1, 6-hexanediol compositions and polymers

Abstract

The purpose of the present invention is to provide a 1, 6-hexanediol composition capable of improving the hydrolysis resistance of a polymer obtained using the 1, 6-hexanediol composition as a reaction raw material, and a polymer obtained by reacting the 1, 6-hexanediol composition. The present invention relates to a 1, 6-hexanediol composition containing an alkali metal element and either or both of 1, 6-hexanediol and a 1, 6-hexanediol derivative, the total content of the alkali metal element being in the range of 0.1-1000 ppm by mass with respect to the total amount of the composition, and the acid value of the composition being in the range of 0.001-1.0 mgKOH / g.

Description

Technical Field

[0001] The present invention relates to 1,6-hexanediol compositions and polymers. Background Art

[0002] 1,6-Hexanediol (1,6-HD) compositions are useful intermediates for making polymers such as polyesters and polyurethanes. 1,6-Hexanediol compositions can generally be made by (1) hydrogenation of adipic acid or a feed stream containing adipic acid, (2) hydrogenation of hydroxycaproic acid or its esters, or (3) hydrogenation of caprolactone.

[0003] Polymers such as polyester and polyurethane obtained by reacting a 1,6-hexanediol composition are widely used in artificial leather and the like.

[0004] Regarding polyurethane, for example, Patent Document 1 discloses that the following polyurethane resin composition has excellent hydrolysis resistance, and is characterized in that it contains a polyester polyol produced using a polyisocyanate, a polyol, and a polycarboxylic acid in the presence of a solid acid catalyst. However, it is necessary to use a special solid catalyst when producing the polyester polyol and to recover the solid catalyst, and the provision of other technologies is also sought.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2010 / 035579 Summary of the invention

[0008] Problems to be solved by the invention

[0009] As the above-mentioned other technology, an object of the present invention is to provide a 1,6-hexanediol composition capable of improving the hydrolysis resistance of a polymer produced using the 1,6-hexanediol composition as a reaction raw material, and a polymer produced using the 1,6-hexanediol composition as a reaction raw material.

[0010] Means for solving problems

[0011] The present inventors have conducted intensive studies and have found that a polymer obtained by reacting a 1,6-hexanediol composition having a specific acid value and containing a specific amount of an alkali metal element has good hydrolysis resistance, thereby completing the present invention.

[0012] That is, the present invention provides the following inventions.

[0013] [1] A 1,6-hexanediol composition comprising one or both of 1,6-hexanediol and a 1,6-hexanediol derivative and an alkali metal element, wherein the total content of the alkali metal element is in the range of 0.1 to 1000 ppm by mass relative to the total amount of the composition, and the acid value of the composition is in the range of 0.001 to 1.0 mgKOH / g.

[0014] [2] The 1,6-hexanediol composition according to [1], further comprising an organic acid, wherein the organic acid has a pKa value of 4.0 or more at 25°C.

[0015] [3] The 1,6-hexanediol composition according to [1] or [2], characterized in that the 1,6-hexanediol composition is derived from a biomass resource.

[0016] [4] A polymer comprising the 1,6-hexanediol composition according to any one of [1] to [3] as a reaction raw material.

[0017] [5] The polymer according to [4], wherein the polymer is polyester or polyurethane.

[0018] Effects of the Invention

[0019] The 1,6-hexanediol composition of the present invention has an acid value of 0.001 to 1.0 mgKOH / g and a total content of alkali metal elements of 0.1 to 1000 mass ppm. Therefore, a polymer produced using the 1,6-hexanediol composition as a reaction raw material has good hydrolysis resistance. DETAILED DESCRIPTION

[0020] <1,6-Hexanediol composition>

[0021] The 1,6-hexanediol composition of the present invention (hereinafter referred to as the composition) contains one or both of 1,6-hexanediol and a 1,6-hexanediol derivative, and an alkali metal element, wherein the total content of the alkali metal element is in the range of 0.1 to 1000 ppm by mass relative to the total amount of the composition, and the acid value of the composition is in the range of 0.001 to 1.0 mgKOH / g.

[0022] <<1,6-Hexanediol, 1,6-Hexanediol derivatives>>

[0023] 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.

[0024] 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 possessed by 1,6-hexanediol contained in the 1,6-hexanediol composition of the present invention. Here, as a method for modifying the hydroxyl group possessed by 1,6-hexanediol, a known method for modifying the hydroxyl group can be used, for example, etherification reaction, esterification reaction, modification with (meth)acrylic acid, etc.

[0025] Examples of the 1,6-hexanediol derivatives include 1,6-hexanediol derivatives containing epoxy groups, such as 1,6-hexanediol diglycidyl ether and 6-hydroxyhexyl glycidyl ether; 1,6-hexanediol derivatives containing (meth)acryloyl groups, such as 1,6-hexanediol di(meth)acrylate, 6-hydroxyhexyl acrylate, and 1,6-hexanediol monoacrylate monomethacrylate; 1,6-hexanediol derivatives containing vinyl ether groups, such as 1,6-hexanediol divinyl ether and 1,6-hexanediol monovinyl ether; 1,6-hexanediol derivatives containing aliphatic alkyl ether groups, such as 6-propoxy-1-hexanol, 1,6-dipropoxy-hexane, 1,6-hexanediol methyl ether, and 1,6-dimethoxyhexane; and 1,6-hexanediol derivatives containing fatty acid ester groups, such as 6-hydroxyhexanoic acid propyl ester, di-n-propyl adipate, 6-hydroxyhexanoic acid methyl ester, and dimethyl adipate. These may be used alone or in combination of two or more.

[0026] In the present 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.

[0027] In the 1,6-hexanediol composition of the present invention, the 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 99.00 to 99.99% by mass, and still more preferably 99.50 to 99.99% by mass. By setting the total content of alkali metal elements within the above range, setting the acid value of the composition within the above range, and setting the purity of the 1,6-hexanediol composition within the above range, the effect of the present invention tends to be more preferably obtained.

[0028] In this specification, the content of 1,6-hexanediol is a value measured by gas chromatography-mass spectrometry (GC-MS).

[0029] <<Alkali metal elements>>

[0030] The composition of the present invention contains alkali metal elements, and the total content of the alkali metal elements is 0.1 to 1000 mass ppm based on the total amount of the composition.

[0031] The alkali metal element is not particularly limited, and examples thereof include lithium, sodium, potassium, rubidium, cesium, etc. These may be used alone or in combination of two or more. Among them, sodium and potassium are preferred.

[0032] 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.

[0033] Specific examples of the alkali metal compound include metal salts of the above-mentioned alkali metal elements and acids such as acetic acid, phosphoric acid, and nitric acid.

[0034] In the 1,6-hexanediol composition of the present invention, the upper limit of the total content of alkali metal elements (preferably the total content of either or both of sodium metal elements and potassium metal elements) is preferably 1000 mass ppm or less. The lower limit of the above-mentioned total content is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, further preferably 100 mass ppm or more, and particularly preferably 500 mass ppm or more. These upper and lower limits can be used in any combination.

[0035] In the 1,6-hexanediol composition of the present invention, the total content of alkali metal elements (preferably the total content of one or both of sodium metal elements and potassium metal elements) is 0.1 to 1000 mass ppm, preferably 1 to 1000 mass ppm, more preferably 100 to 1000 mass ppm, and further preferably 500 to 1000 mass ppm. In this specification, the total content of alkali metal elements is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0036] <<Acid value of 1,6-hexanediol composition of the present invention>>

[0037] The upper limit of the acid value of the 1,6-hexanediol composition of the present invention is preferably 1.0 mgKOH / g or less, more preferably 0.8 mgKOH / g or less, and further preferably 0.6 mgKOH / g or less. The lower limit of the acid value is not particularly limited, but is preferably 0.001 mgKOH / g or more, more preferably 0.01 mgKOH / g or more, and further preferably 0.1 mgKOH / g or more. These upper and lower limits may be used in any combination.

[0038] The acid value of the 1,6-hexanediol composition of the present invention is 0.001 to 1.0 mgKOH / g, preferably 0.01 to 0.8 mgKOH / g, and more preferably 0.1 to 0.6 mgKOH / g.

[0039] When the acid value exceeds the upper limit, when the 1,6-hexanediol composition is used to make a polymer (such as polyester), the performance of the designed polymer (such as polyester) may not be exhibited. In addition, when the acid value is less than the lower limit, the reactivity may be reduced when the 1,6-hexanediol composition is used to synthesize a polymer (such as polyester, polyurethane). If it is within the range, the promotion of the hydrolysis reaction of the polymer (such as polyester) can be appropriately suppressed.

[0040] In this specification, the acid value is a value measured according to JIS K 0070-1992.

[0041] <<Organic Acid>>

[0042] The 1,6-hexanediol composition of the present invention preferably further contains an organic acid having a pKa value of 4.0 or more at 25° C. Thereby, there is a tendency that the effects of the present invention can be more preferably obtained.

[0043] As for the above-mentioned organic acid, there is no particular limitation as long as the pKa value at 25° C. is 4.0 or more, and examples thereof include acetic acid (pKa value 4.56), succinic acid (pKa value 4.00), propionic acid (pKa value 4.67), adipic acid (pKa value 4.26), valeric acid (pKa value 4.64), pivalic acid (pKa value 5.03), catechol (pKa value 9.23), phenol (pKa value 9.82), etc. These may be used alone or in combination of two or more. Among them, acetic acid and succinic acid are preferred, and acetic acid is more preferred.

[0044] In addition, there are compounds showing two or more pKa values ​​among organic acids, but in the present invention, the pKa value of the compound in this case is the lowest value.

[0045] The pKa value of the organic acid at 25°C is 4.0 or more, preferably 4.0 to 10.0, more preferably 4.0 to 8.0, further preferably 4.0 to 6.0, and particularly preferably 4.0 to 5.0. As a result, there is a tendency to obtain the effect more appropriately. In this specification, the pKa value of the organic acid at 25°C is a value measured by neutralization titration. As organic acids having a pKa value of 4.0 or more at 25°C, for example, organic acids described in Chemical Handbook (Basic Edition) Revised 4th Edition, II-317 to II-321, Maruzen Publishing (1993) can be cited.

[0046] In the 1,6-hexanediol composition of the present invention, the content of the organic acid having a pKa value of 4.0 or more at 25°C is sufficient as long as the acid value of the composition of the present invention is within the above numerical range. In the 1,6-hexanediol composition of the present invention, the upper limit of the content of the organic acid having a pKa value of 4.0 or more at 25°C is preferably 2000 mass ppm or less, more preferably 1000 mass ppm or less, and further preferably 500 mass ppm or less. The lower limit of the above content is not particularly limited, but is preferably 0.001 mass ppm or more, more preferably 0.01 mass ppm or more, further preferably 0.05 mass ppm or more, and particularly preferably 0.1 mass ppm or more. These upper and lower limits may be used in any combination.

[0047] When the 1,6-hexanediol composition of the present invention is derived from biomass resources, the content of the organic acid having a pKa value of 4.0 or more at 25° C. is preferably 1 to 2000 mass ppm, and more preferably 10 to 1000 mass ppm, from the perspective of economic efficiency of the purification process. In the 1,6-hexanediol composition of the present invention, the content of the organic acid having a pKa value of 4.0 or more at 25° C. is preferably 0.001 to 2000 mass ppm, more preferably 0.001 to 1000 mass ppm, further preferably 0.01 to 500 mass ppm, and particularly preferably 0.1 to 500 mass ppm. As a result, there is a tendency that the effect of the present invention can be more preferably obtained.

[0048] Here, when a plurality of organic acids are contained, the content of the organic acid refers to the total content. The same applies to the contents of other components. In addition, the content of the organic acid in the 1,6-hexanediol composition refers to the content of the free organic acid in principle, but may also include the content of the organic acid in the form of a salt.

[0049] If an organic acid having a pKa value of less than 4.0 at 25°C is present in the 1,6-hexanediol composition, such an organic acid is easily oxidized to form an aldehyde, and a polymer such as polyester may be colored or generate an odor. In addition, in 1,6-hexanediol derived from biomass resources, amino acids are likely to remain as organic acids having a pKa value of less than 4.0, and if these amino acids are present, a polymer such as polyester or polyurethane may be colored.

[0050] Therefore, in the 1,6-hexanediol composition of the present invention, the content of the organic acid having a pKa value of less than 4.0 at 25° C. is preferably 2000 mass ppm or less, more preferably 1000 mass ppm or less, further preferably 500 mass ppm or less, and particularly preferably 0 mass ppm (not blended).

[0051] In this specification, the content of the organic acid is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0052] The organic acid having a pKa value of less than 4.0 at 25°C is not particularly limited as long as the pKa value at 25°C is less than 4.0, and examples thereof include glycine (pKa value 2.36), alanine (pKa value 2.30), valine (pKa value 2.26), leucine (pKa value 2.35), isoleucine (pKa value 2.21), serine (pKa value 2.13), cysteine ​​(pKa value 1.88), methionine (pKa value 2.15 ), aspartic acid (pKa value 1.93), asparagine (pKa value 2.14), glutamic acid (pKa value 2.18), glutamine (pKa value 2.17), arginine (pKa value 2.05), lysine (pKa value 2.04), histidine (pKa value 1.70), phenylalanine (pKa value 2.26), tyrosine (pKa value 2.17), tryptophan (pKa value 2.35), proline (pKa value 1.90) and the like. These may be used alone or in combination of two or more.

[0053] When an organic acid having a pKa value of less than 4.0 at 25° C. is used, it is desirable to use an organic acid that does not contain a nitrogen atom and has a pKa value as high as possible.

[0054] The 1,6-hexanediol composition of the present invention can be manufactured in such a manner that the total content of alkali metal elements reaches the above range. For example, the total content of alkali metal elements in the commercially available 1,6-hexanediol composition is less than 0.1 mass ppm, so the total content of alkali metal elements can be adjusted to the above range by adding an acid such as acetic acid, phosphoric acid, nitric acid and a metal salt of an alkali metal to the commercially available 1,6-hexanediol composition. Similarly, the acid value of the commercially available 1,6-hexanediol composition is 0, so an acid (preferably an organic acid having a pKa value of 4.0 or more at 25°C) is added to the commercially available 1,6-hexanediol composition to adjust the acid value to the above range. Here, if the amount of acid added is increased, the acid value also increases.

[0055] By setting the content of the alkali metal element and the acid value in the composition of the present invention to the above ranges, a polymer (such as polyester, polyurethane having an ester bond, etc.) using the 1,6-hexanediol composition as a reaction raw material has good hydrolysis resistance. The reason for exerting such an effect is not clear, but it is speculated as follows.

[0056] Generally, when polyester is heated in the presence of water, the catalyst residue during the dehydration condensation reaction coordinates and bonds with the ester bond portion of the polyester, and a hydrolysis reaction of the ester occurs, and the alkali metal element inhibits the coordination of the catalyst residue with the ester portion of the polyester. Thus, the hydrolysis of the polyester and the polyurethane having an ester bond can be appropriately suppressed, and good hydrolysis resistance can be obtained.

[0057] On the other hand, when the composition contains a large amount of alkali metal elements, there is a possibility that the alkali metal elements may coordinate with the catalyst when synthesizing a polymer such as polyester, thereby reducing the original effect of the catalyst, that is, the effect of increasing the rate of the polymerization reaction. Therefore, in the 1,6-hexanediol composition of the present invention, by containing only a specific amount of alkali metal elements, it is possible to suppress the original effect of the catalyst from being excessively reduced by the alkali metal elements, so that no adverse effects are caused when synthesizing a polymer such as polyester or polyurethane.

[0058] Therefore, the 1,6-hexanediol composition of the present invention has a specific acid value and contains a specific amount of alkali metal elements, so that good hydrolysis resistance can be imparted to the polymer, and no adverse effect is generated when synthesizing polymers such as polyesters and polyurethanes. The polymer (for example, polyester, polyurethane having an ester bond) obtained by reacting the 1,6-hexanediol composition has good hydrolysis resistance.

[0059] <1,6-Hexanediol composition derived from biomass resources>

[0060] In recent years, environmental awareness has increased, and raw materials derived from biomass resources such as plants are desired, rather than raw materials derived from petroleum that affect global warming. Biomass resources refer to reusable organic resources produced from animals and plants. Preferred resources are plant resources such as wood, rice straw, rice husk, rice bran, ancient rice, corn, sugarcane, cassava, soybeans, bean curd residue, bagasse, vegetable oil, grease, waste paper, and papermaking residues. These biomass resources usually contain many alkali metal elements and alkaline earth metal elements such as nitrogen, sodium, potassium, magnesium, and calcium. In addition, a method for obtaining raw materials derived from biomass resources from biomass resources using microorganisms such as coryneform bacteria and Escherichia coli is also disclosed. In the present invention, for example, a 1,6-hexanediol composition derived from biomass resources obtained by the manufacturing method described in Japanese Patent Publication No. 2020-114227 can also be appropriately used. 1,6-hexanediol compositions derived from biomass resources such as 1,6-hexanediol compositions derived from biomass resources can also be used. In the case of fermentation based on microorganisms, in order to effectively carry out fermentation, a neutralizer is usually used to adjust the hydrogen ion concentration (pH) of the fermentation liquid. Many alkali metal elements and alkaline earth metals are contained in the neutralizer and the culture solution. In addition, the results of in-depth research by the present inventors have made it clear that in the 1,6-hexanediol derived from biomass resources obtained by the manufacturing method described in Japanese Patent Gazette No. 2020-114227, organic acids such as acetic acid and succinic acid are mixed in as impurities. If the cost permits, these impurities are removed as unnecessary impurities using a purification method. However, the results of in-depth research by the present inventors have made it clear that organic acids and alkali metal elements are not unnecessary as components coexisting with 1,6-hexanediol, and the coexistence of a specific amount is instead an essential component for improving the hydrolysis resistance of polymers such as polyesters. By combining known purification methods, a 1,6-hexanediol composition having a total content of alkali metal elements within the above range and an acid value within the above range can be obtained.

[0061] <Polymer>

[0062] The polymer of the present invention uses the 1,6-hexanediol composition of the present invention as a reaction raw material.

[0063] The polymer is not particularly limited as long as it is a polymer having a structural unit derived from the 1,6-hexanediol composition of the present invention, and includes oligomers. For example, polyesters, polyurethanes, polycarbonates, polyethers, epoxy polymers using the above-mentioned epoxy-containing 1,6-hexanediol derivatives as raw materials, acrylic polymers using the above-mentioned (meth)acryloyl-containing 1,6-hexanediol derivatives as raw materials, etc. can be mentioned. These can be used alone or in combination of two or more.

[0064] Among them, polyester, polyurethane, polycarbonate, and polyether are preferred, polyester, polyurethane, and polyether are more preferred, and polyester and polyurethane are further preferred because the effect of improving hydrolysis resistance can be more suitably exhibited.

[0065] It should be noted that the polymer of the present invention has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, and contains an alkali metal element and an organic acid derived from the 1,6-hexanediol composition. Here, in this specification, the polymer of the present invention contains an organic acid, and in addition to the embodiment in which the polymer of the present invention contains a free organic acid, it also includes an embodiment in which a structural unit derived from an organic acid is present in the polymer skeleton. This is because there is also a case in which an acid such as an organic acid is introduced into the polymer skeleton during polymerization.

[0066] The content of the structural unit 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.

[0067] In this specification, the content of each structural unit in a polymer is measured by NMR.

[0068] In the polymer of the present invention, the total content of alkali metal elements (preferably the total content of one or both of sodium metal elements 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. This tends to more preferably achieve the effects of the present invention.

[0069] In the polymer of the present invention, the content of the organic acid having a pKa value of 4.0 or more at 25°C is preferably 0.001 to 1000 mass ppm, more preferably 0.001 to 500 mass ppm, and even more preferably 0.05 to 250 mass ppm. This tends to provide more favorable effects.

[0070] Here, as described above, in this specification, the polymer of the present invention contains an acid, which includes not only a mode in which the polymer of the present invention contains a free organic acid, but also a mode in which the polymer skeleton has a structural unit derived from an organic acid. Therefore, the content of the organic acid includes the content of the free organic acid and the content of the structural unit derived from the organic acid present in the polymer skeleton.

[0071] In the polymer of the present invention, the content of the organic acid having a pKa value of less than 4.0 at 25° C. is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, further preferably 250 mass ppm or less, and particularly preferably 0 mass ppm (not blended). This can suppress coloration of the polymer.

[0072] The above polymer may be modified. There is no particular limitation on the modification, and examples thereof include the modifications described in the 1,6-hexanediol derivatives. They may be used alone or in combination of two or more. Among them, modification using (meth)acrylic acid is preferred. In particular, when the above polymer is a polyester, modification using (meth)acrylic acid is preferred.

[0073] The number average molecular weight (Mn) of the polymer of the present invention is preferably 500 to 1,000,000, and more preferably 3,000 to 500,000. In addition, in the present specification, the number average molecular weight (Mn) of the polymer is a value measured by gel permeation chromatography (GPC).

[0074] 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.

[0075] <<Polyester>>

[0076] The polyester of the present invention is a compound using the 1,6-hexanediol composition of the present invention as a reaction raw material.

[0077] Specifically, the polyester of the present invention is a polycondensate synthesized by forming an ester bond by dehydration condensation of a carboxylic acid and an alcohol, and at least the 1,6-hexanediol composition of the present invention is used as the alcohol. Therefore, the polyester of the present invention is a reaction product (polycondensate) obtained by the polycondensation reaction of a carboxylic acid and an alcohol, and the polyester of the present invention has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, and contains an alkali metal element and an organic acid derived from the 1,6-hexanediol composition.

[0078] The polyester of the present invention is preferably a polyester polyol.

[0079] Examples of the polyester polyol include condensation polyester polyols and lactone polyester polyols. Examples of the condensation polyester polyols include reaction products of low molecular weight polyols (such as ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-) butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, 1,4-cyclohexanedimethanol and other low molecular weight polyols, saccharides such as sorbitol, etc.) and polycarboxylic acids (Japanese: polyvalent carboxylic acids) (such as 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, oligomer acid, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, etc.). Examples of the lactone polyester polyols include polycaprolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, etc.

[0080] Examples of the above carboxylic acids include 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; 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-cyclohexanedicarboxylic acid); 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; aliphatic monocarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid, acrylic acid, methacrylic acid; aromatic monocarboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid; fatty acids derived from various animal and vegetable oils such as soybean oil fatty acid, tall oil fatty acid, linoleic acid, eicosapentaenoic acid; and their acid anhydrides, etc. They can be used alone or in combination of two or more. Among them, aliphatic polycarboxylic acids are preferred, and dodecanedicarboxylic acid is more preferred.

[0081] The alcohols other than the 1,6-hexanediol composition of the present invention can be used as long as they are compounds having a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group) without particular limitation. Examples of the above alcohols include aliphatic monohydric alcohols such as ethanol, butanol, 2-ethylhexanol; aliphatic polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane; aromatic mono / polyhydric phenols such as phenol, cresol, bisphenol-A; and their ethylene oxide adducts (Japanese: adducts), hydrogenated alicyclics, etc. They can be used alone or in combination of two or more.

[0082] The content of the 1,6-hexanediol composition of the present invention in 100% by mass of the alcohol is preferably 10 to 100% by mass, and more preferably 50 to 100% by mass. This tends to provide more suitable effects.

[0083] The polyester of the present invention can be obtained by a known polyester production method. Specifically, it can be synthesized by a production method in which the carboxylic acid and the alcohol are reacted at a reaction temperature of 150 to 280° C. while removing the generated water to the outside of the system. In addition, a reaction catalyst, an antioxidant, etc. can also be used in combination during the synthesis.

[0084] 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, and more preferably 20 to 70% by mass. This tends to achieve more suitable effects. In this specification, the content of each structural unit in the polyester is measured by NMR.

[0085] In the polyester of the present invention, the total content of alkali metal elements (preferably the total content of one or both of sodium metal elements and potassium metal elements) is preferably 0.05 to 500 mass ppm, more preferably 0.05 to 400 mass ppm, and further preferably 0.05 to 300 mass ppm.

[0086] This tends to result in more favorable effects.

[0087] In the polyester of the present invention, the content of the organic acid having a pKa value of 4.0 or more at 25°C is preferably 0.001 to 1000 mass ppm, more preferably 0.001 to 500 mass ppm, and even more preferably 0.05 to 250 mass ppm. This tends to provide more favorable effects.

[0088] In the polyester of the present invention, the content of the organic acid having a pKa value of less than 4.0 at 25°C is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, further preferably 250 mass ppm or less, and particularly preferably 0 mass ppm (not compounded). This can suppress coloration. Here, as described above, in this specification, the so-called polymer of the present invention contains an acid, and in addition to the mode in which the polymer of the present invention contains a free organic acid, it also includes a mode in which the polymer skeleton has a structural unit derived from an organic acid. Therefore, the content of the organic acid includes the content of the free organic acid and the content of the structural unit derived from the organic acid present in the polymer skeleton.

[0089] The number average molecular weight (Mn) of the polyester of the present invention is preferably 500 to 120,000, and more preferably 3,000 to 50,000. In addition, in the present specification, the number average molecular weight (Mn) of the polyester is a value measured by gel permeation chromatography (GPC).

[0090] <<Polyurethane>>

[0091] 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. In addition, a polyol not using the 1,6-hexanediol composition as a reaction raw material, a chain extender, a chain terminator, a crosslinking agent, etc. may be used in combination as a reaction raw material for the polyurethane of the present invention as needed.

[0092] Therefore, the polyurethane of the present invention has structural units derived from polyols and structural units derived from polyisocyanates, has structural units derived from at least the 1,6-hexanediol composition of the present invention, and optionally contains an alkali metal or an organic acid contained in the 1,6-hexanediol composition of the present invention.

[0093] Examples of the polyol include polycarbonate polyol, polyether polyol, polyester polyol, etc. These polyols may or may not use a 1,6-hexanediol composition as a reaction raw material. The polyurethane of the present invention may use at least a polyol using a 1,6-hexanediol composition as a reaction raw material as a reaction raw material.

[0094] Polycarbonate polyol is a polyol obtained by the reaction of a diol and a carbonate. Examples of the diol include 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-butylene glycol, 1,4-butylene glycol, neopentyl glycol, pentylene glycol, 3-methyl-1,5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, tripropylene glycol, polytetramethylene ether glycol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl 1,3-propanediol, and alicyclic diols such as 1,4-cyclohexanediglycol and 1,4-cyclohexanedimethanol.

[0095] Examples of carbonate esters include dialkyl carbonates (dimethyl carbonate, diethyl carbonate, etc.), ethylene carbonate, and diphenyl carbonate.

[0096] Polyether polyols are, for example, polyether polyols obtained by addition polymerization of alkylene oxides using various diols as initiators. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc. Examples of various diols include the same diols as those of the polycarbonate diols described above.

[0097] As the polyol, in addition to the above-mentioned 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.

[0098] 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 can be used; water; 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). Regarding these chain extenders, chain extenders derived from biomass resources can also be used. These chain extenders can be used alone or in combination of two or more. Among them, neopentyl glycol, 1,4-butanediol, trimethylolpropane, isophoronediamine, and 4,4'-methylenebis(2-chloroaniline) are more preferred.

[0099] As the polyol, it is particularly preferable to use a polyester polyol made from the composition of the present invention. The content of the polyester polyol 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.

[0100] 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, and toluene diisocyanate; aliphatic polyisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate Isocyanates; alicyclic polyisocyanates such as 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, etc. Regarding these polyisocyanates, polyisocyanates derived from biomass resources can also be used. They can be used alone or in combination of two or more. Among them, aromatic polyisocyanates are preferred, and 4,4'-diphenylmethane diisocyanate and toluene diisocyanate are more preferred.

[0101] For the purpose of controlling the molecular weight of the obtained polyurethane, a chain terminator having one active hydrogen group may be used as required. Examples of these chain terminators include aliphatic monohydroxy compounds such as methanol, ethanol, propanol, butanol and hexanol having a hydroxyl group, and aliphatic monoamines such as morpholine, diethylamine, dibutylamine, monoethanolamine and diethanolamine having an amino group. These may be used alone or in combination of two or more.

[0102] For the purpose of improving the heat resistance and strength of the obtained polyurethane, a crosslinking agent having three or more active hydrogen groups or an isocyanate group may be used as necessary.

[0103] The polyurethane of the present invention can be obtained by a known method for producing polyurethane. Specifically, for example, a method for producing by adding the above-mentioned polyol, the above-mentioned polyisocyanate and the above-mentioned chain extender and reacting them can be cited. These reactions are preferably carried out at a temperature of 50 to 100° C. for 3 to 10 hours. In addition, the above-mentioned reaction can be carried out in an organic solvent.

[0104] As the organic solvent, for example, 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, isopropanol, and butanol can be used. In addition, these organic solvents can also be organic solvents derived from biomass resources. These organic solvents can be used alone or in combination of two or more.

[0105] When the polyurethane is made of a polyester polyol made of the 1,6-hexanediol composition of the present invention, the content of the structural unit 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 suitable effects.

[0106] The content of the structural unit 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.

[0107] In this specification, the content of each structural unit in the polyurethane is measured by NMR.

[0108] In the polyurethane of the present invention, the total content of alkali metal elements (preferably the total content of one or both of sodium metal elements and potassium metal elements) is preferably 0.05 to 500 mass ppm, more preferably 0.05 to 400 mass ppm, and further preferably 0.05 to 300 mass ppm.

[0109] In the polyurethane of the present invention, the content of the organic acid having a pKa value of 4.0 or more at 25°C is preferably 0.001 to 1000 mass ppm, more preferably 0.001 to 500 mass ppm, and even more preferably 0.05 to 250 mass ppm. This tends to provide more favorable effects.

[0110] In the polyurethane of the present invention, the content of the organic acid having a pKa value of less than 4.0 at 25°C is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, further preferably 250 mass ppm or less, and particularly preferably 0 mass ppm (not mixed). Thus, coloring can be suppressed. Here, as described above, in this specification, the so-called polymer of the present invention contains an acid, in addition to the mode in which the polymer of the present invention contains a free organic acid, and also includes a mode in which the polymer skeleton has a structural unit derived from an organic acid. Therefore, the content of the organic acid includes the content of the free organic acid and the content of the structural unit derived from the organic acid present in the polymer skeleton.

[0111] 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 a value measured by gel permeation chromatography (GPC).

[0112] The polymer of the present invention can be used for various purposes. Specifically, it can be used for a wide range of purposes such as artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, coatings, laminating adhesives, elastic fibers, urethane raw materials, automobile parts, sporting goods, vibration-proof materials, vibration-damping materials, fiber treatment agents, adhesives, etc.

[0113] The polyester of the present invention can be used for various purposes. Specifically, it can be used for solvent-based, water-based, powder, metal, automobile, woodworking, and plastic coatings; packaging materials, containers, optical films, and modifiers for molded products; the surface layer, middle layer, foam layer, and adhesive layer of artificial leather and synthetic leather; adhesives such as laminating adhesives; shoes, thermoplastic resins, foamed resins, thermosetting resins, elastic fibers, polyurethane raw materials, automobile parts, sports goods, and other wide applications.

[0114] The polyurethane of the present invention can be used for various purposes. Specifically, it can be used for the surface layer, middle layer, foam layer, and adhesive layer of artificial leather and synthetic leather; various coating agents such as paint, metal surface treatment agent, and film primer; binders for inkjet, ink, printing and dyeing, and glass fiber bundling agent; adhesives such as shoes, thermoplastic resins, foamed resins, thermosetting resins, and laminating adhesives, vibration-proof materials, vibration-damping materials, automobile parts, sports goods, and fiber treatment agents, etc.

[0115] The epoxy polymers produced from the epoxy-containing 1,6-hexanediol derivatives can be used in a variety of applications, including coatings, metal surface treatment agents, and other coating agents, as well as molded articles such as windmill base resins.

[0116] The acrylic polymers made from the (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, such as coatings, metal surface treatment agents, film coating agents, and adhesives for inks and UV inkjet.

[0117] 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.

[0118] It should be noted that, in this specification, the expression of "~" means more than the value before the description of "~" and less than the value after the description of "~". In addition, in this specification, with respect to a certain characteristic, when multiple numerical ranges are disclosed by the expression of "~", 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.

[0119] [Example]

[0120] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0121] (Example 1: Preparation of 1,6-hexanediol composition 1 (1,6-HD composition 1))

[0122] 1,6-hexanediol manufactured by Ube Industries, Ltd., having an alkali metal element content of 0.02 mass ppm of sodium and an acid value of 0 mgKOH / g in ICP-MS analysis, was heated to melt at 80°C, potassium acetate was added in such a manner that potassium became 1.7 mass ppm, and 15 mass ppm of acetic acid was further added. The mixed substance was cooled to obtain 1,6-hexanediol composition 1. The acid value of 1,6-hexanediol composition 1 was 0.02 mgKOH / g.

[0123] (Example 2: Preparation of 1,6-hexanediol composition 2 (1,6-HD composition 2))

[0124] 1,6-hexanediol manufactured by Ube Industries, Ltd., having an alkali metal element content of 0.02 ppm sodium and an acid value of 0 mgKOH / g in ICP-MS analysis, was heated to melt at 80°C, sodium acetate was added in such a manner that the sodium content was 995 mass ppm, and 400 mass ppm of acetic acid was further added. The mixed substance was cooled to obtain 1,6-hexanediol composition 2. The acid value of 1,6-hexanediol composition 2 was 0.48 mgKOH / g.

[0125] (Example 3: Preparation of 1,6-hexanediol composition 3 (1,6-HD composition 3))

[0126] 1,6-hexanediol manufactured by Ube Industries, Ltd., having an alkali metal element content of 0.02 mass ppm of sodium and an acid value of 0 mgKOH / g in ICP-MS analysis, was heated to melt at 80°C, potassium acetate was added in such a manner that potassium became 998 mass ppm, and 200 mass ppm of succinic acid was further added. The mixed substance was cooled to obtain 1,6-hexanediol composition 3. The acid value of 1,6-hexanediol composition 3 was 0.11 mgKOH / g.

[0127] (Production Example 1) (Production of genetically modified Escherichia coli)

[0128] Plasmid A was prepared by introducing the glycerol dehydrogenase α, β, and γ subunit genes and the dehydrogenase reactivation factor gene derived from Citrobacter freundii into pACYC184 (Nippon Gene Co., Ltd.) between the BamHI and HindIII restriction enzyme cleavage sites.

[0129] The HpaI gene derived from Escherichia coli as 4,6-dihydroxy-2-oxohexanoic acid aldolase, the HpcG gene derived from Escherichia coli as 4,6-dihydroxy-2-oxohexanoic acid 4-dehydrogenase, the NADPH-dependent oxidoreductase2-alkenal reductase (GenBank: CAC01710.1) gene derived from Arabidopsis thaliana as 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase, the PanE gene of Lactococcus lactis as 6-hydroxy-2-oxohexanoic acid 2-reductase, and the HadA gene derived from Clostridium difficile as 2,6-dihydroxy-hexanoic acid CoA-transferase and 6-hydroxyhexanoyl-CoA-transferase were introduced between the BamHI and EcoRI restriction enzyme cleavage sites of the multiple cloning site (MCS) of pUC19 (Nippon Gene Co., Ltd.) to prepare plasmid B.

[0130] The HadB and HadC genes from Clostridium difficile as the α and β subunit genes of 2-hydroxyisohexanoyl-CoA dehydrogenase, the HadI gene from Clostridium difficile as the 2-hydroxyisohexanoyl-CoA dehydrogenase activating enzyme, the trans-2-enoyl-CoA reductase gene (GenBank: AE017248) from Treponema denticola as the 6-hydroxy-2,3-dehydro-hexanoyl-CoA2,3-reductase, and the trans-2-enoyl-CoA reductase gene (GenBank: AE017248) from Treponema denticola as the 6-hydroxyhexanoic acid 1-reductase The carboxylic acid reductase gene (GenBank: AAR91681.1) derived from Nocardia iocardia 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 other genes were introduced into MCS2 to prepare plasmid C.

[0131] The gene in this item refers to a decipherable frame including a stop codon encoding each enzyme, and each gene is introduced into a plasmid in such a manner that a sequence including a T7 promoter and a ribosome binding site is present upstream and a sequence including a T7 terminator is present downstream. Each gene can be expressed in large quantities in a host strain Escherichia coli such as T7 RNA polymerase by appropriate expression induction.

[0132] Plasmids A, B, and C were sequentially transformed into chemically competent BL21 Star (DE3) (Invitrogen) cells by heat shock method, and selection was performed on LB plates containing appropriate antibiotics. As a result, BL21 Star (DE3) strains containing all plasmids A, B, and C were obtained. Thus, Escherichia coli having genes encoding 10 enzymes of the 1,6-hexanediol pathway were prepared, and the 10 enzymes were 4,6-dihydroxy-2-oxohexanoic acid aldolase (2A in the figure of Japanese Patent No. 6680671), 4,6-dihydroxy-2-oxohexanoic 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 6-hydroxy-2-oxohexanoic acid 2-reductase (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-dehydrogenation-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-hydroxyhexanoic acid 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).

[0133] (Example 4: Preparation of 1,6-hexanediol composition 4 (1,6-HD composition 4))

[0134] The above-mentioned E. coli was inoculated into an autoclave-sterilized 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, and glucose and glycerol are raw materials derived from biomass resources) and cultured at 30°C under aerobic conditions for 2 to 3 hours. Then, when the optical density of E. coli at 600 nm reached 0.3 to 0.6, isopropyl-β-thiogalactoside was added to a final concentration of 0.5mM, and iron (II) sulfate was added to a final concentration of 10μM, and 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) was added, and the culture vessel was placed under a nitrogen atmosphere, thereby setting anaerobic conditions. Under these conditions, culture was performed at 30°C for 48 hours to produce 1,6-hexanediol. The culture solution was centrifuged at 4°C for 20 minutes, and the supernatant was recovered and filtered using an appropriate membrane filter having a pore size of 0.2 to 0.4 μm to obtain a 1,6-hexanediol composition as a filtrate.

[0135] [Purification of 1,6-hexanediol composition]

[0136] <Step (a): Ion exchange to remove cations>

[0137] The cations contained in the 1,6-hexanediol composition are removed. Step (a) is to perform cation exchange in an intermittent manner. The temperature for contact with the cation exchange resin is set to 40°C, and DIAION SK1BH manufactured by Mitsubishi Chemical Co., Ltd. is added to the 1,6-hexanediol composition as a cation exchange resin, and stirred for 3 hours. After stirring, the mixture is filtered to obtain a 1,6-hexanediol composition A as a filtrate.

[0138] <Step (b): Ion exchange to remove anions>

[0139] Anions contained in the 1,6-hexanediol composition A were removed. In step (b), anion exchange was performed in a batch process. The temperature for contact with the anion exchange resin was set to 40° C., and DIAION SA10AOH manufactured by Mitsubishi Chemical Co., Ltd. was added to the 1,6-hexanediol composition as an anion exchange resin, and stirred for 3 hours. After stirring, filtration was performed to obtain a 1,6-hexanediol composition B as a filtrate.

[0140] <Step (c): Step of removing water>

[0141] Remove water contained in the 1,6-hexanediol composition. As the apparatus for step (c), a thin-film distiller is used. The jacket temperature is set to 70°C, and a composition containing 1,6-hexanediol is continuously introduced to distill water from the top. While distilling the water, the dehydrated 1,6-hexanediol composition C is continuously extracted from the bottom in the form of a bottom liquid. The water concentration in the 1,6-hexanediol composition C is 0.020% by mass (200 ppm by mass).

[0142] <Step (d): Distillation separation of low boiling point components>

[0143] The components with a boiling point lower than 1,6-hexanediol contained in the 1,6-hexanediol composition C are removed by a continuous distillation tower. As the distillation tower of step (d), an Oldershaw distillation tower is used. The 1,6-hexanediol composition C obtained in step (c) is continuously supplied to the distillation tower, and the tower top temperature is controlled to a constant temperature of 240°C. Continuous distillation is performed from the top of the tower, and continuous extraction is performed from the bottom of the tower to remove the low-boiling-point components in the 1,6-hexanediol composition C, and the 1,6-hexanediol composition D from which the components with a boiling point lower than 1,6-hexanediol are removed is taken out from the bottom of the tower.

[0144] <Step (e): Distillation separation of high boiling point components>

[0145] The components with a boiling point higher than 1,6-hexanediol contained in the 1,6-hexanediol composition D were removed by a continuous distillation tower. As the distillation tower of step (e), an Oldershaw distillation tower was used. The 1,6-hexanediol composition D obtained in step (d) was continuously supplied to the distillation tower, and the tower bottom temperature was controlled to be constant at 260°C. The high-boiling-point components in the 1,6-hexanediol composition D were removed by continuous extraction from the bottom of the tower. The 1,6-hexanediol composition E (tower top distillate) from which the components with a boiling point higher than 1,6-hexanediol were removed was obtained from the top of the tower. Potassium acetate was added to the 1,6-hexanediol composition E in such a way that the potassium metal element concentration in the ICP-MS analysis was 110 mass ppm, and sodium acetate was added in such a way that the sodium metal element concentration was 190 mass ppm, and 1,6-hexanediol composition 4 (1,6-HD composition 4) was prepared.

[0146] (Example 5: Preparation of 1,6-hexanediol composition 5 (1,6-HD composition 5))

[0147] 1,6-hexanediol manufactured by Ube Industries, Ltd., having an alkali metal element content of 0.02 mass ppm of sodium and an acid value of 0 mgKOH / g in ICP-MS analysis, was heated to melt at 80°C, potassium acetate was added in such a manner that the potassium content became 500 mass ppm, and 1000 mass ppm of acetic acid was further added, and the mixed substance was cooled to obtain 1,6-hexanediol composition 5. The acid value of 1,6-hexanediol composition 5 was 0.95 mgKOH / g.

[0148] (Comparative Example 1: Preparation of 1,6-hexanediol composition 6 (1,6-HD composition 6))

[0149] 1,6-hexanediol produced by Ube Industries, Ltd., whose alkali metal content was 0.02 ppm sodium and acid value was 0 mgKOH / g, was used as it is in ICP-MS analysis. The purity of the 1,6-hexanediol used was 99.93% in gas chromatography analysis, and no peak other than 1,6-hexanediol was observed.

[0150] (Comparative Example 2: Preparation of 1,6-hexanediol composition 7 (1,6-HD composition 7))

[0151] 1,6-hexanediol manufactured by Ube Industries, Ltd., having an alkali metal element content of 0.02 mass ppm of sodium and an acid value of 0 mgKOH / g in ICP-MS analysis, was heated to melt at 80°C, sodium hydroxide was added so that the sodium content was 997 mass ppm, and the mixed substance was cooled to obtain 1,6-hexanediol composition 7. The acid value of 1,6-hexanediol composition 7 was 0 mgKOH / g.

[0152] (Comparative Example 3: Preparation of 1,6-hexanediol composition 8 (1,6-HD composition 8))

[0153] 1,6-hexanediol composition 8 (1,6-HD composition 8) was obtained in the same manner as in Example 4, except that potassium acetate was added to the 1,6-hexanediol composition E of Example 4 so that the potassium metal element concentration became 610 mass ppm and sodium acetate was added to the 1,6-hexanediol composition E of Example 4 so that the sodium metal element concentration became 190 mass ppm.

[0154] (Comparative Example 4: Preparation of 1,6-hexanediol composition 9 (1,6-HD composition 9))

[0155] 1,6-hexanediol manufactured by Ube Industries, Ltd., having an alkali metal element amount of 0.02 mass ppm of sodium and an acid value of 0 mgKOH / g in ICP-MS analysis, was heated and melted at 80°C, 200 mass ppm of succinic acid was added, and the mixed substance was cooled to obtain 1,6-hexanediol composition 9. The acid value of 1,6-hexanediol composition 9 was 0.11 mgKOH / g.

[0156] Tables 1 and 2 show the analysis results of the 1,6-hexanediol compositions obtained in the above-mentioned Examples and Comparative Examples.

[0157] In addition, in Table 1 and Table 2, the detection limits of potassium metal element and sodium metal element are 0.003 mass ppm and 0.003 mass ppm, respectively.

[0158] [Table 1]

[0159]

[0160] [Table 2]

[0161]

[0162] <Polyester Synthesis Example>

[0163] (Synthesis of polyester (A-1))

[0164] In a reaction vessel having a stirring rod, a temperature sensor, and a distillation tube, 1048.5 parts by mass of 1,6-hexanediol composition 1 and 2093.4 parts by mass of dodecanedioic acid (manufactured by INVISTA) were added, and the mixture was stirred while flowing dry nitrogen in the reaction vessel, and the generated water was distilled out of the system at 190-210°C under normal pressure, while a dehydration condensation reaction was performed. When the acid value of the reactant reached 30 or less, 16 mg of tetraisopropyl titanate was added, and the reaction was continued while the pressure was reduced to 200-100 mmHg. When the acid value became 1.0, the vacuum was slowly increased using a vacuum pump to complete the reaction. In this way, a polyester A-1 with a hydroxyl value of 37.4 mgKOH / g, an acid value of 0.01 mgKOH / g, and a number average molecular weight (Mn) of 3000 was obtained.

[0165] (Synthesis of Polyesters A-2 to 9)

[0166] Polyesters A-2 to A-9 were synthesized in the same manner as for 1,6-HD compositions 2 to 9. When 1,6-HD compositions 7 and 8 were used, the reaction did not proceed smoothly, and thus the reaction was terminated.

[0167] Tables 3 and 4 show the analysis results of the polyesters obtained in the above-mentioned Examples and Comparative Examples.

[0168] (Evaluation of Hydrolysis Resistance of Polyester [Hydrolysis Resistance])

[0169] The obtained polyester was immersed in hot water at 100° C. for 4 days, and the increase in acid value due to hydrolysis was determined to evaluate hydrolysis resistance.

[0170] [Table 3]

[0171]

[0172] [Table 4]

[0173]

[0174] <Polyurethane Synthesis Example>

[0175] (Synthesis of polyurethane (A-3))

[0176] In a four-necked flask equipped with a thermometer, a stirrer, and an inert gas inlet, 300.00 parts by mass (0.100 mol) of polyester A-3, 20.83 parts by mass (0.200 mol) of neopentyl glycol (NPG), and 395.9 parts by mass of N,N-dimethylformamide (DMF) as a solvent were added and dissolved. Next, 75.08 parts by mass (0.300 mol) of 4,4'-diphenylmethane diisocyanate (MDI) and 34.8 parts by mass (0.200 mol) of Coronate T-80 were added at 40°C, and the reaction was carried out at 90°C until the NCO% reached 0.1% or less, thereby obtaining a DMF solution of polyurethane (A-3) with a non-volatile content of 50.0% by mass. The ratio of A-3, NPG, and MDI was A-3:NPG:MDI=1:2:3.

[0177] (Synthesis of polyurethanes A-4, A-6 and A-9)

[0178] Regarding polyesters A-4, A-6, and A-9, polyurethanes A-4, A-6, and A-9 were synthesized in the same manner.

[0179] Tables 5 and 6 show the analysis results of the polyurethanes obtained in the above-mentioned Examples and Comparative Examples.

[0180] (Evaluation of hydrolysis resistance of polyurethane)

[0181] After adding a polyisocyanate crosslinking agent to the obtained polyurethane (polyurethane solid content / crosslinking agent solid content = 10 / 1 mass ratio), it was immediately pre-dried at 70°C for 1 minute using Werner Mathis, and then dried at 120°C for 2 minutes to obtain a polyurethane film. After the film was aged at 40°C for 2 days, the film properties (initial; breaking strength) were measured using Autograph (manufactured by Shimadzu Corporation) under an environment of 23°C and 65% RH. In addition, for the hydrolysis resistance test, the polyurethane film was placed under the conditions of 70°C and 95% RH for 1 week, and after the water was further dried at room temperature for 1 day, the same film properties as the initial ones were measured to measure the degree of deterioration of the film.

[0182] The hydrolysis resistance was evaluated based on the retention rate of the breaking strength from the initial value according to the following criteria.

[0183] The results are shown in Tables 5 and 6.

[0184] ○: The retention rate of breaking strength is more than 90%

[0185] △: The retention rate of breaking strength is 80% or more and less than 90%

[0186] ×: The retention rate of breaking strength is less than 80%

[0187] [Table 5]

[0188]

[0189] [Table 6]

[0190]

[0191] As can be seen from Tables 1 to 6, the 1,6-hexanediol composition of the present invention has an acid value of 0.001 to 1.0 mgKOH / g and a total content of alkali metal elements of 0.1 to 1000 mass ppm. Therefore, a polymer obtained by reacting the 1,6-hexanediol composition (e.g., a polyester, a polyurethane obtained by reacting the polyester) has good hydrolysis resistance.

[0192] In addition, in this specification, the number average molecular weight (Mn) of a polyester is a value measured by gel permeation chromatography (GPC) under the following conditions.

[0193] Measuring device: HLC-8320GPC manufactured by Tosoh Corporation

[0194] Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, and TSKgel 1000HXL manufactured by Tosoh Corporation were connected in series and used.

[0195] Detector: RI (differential refractometer)

[0196] Data processing: MultiStation GPC-8020modelII manufactured by Tosoh Corporation

[0197] Determination conditions: column temperature 40°C

[0198] Solvent Tetrahydrofuran

[0199] Flow rate 0.1ml / min

[0200] Standard: Monodisperse polystyrene

[0201] Sample: A tetrahydrofuran solution containing 0.2% of the resin solid content was filtered through a microfilter (100 μl)

[0202] Standard samples: The following standard polystyrene was used to prepare a calibration curve.

[0203] (Standard Polystyrene)

[0204] "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation

[0205] "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation

[0206] "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation

[0207] "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation

[0208] "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

[0209] "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation

[0210] "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation

[0211] "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

[0212] "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

[0213] "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

[0214] "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

[0215] "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

[0216] "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

[0217] "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0218] In addition, in this specification, the number average molecular weight (Mn) of polyurethane is a value measured by gel permeation chromatography (GPC) under the following conditions.

[0219] Measuring device: High-speed GPC device (Tosoh Corporation "HLC-8220GPC")

[0220] Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

[0221] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 piece

[0222] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 piece

[0223] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 piece

[0224] "TSKgel G2000" (7.8mm I.D. × 30cm) × 1 piece

[0225] Detector: RI (differential refractometer)

[0226] Column temperature: 40°C

[0227] Eluent: Tetrahydrofuran (THF)

[0228] Flow rate: 1.0mL / min

[0229] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass %)

[0230] Standard samples: The following standard polystyrene was used to prepare a calibration curve.

[0231] (Standard Polystyrene)

[0232] "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation

[0233] "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation

[0234] "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation

[0235] "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation

[0236] "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

[0237] "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation

[0238] "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation

[0239] "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

[0240] "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

[0241] "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

[0242] "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

[0243] "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

[0244] "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

[0245] "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

Claims

1. A 1,6-hexanediol composition comprising one or both of 1,6-hexanediol and a 1,6-hexanediol derivative, and an alkali metal element, The total content of the alkali metal elements is in the range of 0.1 to 1000 mass ppm relative to the total amount of the composition, and the acid value of the composition is in the range of 0.001 to 1.0 mgKOH / g. 2 . The 1,6-hexanediol composition according to claim 1 , further comprising an organic acid having a pKa value of 4.0 or more at 25° C.

3. The 1,6-hexanediol composition according to claim 1 or 2, characterized in that The 1,6-hexanediol composition is derived from a biomass resource.

4. A polymer using the 1,6-hexanediol composition according to claim 1 or 2 as a reaction raw material.

5. The polymer according to claim 4, wherein The polymer is polyester or polyurethane.

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