1,6-HD composition 3 obtained in Example 3, glycerin was added so as to give a glycerin content of 1500 mass ppm, thereby preparing a 1,6-hexanediol composition 6 (1,6-HD composition 6).

[0418] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0419] (Evaluation results)

[0420] Polyester evaluation reaction time: 0 Color number: <1 Odor: 0

[0421] Polyurethane evaluation reaction time: 0 Film breaking strength: 0

[0422] Elongation at break of film: △ Hydrolysis resistance: ○

[0423] (Example 7: Preparation of 1,6-hexanediol composition 7 (1,6-HD composition 7))

[0424] 1,4-cyclohexanediol was added to the 1,6-HD composition 3 obtained in Example 3 so that the content of 1,4-cyclohexanediol became 100 ppm by mass, thereby preparing a 1,6-hexanediol composition 7 (1,6-HD composition 7).

[0425] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0426] (Evaluation results)

[0427] Polyester evaluation reaction time: 0 Color number: <1 Odor: 0

[0428] Polyurethane evaluation reaction time: △ Film breaking strength: ○

[0429] Elongation at break of film: ○ Hydrolysis resistance: ○

[0430] (Example 8: Preparation of 1,6-Hexanediol Composition 8 (1,6-HD Composition 8))

[0431] 6-hydroxyhexanal was added to the 1,6-HD composition 3 obtained in Example 3 so as to give 1500 mass ppm of 6-hydroxyhexanal, thereby preparing a 1,6-hexanediol composition 8 (1,6-HD composition 8).

[0432] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0433] (Evaluation results)

[0434] Polyester evaluation reaction time: 0 Color number: 2 Odor: △

[0435] Polyurethane evaluation reaction time: 0 Film breaking strength: 0

[0436] Elongation at break of film: ○ Hydrolysis resistance: ○

[0437] (Comparative Example 1: Preparation of 1,6-Hexanediol Composition 9 (1,6-HD Composition 9))

[0438] Glucose was added to the 1,6-HD composition 3 obtained in Example 3 so as to be 150 ppm by mass, thereby preparing a 1,6-hexanediol composition 9 (1,6-HD composition 9).

[0439] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0440] (Evaluation results)

[0441] Polyester evaluation reaction time: 0 (pitting occurs) Number of colors: 3

[0442] Odor: 0

[0443] Polyurethane evaluation was not performed due to the occurrence of pitting during polyesterification.

[0444] (Comparative Example 2: Preparation of 1,6-Hexanediol Composition 10 (1,6-HD Composition 10))

[0445] 1,4-cyclohexanediol was added to the 1,6-HD composition 3 obtained in Example 3 so as to provide 150 ppm by mass of 1,4-cyclohexanediol, thereby preparing a 1,6-hexanediol composition 10 (1,6-HD composition 10).

[0446] The synthesis and evaluation of the polyester resin and the synthesis and evaluation of the polyurethane resin were carried out in the same manner as in Example 1.

[0447] (Evaluation results)

[0448] Polyester evaluation reaction time: △ Color number: <1 Odor: ○

[0449] Polyurethane evaluation reaction time: △ Film breaking strength: △

[0450] Elongation at break of film: △ Hydrolysis resistance: ×

[0451] The results of the above-mentioned Examples and Comparative Examples are summarized in Tables 1 to 3 below.

[0452] [Table 1]

[0453]

[0454] [Table 2]

[0455]

[0456] [Table 3]

[0457]

[0458] According to the above-mentioned examples and comparative examples, the method for producing a 1,6-hexanediol composition of the present invention includes: a step (1) of producing a 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from biomass resources; and a step (2) of purifying the 1,6-hexanediol composition obtained in the step (1) by ion exchange and / or distillation. Since the method is a method for producing a 1,6-hexanediol composition in which the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule is 100 mass ppm or less and the total content of 6-hydroxyhexanal and / or its derivatives (B) is 1500 mass ppm or less, it is possible to produce a 1,6-hexanediol composition having excellent reactivity while taking environmental considerations into account.

[0459] Furthermore, it was found that the 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition of the present invention has excellent reactivity, and the polyester obtained using the 1,6-hexanediol composition as a reaction raw material also has excellent reactivity.

[0460] It was also found that the polyurethane produced using the 1,6-hexanediol composition of the present invention as a reaction raw material had excellent tensile strength and elongation.

[0461] In addition, in this specification, the number average molecular weight (Mn) of polyester is a value measured by gel permeation chromatography (GPC) under the following conditions.

[0462] Measuring device: HLC-8320GPC manufactured by Tosoh Corporation

[0463] Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, and TSKgel 1000HXL manufactured by Tosoh Corporation were connected in series and used.

[0464] Detector: RI (differential refractometer)

[0465] Data processing: MultiStation GPC-8020modelII manufactured by Tosoh Corporation

[0466] Determination conditions: column temperature 40°C

[0467] Solvent tetrahydrofuran (THF)

[0468] Flow rate 0.1ml / min

[0469] Standard: Monodisperse polystyrene

[0470] Sample: A 0.2% tetrahydrofuran solution calculated as resin solids was filtered through a microfilter (100 μl)

[0471] Standard samples: The following polystyrene standards were used to create a calibration curve.

[0472] (Standard polystyrene)

[0473] TSKgel Standard Polystyrene A-500 manufactured by Tosoh Corporation

[0474] TSKgel Standard Polystyrene A-1000 manufactured by Tosoh Corporation

[0475] TSKgel Standard Polystyrene A-2500 manufactured by Tosoh Corporation

[0476] TSKgel Standard Polystyrene A-5000 manufactured by Tosoh Corporation

[0477] TSKgel Standard Polystyrene F-1 manufactured by Tosoh Corporation

[0478] TSKgel Standard Polystyrene F-2 manufactured by Tosoh Corporation

[0479] TSKgel Standard Polystyrene F-4 manufactured by Tosoh Corporation

[0480] TSKgel Standard Polystyrene F-10 manufactured by Tosoh Corporation

[0481] TSKgel Standard Polystyrene F-20 manufactured by Tosoh Corporation

[0482] TSKgel Standard Polystyrene F-40 manufactured by Tosoh Corporation

[0483] TSKgel Standard Polystyrene F-80 manufactured by Tosoh Corporation

[0484] TSKgel Standard Polystyrene F-128 manufactured by Tosoh Corporation

[0485] TSKgel Standard Polystyrene F-288 manufactured by Tosoh Corporation

[0486] TSKgel Standard Polystyrene F-550 manufactured by Tosoh Corporation

[0487] In this specification, the number average molecular weight (Mn) of polyurethane is a value measured by gel permeation chromatography (GPC) under the following conditions.

[0488] Measuring device: High-speed GPC device (Tosoh Corporation "HLC-8220GPC")

[0489] Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

[0490] TSKgel G5000 (7.8mm I.D. x 30cm) x 1 piece

[0491] TSKgel G4000 (7.8mm I.D. x 30cm) x 1 piece

[0492] TSKgel G3000 (7.8mm I.D. x 30cm) x 1 piece

[0493] TSKgel G2000 (7.8mm I.D. x 30cm) x 1 piece

[0494] Detector: RI (differential refractometer)

[0495] Column temperature: 40°C

[0496] Eluent: tetrahydrofuran (THF)

[0497] Flow rate: 1.0 mL / min

[0498] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass %)

[0499] Standard samples: The following polystyrene standards were used to create a calibration curve.

[0500] (Standard polystyrene)

[0501] TSKgel Standard Polystyrene A-500 manufactured by Tosoh Corporation

[0502] TSKgel Standard Polystyrene A-1000 manufactured by Tosoh Corporation

[0503] TSKgel Standard Polystyrene A-2500 manufactured by Tosoh Corporation

[0504] TSKgel Standard Polystyrene A-5000 manufactured by Tosoh Corporation

[0505] TSKgel Standard Polystyrene F-1 manufactured by Tosoh Corporation

[0506] TSKgel Standard Polystyrene F-2 manufactured by Tosoh Corporation

[0507] TSKgel Standard Polystyrene F-4 manufactured by Tosoh Corporation

[0508] TSKgel Standard Polystyrene F-10 manufactured by Tosoh Corporation

[0509] TSKgel Standard Polystyrene F-20 manufactured by Tosoh Corporation

[0510] TSKgel Standard Polystyrene F-40 manufactured by Tosoh Corporation

[0511] TSKgel Standard Polystyrene F-80 manufactured by Tosoh Corporation

[0512] TSKgel Standard Polystyrene F-128 manufactured by Tosoh Corporation

[0513] TSKgel Standard Polystyrene F-288 manufactured by Tosoh Corporation

[0514] "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation.

Claims

1. A method for producing a 1,6-hexanediol composition, comprising: A step (1) of producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and / or a derivative thereof obtained from a raw material derived from a biomass resource, and a step (2) of purifying the 1,6-hexanediol composition obtained in the step (1) by ion exchange and / or distillation, The 1,6-hexanediol composition comprises: one or both of 1,6-hexanediol and a 1,6-hexanediol derivative, a compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and / or a derivative thereof (B), The content of the compound (A) having two or more secondary hydroxyl groups in one molecule is 100 ppm by mass or less relative to the total amount of the 1,6-hexanediol composition, and The total content of 6-hydroxyhexanal and / or its derivative (B) is 1500 ppm by mass or less based on the total amount of the 1,6-hexanediol composition.

2. The method for producing a 1,6-hexanediol composition according to claim 1, wherein The step (1) is a step of producing the 1,6-hexanediol composition at 70° C. or lower.

3. The method for producing a 1,6-hexanediol composition according to claim 1, wherein The step (1) is a step of producing the 1,6-hexanediol composition at 50° C. or lower.

4. The method for producing a 1,6-hexanediol composition according to claim 1, wherein The step (1) is a step of producing the 1,6-hexanediol composition using microorganisms.

5. A 1,6-hexanediol composition, wherein The 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition according to any one of claims 1 to 4 comprises: one or both of 1,6-hexanediol and a 1,6-hexanediol derivative, a compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and / or a derivative thereof (B), The total content of the compound (A) having two or more secondary hydroxyl groups in one molecule is 100 ppm by mass or less relative to the total amount of the 1,6-hexanediol composition, and The total content of 6-hydroxyhexanal and / or its derivative (B) is 1500 ppm by mass or less based on the total amount of the 1,6-hexanediol composition. 6 . A polymer using the 1,6-hexanediol composition according to claim 5 as a reaction raw material.

7. The polymer according to claim 6, wherein The polymer is polyester or polyurethane.

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