Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/18—Polyhydroxylic acyclic alcohols
  • C07C31/20—Dihydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
  • C07C29/94—Use of additives, e.g. for stabilisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
  • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
  • C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric

Definitions

• the present invention relates to 1,6-hexanediol compositions and polymers.
• 1,6-hexanediol (1,6-HD) compositions are useful intermediates for the production of polymers such as polyesters and polyurethanes.
• 1,6-Hexanediol compositions are generally prepared (1) by hydrogenation of adipic acid or an adipic acid-containing feed stream, (2) by hydrogenation of hydroxycaproic acid or an ester thereof, or (3) by hydrogenation of caprolactone. It can be manufactured by
• Patent Document 1 describes a polyurethane resin composition characterized by containing a polyester polyol produced using a polyisocyanate, a polyhydric alcohol, and a polyhydric carboxylic acid in the presence of a solid acid catalyst.
• the present invention provides a 1,6-hexanediol composition capable of improving the hydrolysis resistance of a polymer using the 1,6-hexanediol composition as a reaction raw material, and the 1,6-hexanediol composition.
• the purpose is to provide a polymer using as a reaction raw material.
• the present inventors have found that a polymer obtained by reacting a 1,6-hexanediol composition containing a specific amount of an alkali metal element and having a specific acid value has good hydrolysis resistance. They discovered this and completed the present invention. That is, the present invention provides the following inventions.
• a 1,6-hexanediol composition containing one or both of 1,6-hexanediol and a 1,6-hexanediol derivative, and an alkali metal element, based on the total amount of the composition A 1,6-hexanediol composition in which the total content of the alkali metal elements is in the range of 0.1 to 1000 mass ppm, and the acid value of the composition is in the range of 0.001 to 1.0 mgKOH/g. .
• 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 ppm by mass.
• a polymer using a hexanediol composition as a reaction raw material has good hydrolysis resistance.
• the 1,6-hexanediol composition (hereinafter simply referred to as composition) of the present invention contains either or both of 1,6-hexanediol and 1,6-hexanediol derivatives, and an alkali metal element,
• the total content of the alkali metal elements is in the range of 0.1 to 1000 ppm by mass based on 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.
• 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 1,6-hexanediol derivatives.
• the 1,6-hexanediol derivative contained in the composition of the present invention modifies one or both of the two hydroxyl groups possessed by the 1,6-hexanediol contained in the 1,6-hexanediol composition of the present invention.
• This is a compound that has
• as a method for modifying the hydroxyl group of 1,6-hexanediol known methods for modifying hydroxyl groups can be used, such as etherification reaction, esterification reaction, modification with (meth)acrylic acid, etc. .
• 1,6-hexanediol derivatives examples include epoxy group-containing 1,6-hexanediol derivatives such as 1,6-hexanediol diglycidyl ether and 6-hydroxyhexylglycidyl ether; (meth)acryloyl group-containing 1,6-hexanediol derivatives such as meth)acrylate, 6-hydroxyhexyl acrylate, 1,6-hexanediol monoacrylate monomethacrylate; 1,6-hexanediol divinyl ether, 1,6- Vinyl ether group-containing 1,6-hexanediol derivatives such as hexanediol monovinyl ether; 6-propyloxy-1-hexanol, 1,6-dipropoxy-hexane, 1,6-hexanediol methyl ether, 1,6-dimethoxyhexane, etc.
• aliphatic alkyl ether group-containing 1,6-hexanediol derivatives fatty acid ester group-containing 1,6- such as propyl 6-hydroxyhexanoate, di-n-propyl adipate, methyl 6-hydroxycaproate, dimethyl adipate, etc.
• Hexanediol derivatives and the like. These may be used alone or in combination of two or more.
• a (meth)acryloyl group means one or both of an acryloyl group and a methacryloyl group
• (meth)acrylate means one or both of an acrylate and a methacrylate
• the content of either or both of 1,6-hexanediol and 1,6-hexanediol derivatives is preferably 96.00 to 99.99% by mass, More preferably 99.00 to 99.99% by mass, still more preferably 99.50 to 99.99% by mass.
• the effects of the present invention are more preferably achieved by keeping the total content of alkali metal elements within the above range, the acid value of the composition within the above range, and the purity of the 1,6-hexanediol composition within the above range. There is a tendency to obtain In this specification, the content of 1,6-hexanediol is a value measured by gas chromatography mass spectrometry (GC-MS).
• composition of the present invention contains an alkali metal element, and the total content of the alkali metal element is 0.1 to 1000 ppm by mass based on the total amount of the composition.
• the alkali metal element is not particularly limited, and includes lithium, sodium, potassium, rubidium, cesium, and the like. These may be used alone or in combination of two or more. Among these, sodium and potassium are preferred.
• the state of the alkali metal element contained in the composition of the present invention is not particularly limited, and may be an alkali metal alone, an alkali metal compound, an alkali metal ion, or the like.
• 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.
• the upper limit of the total content of alkali metal elements is preferably 1000 ppm by mass. It is as follows.
• the lower limit of the total content is not particularly limited, and is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, still more preferably 100 mass ppm or more, particularly preferably 500 mass ppm or more. Any combination of these upper and lower limits can be used.
• the total content of alkali metal elements is 0.1 to 1000 ppm by mass. However, it is preferably 1 to 1000 ppm by mass, more preferably 100 to 1000 ppm by mass, and still more preferably 500 to 1000 ppm by mass.
• the total content of alkali metal elements is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).
• 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, even more preferably 0.6 mgKOH/g or less.
• the lower limit of the acid value is not particularly limited, and is preferably 0.001 mgKOH/g or more, more preferably 0.01 mgKOH/g or more, even more preferably 0.1 mgKOH/g or more. Any combination of these upper and lower limits can be used.
• 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, more preferably 0.1 to 0. It is 6mgKOH/g. If the acid value exceeds the above upper limit, when the 1,6-hexanediol composition is used to make a polymer (e.g., polyester), there is a risk that the designed polymer (e.g., polyester) will not exhibit its performance. .
• a polymer e.g., polyester
• the acid value is less than the above-mentioned lower limit, there is a risk that the reactivity will decrease when synthesizing a polymer (eg, polyester or polyurethane) using the 1,6-hexanediol composition. Within this range, acceleration of the hydrolysis reaction of the polymer (for example, polyester) can be suitably suppressed.
• the acid value is a value measured according to JIS K 0070-1992.
• 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, the effects of the present invention tend to be obtained more favorably.
• the organic acid is not particularly limited as long as it has a pKa value of 4.0 or more at 25°C; for example, 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 these, acetic acid and succinic acid are preferred, and acetic acid is more preferred. Note that among organic acids, there are compounds that exhibit two or more pKa values, but in the present invention, the pKa value of the compound in such a case is the lowest value.
• the pKa value at 25° C. of the organic acid is 4.0 or more, preferably 4.0 to 10.0, more preferably 4.0 to 8.0, even more preferably 4.0 to 6.0, Particularly preferred is 4.0 to 5.0. Thereby, there is a tendency for more favorable effects to be obtained.
• the pKa value of an organic acid at 25°C is a value measured by neutralization titration. Examples of organic acids having a pKa value of 4.0 or more at 25°C include the organic acids described in Chemistry Handbook (Basic Edition) Revised 4th Edition, II-317 to II-321, Maruzen Publishing (1993). Can be mentioned.
• the content of the organic acid having a pKa value of 4.0 or more at 25°C may be such that the acid value of the composition of the present invention falls within the above numerical range.
• 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. It is more preferably 500 mass ppm or less.
• the lower limit of the content is not particularly limited, and is preferably 0.001 mass ppm or more, more preferably 0.01 mass ppm or more, still more preferably 0.05 mass ppm or more, particularly preferably 0.1 Mass ppm or more. Any combination of these upper and lower limits can be used.
• 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 in the 1,6-hexanediol composition is determined during the purification process.
• the amount is preferably 1 to 2000 ppm by mass, more preferably 10 to 1000 ppm by mass.
• the content of the organic acid having a pKa value of 4.0 or more at 25°C is preferably 0.001 to 2000 ppm by mass, more preferably 0.001 to 1000 mass ppm. ppm, more preferably 0.01 to 500 ppm by weight, particularly preferably 0.1 to 500 ppm by weight.
• the content of organic acids means the total content when a plurality of organic acids are contained.
• the contents of other components are also the same.
• the content of organic acid in the 1,6-hexanediol composition basically means the content of free organic acid, but may also include the content of organic acid forming a salt. .
• an organic acid with a pKa value of less than 4.0 at 25°C is present in the 1,6-hexanediol composition, such an organic acid will easily oxidize to an aldehyde, causing coloration of polymers such as polyester. There is a risk that odor may be generated.
• amino acids tend to remain as organic acids with a pKa value of less than 4.0, and the presence of these amino acids may cause coloring of polymers such as polyester and polyurethane.
• the content of an 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, and even more preferably is 500 mass ppm or less, particularly preferably 0 mass ppm (not blended).
• the content of organic acid is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).
• Organic acids having a pKa value of less than 4.0 at 25°C are not particularly limited as long as they have a pKa value of less than 4.0 at 25°C; for example, glycine (pKa value 2.36), alanine (pKa value 2.
• valine 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 Amino acids such as (pKa value 1.90); and the like. These may be used alone or in combination of two or more.
• the 1,6-hexanediol composition of the present invention may be produced so that the total content of alkali metal elements is within the above range.
• a commercially available 1,6-hexanediol composition has a total content of alkali metal elements of less than 0.1 mass ppm, so acetic acid, phosphorus, etc.
• An acid, such as nitric acid, and a metal salt of an alkali metal may be added so that the total content of alkali metal elements falls within the above range.
• the commercially available 1,6-hexanediol composition has an acid value of 0
• the commercially available 1,6-hexanediol composition has an acid (preferably a pKa value of 4.0 or more at 25°C). (organic acid) so that the acid value falls within the above range.
• the acid value will also increase.
• the composition contains a large amount of alkali metal elements, when synthesizing polymers such as polyester, there is a risk that they will coordinate to the catalyst and reduce the original function of the catalyst, that is, the effect of increasing the speed of the polymerization reaction. There is. Therefore, in the 1,6-hexanediol composition of the present invention, by containing only a specific amount of the alkali metal element, it is possible to suppress the original action of the catalyst from being excessively reduced by the alkali metal element. It does not have any adverse effects when synthesizing polymers such as polyurethane.
• the 1,6-hexanediol composition of the present invention has a specific acid value and contains a specific amount of alkali metal element, it can impart good hydrolysis resistance to polymers, and can also be used in polyesters and polyurethanes.
• the polymer obtained by reacting the 1,6-hexanediol composition (for example, polyester or polyurethane having an ester bond) has good hydrolysis resistance.
• biomass resources are reusable organic resources derived from animals and plants.
• Preferred resources include wood, rice straw, rice husks, rice bran, old rice, corn, sugar cane, cassava, soybeans, okara, bagasse, These are plant resources such as vegetable oils, fats and oils, waste paper, and papermaking residues.
• These biomass resources generally contain many alkali metal elements and alkaline earth metal elements such as nitrogen element, sodium, potassium, magnesium, and calcium.
• raw materials obtained from biomass resources are obtained by the production method described in JP-A-2020-114227.
• 1,6-hexanediol compositions derived from biomass resources such as 1,6-hexanediol compositions derived from biomass resources, can be suitably used.
• the hydrogen ion concentration (pH) of the fermentation liquid is usually adjusted using a neutralizing agent in order to proceed with the fermentation efficiently. Contains many alkali metal elements and alkaline earth metals in the neutralizing agent and culture solution.
• organic acids such as acetic acid and succinic acid are mixed in as impurities in 1,6-hexanediol derived from biomass resources obtained by the production method described in JP-A-2020-114227. This was discovered as a result of intensive study. These impurities are considered unnecessary and are removed using purification methods as long as cost permits.
• organic acids and alkali metal elements are not unnecessary components to coexist with 1,6-hexanediol; rather, their coexistence in specific amounts is an essential component to improve the hydrolysis resistance of polymers such as polyester.
• the inventors of the present invention have discovered something as a result of their intensive research. 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.
• the polymer of the present invention uses the 1,6-hexanediol composition of the present invention as a reaction raw material.
• 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.
• examples include polymers. These may be used alone or in combination of two or more.
• polyester, polyurethane, polycarbonate, and polyether are preferred, polyester, polyurethane, and polyether are more preferred, and polyester and polyurethane are even more preferred, since they tend to more effectively exhibit the effect of improving hydrolysis resistance.
• the polymer of the present invention has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, and also contains an alkali metal element and an organic acid derived from the 1,6-hexanediol composition.
• the term "the polymer of the present invention contains an organic acid” means that the polymer of the present invention has a structural unit derived from an organic acid in the polymer skeleton, in addition to an embodiment in which the polymer of the present invention contains a free organic acid. It also includes aspects. This is because acids such as organic acids may be incorporated into the polymer skeleton during polymerization.
• the content of the structural unit derived from the 1,6-hexanediol composition of the present invention in 100 mass% of the polymer of the present invention is preferably 10 to 100 mass%, more preferably 20 to 100 mass%. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of each structural unit in the polymer is measured by NMR.
• the total content of alkali metal elements is preferably 0.05 to 500 ppm by mass, more preferably 0. 0.05 to 400 mass ppm, more preferably 0.05 to 300 mass ppm.
• 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 0.001 to 1000 mass ppm. 05 to 250 ppm by mass.
• the term "the polymer of the present invention contains an acid” means that the polymer of the present invention contains a structure derived from an organic acid in the polymer skeleton, in addition to the embodiment in which the polymer of the present invention contains a free organic acid. Since embodiments having units are also included, the organic acid content includes the content of free organic acids and the content of structural units derived from organic acids present in the polymer skeleton.
• 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, still more preferably 250 mass ppm or less, and particularly preferably 0 mass ppm (not blended). Thereby, coloring of the polymer can be suppressed.
• the polymer may be modified. Modification is not particularly limited, and includes, for example, the modification described for 1,6-hexanediol derivatives. These may be used alone or in combination of two or more. Among these, modification with (meth)acrylic acid is preferred. In particular, when the polymer is polyester, it is preferably modified with (meth)acrylic acid.
• 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.
• the number average molecular weight (Mn) of a polymer is a value measured by gel permeation chromatography (GPC).
• polyester and polyurethane will be explained in detail, but the polymers are not limited to polyester and polyurethane.
• the polyester of the present invention is a compound using the 1,6-hexanediol composition of the present invention as a reaction raw material.
• the polyester of the present invention is a polycondensate synthesized by dehydration condensation of a carboxylic acid and an alcohol to form an ester bond, and at least the 1,6-hexane of the present invention is used as the alcohol.
• a diol composition is used. Therefore, the polyester of the present invention is a reaction product (polycondensate) obtained by a polycondensation reaction of carboxylic acid and alcohol, and the polyester of the present invention is at least derived from the 1,6-hexanediol composition of the present invention. It has a structural unit of 1,6-hexanediol and also contains an alkali metal element and an organic acid derived from the 1,6-hexanediol composition.
• the polyester of the present invention is preferably a polyester polyol.
• the polyester polyol include condensed polyester polyols, lactone polyester polyols, and the like.
• Condensed polyester polyols include, for example, low-molecular polyhydric alcohols (ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-)butanediol, pentanediol, neo Low molecular polyols such as pentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, 1,4-cyclohexanedimethanol, sugars such as sorbitol) and polybasic carboxylic acids (glutaric acid, adipic acid, azelaic
• the lactone-based polyester polyol is, for example, a polycaprolactone polyol obtained by ring-opening polymerization of a lactone such as ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, and ⁇ -methyl- ⁇ -caprolactone.
• carboxylic acids examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid; -Alicyclic polyesters such as cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, etc.
• aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid
• Aromatic polyvalent carboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic 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
• Aromatic monocarboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid
• Examples include fatty acids derived from various animal and vegetable oils, such as soybean oil fatty acids, tall oil fatty acids, linoleic acid, and eicosapentaenoic acid; and anhydrides thereof. These may be used alone or in combination of two or more.
• aliphatic polycarboxylic acids are preferred, and dodecanedicarboxylic acid is more preferred.
• the alcohol that can be used in addition to 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).
• the alcohol include aliphatic monoalcohols such as ethanol, butanol, and 2-ethylhexanol; aliphatic polyols such as ethylene glycol, neopentyl glycol, and trimethylolpropane; and aromatic mono/polymer alcohols such as phenol, cresol, and bisphenol-A. and ethylene oxide extension products thereof, hydrogenated alicyclic groups, and the like. These may be used alone or in combination of two or more.
• 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, more preferably 50 to 100% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• the polyester of the present invention can be obtained by a known method for producing polyester. 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 generated water from the system. Further, a reaction catalyst, an antioxidant, etc. may be used in combination during the synthesis.
• the content of structural units derived from the 1,6-hexanediol composition of the present invention in 100 mass% of the polyester of the present invention is preferably 10 to 70 mass%, more preferably 20 to 70 mass%. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of each structural unit in polyester is measured by NMR.
• the total content of alkali metal elements is preferably 0.05 to 500 ppm by mass, more preferably 0. 0.05 to 400 mass ppm, more preferably 0.05 to 300 mass ppm.
• 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 still more preferably 0.001 to 1000 mass ppm. 05 to 250 ppm by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• 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, still more preferably 250 mass ppm or less, and particularly preferably 0 mass ppm (not blended).
• coloring can be suppressed.
• the term "the polymer of the present invention contains an acid” means that the polymer of the present invention contains a structure derived from an organic acid in the polymer skeleton, in addition to the embodiment in which the polymer of the present invention contains a free organic acid. Since embodiments having units are also included, the organic acid content includes the content of free organic acids and the content of structural units derived from organic acids present in the polymer skeleton.
• 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.
• the number average molecular weight (Mn) of polyester is a value measured by gel permeation chromatography (GPC).
• the polyurethane of the present invention is a reaction product obtained by reacting a polyol and polyisocyanate using the 1,6-hexanediol composition of the present invention as a reaction raw material. Furthermore, if necessary, a polyol, a chain extender, a chain terminator, a crosslinking agent, etc. that do not use the 1,6-hexanediol composition as a reaction raw material may be used in combination as a reaction raw material for the polyurethane of the present invention.
• the polyurethane of the present invention has a structural unit derived from a polyol and a structural unit derived from a polyisocyanate, and has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, and optionally a polyurethane derived from the 1,6-hexanediol composition of the present invention.
• 6-hexanediol The composition contains an alkali metal and an organic acid.
• polyols examples include polyols such as polycarbonate polyols, polyether polyols, and polyester polyols. These polyols may or may not use a 1,6-hexanediol composition as a reaction raw material, and the polyurethane of the present invention may use a 1,6-hexanediol composition as a reaction raw material at least as long as a polyol is used as a reaction raw material. good.
• Polycarbonate polyol is a polyol obtained by the reaction of glycol and carbonate.
• the glycol include the 1,6-hexanediol composition of the present invention, diethylene glycol, ethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 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- Various saturated or unsaturated glycols such as 1,3-propanediol and 2-ethyl-2-butyl 1,3-propanediol; fats such as 1,4-cyclohexane diglycol and 1,4
• the polyether polyol is, for example, a polyether polyol obtained by addition polymerizing alkylene oxide using various glycols as an initiator.
• alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
• examples of the various glycols include those similar to the glycols of the polycarbonate diol described above.
• polycaprolactone polyol in addition to those mentioned above, polycaprolactone polyol, polyacrylic polyol, dimer diol, polybutadiene polyol, hydrogenated polybutadiene polyol, etc. can be used. These polyols may be used alone or in combination of two or more.
• chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol , sucrose, methylene glycol, glycerin, sorbitol, neopentyl glycol and other aliphatic polyol compounds; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenation Aromatic polyol compounds such as bisphenol A and hydroquinone; water; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4 '-dicyclohexylmethanediamine, 3,3'-d
• chain extenders those derived from biomass resources can also be used. These chain extenders may 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.
• polyester polyol made from the composition of the present invention is particularly preferable to use as the polyol, and 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.
• polyisocyanate examples include 1,3- and 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, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5- Diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,
• polyisocyanates can also be derived from biomass resources. These may 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.
• chain terminator having one active hydrogen group may be used if necessary.
• 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. is exemplified. These may be used alone or in combination of two or more.
• a crosslinking agent having three or more active hydrogen groups or isocyanate groups can be used as necessary.
• the polyurethane of the present invention can be obtained by a known method for producing polyurethane. Specifically, for example, a method for producing the polyol, the polyisocyanate, and the chain extender may be introduced and reacted. These reactions are preferably carried out, for example, at a temperature of 50 to 100°C for 3 to 10 hours. Further, the reaction may be performed in an organic solvent.
• organic solvents examples 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; methyl formate; , ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, sec-butyl acetate, and other ester solvents; methanol, ethanol, isopropyl alcohol, butanol, and other alcohol solvents can be used. Further, these organic solvents may be derived from biomass resources. These organic solvents may be used alone or in combination of two or more.
• 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 weight, more preferably 20 to 90% by weight. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of the structural unit derived from the 1,6-hexanediol composition of the present invention in 100 mass% of the polyurethane of the present invention is preferably 1 to 63 mass%, more preferably 2 to 63 mass%. Thereby, there is a tendency for more favorable effects to be obtained.
• the content of each structural unit in polyurethane is measured by NMR.
• the total content of alkali metal elements is preferably 0.05 to 500 ppm by mass, more preferably 0. 0.05 to 400 mass ppm, more preferably 0.05 to 300 mass ppm.
• 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 0.001 to 1000 mass ppm. 05 to 250 ppm by mass. Thereby, there is a tendency for more favorable effects to be obtained.
• 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, still more preferably 250 mass ppm or less, particularly preferably 0 mass ppm (not blended).
• coloring can be suppressed.
• the term "the polymer of the present invention contains an acid” means that the polymer of the present invention contains a structure derived from an organic acid in the polymer skeleton, in addition to the embodiment in which the polymer of the present invention contains a free organic acid. Since embodiments having units are also included, the organic acid content includes the content of free organic acids and the content of structural units derived from organic acids present in the polymer skeleton.
• the number average molecular weight (Mn) of the polyurethane of the present invention is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000. Thereby, there is a tendency for more favorable effects to be obtained.
• the number average molecular weight (Mn) of polyurethane is a value measured by gel permeation chromatography (GPC).
• the polymer of the present invention can be used for various purposes. Specifically, artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, paints, laminating adhesives, elastic fibers, urethane raw materials, automobile parts, sporting goods, vibration isolation materials, and damping materials. It can be used in a wide range of applications, including as a fiber treatment agent and binder.
• the polyester of the present invention can be used for various purposes. Specifically, solvent-based, water-based, powder, paints for metals, automobiles, woodworking, and plastics; modifiers for packaging materials and containers, optical films, and molded products; artificial leather, and the skin of synthetic leather. Layer, intermediate layer, foam layer, adhesive layer; Adhesives such as laminating adhesives; For a wide range of applications such as shoes, thermoplastic resins, foamed resins, thermosetting resins, elastic fibers, polyurethane raw materials, automobile parts, and sporting goods. Can be used.
• the polyurethane of the present invention can be used for various purposes. Specifically, the skin layer, intermediate layer, foam layer, and adhesive layer of artificial leather and synthetic leather; various coating agents such as paints, metal surface treatment agents, and film primers; inkjet products, inks, textile printing, and glass fibers. Binder for sizing agents; For a wide range of applications such as shoes, thermoplastic resins, foamed resins, thermosetting resins, adhesives such as laminating adhesives, vibration isolating materials, vibration damping materials, automobile parts, sporting goods, textile processing agents, etc. Can be used.
• Epoxy polymers made from the epoxy group-containing 1,6-hexanediol derivatives can be used for various purposes. Specifically, it can be used in a wide range of applications, such as paints, various coating agents such as metal surface treatment agents, and molded products such as matrix resins for wind turbines.
• the acrylic polymer made from the above-mentioned (meth)acryloyl group-containing 1,6-hexanediol derivative can be used for various purposes. Specifically, it can be used in a wide range of applications, such as various coating agents such as paints, metal surface treatment agents, and film coatings; binders for inks and UV inkjet.
• PBS resin PET resin
• PTT resin PBT resin
• the notation " ⁇ " means a value greater than or equal to the value before the description " ⁇ ” and less than or equal to the value after the description " ⁇ ".
• the upper and lower limits of each numerical range can be used in any combination. For example, when two numerical ranges of 0.001 to 500 mass ppm and 0.05 to 250 mass ppm are disclosed for the content of a certain compound, 0.001 to 500 mass ppm and 0.05 to 250 mass ppm are disclosed. This means that in addition to ppm, numerical ranges of 0.001 to 250 mass ppm and 0.05 to 500 mass ppm are also disclosed.
• Example 1 Preparation of 1,6-hexanediol composition 1 (1,6-HD composition 1)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm of sodium and acid value of 0 mgKOH/g by ICP-MS analysis, was heated and melted at 80°C, and the potassium content was 1.
• Potassium acetate was added to give a concentration of .7 ppm by mass, and 15 ppm by mass of acetic acid was further added and the mixture was cooled to obtain 1,6-hexanediol composition 1.
• the acid value of 1,6-hexanediol composition 1 was 0.02 mgKOH/g.
• Example 2 Preparation of 1,6-hexanediol composition 2 (1,6-HD composition 2)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 ppm sodium and acid value 0 mg KOH/g by ICP-MS analysis, was heated and melted at 80 ° C., and the sodium content was 995 mass ppm.
• Sodium acetate was added so as to give 400 mass ppm of acetic acid, and the mixture was cooled to obtain 1,6-hexanediol composition 2.
• the acid value of 1,6-hexanediol composition 2 was 0.48 mgKOH/g.
• Example 3 Preparation of 1,6-hexanediol composition 3 (1,6-HD composition 3)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm of sodium and acid value of 0 mgKOH/g by ICP-MS analysis, was heated and melted at 80°C, and the potassium content was 998.
• Potassium acetate was added to give a mass ppm, and 200 mass ppm of succinic acid was added, and the mixture was cooled to obtain 1,6-hexanediol composition 3.
• the acid value of 1,6-hexanediol composition 3 was 0.11 mgKOH/g.
• Plasmid A was created by introducing glycerol dehydratase ⁇ , ⁇ , ⁇ subunit genes and dehydratase reactivator gene derived from Citrobacter freundii between the BamHI and HindIII restriction enzyme cleavage sites of pACYC184 (Nippon Gene). .
• MCS was introduced between the BamHI and EcoRI restriction enzyme cleavage sites to create plasmid B.
• HadB and HadC genes derived from Clostridium difficile as ⁇ and ⁇ subunit genes of 2-hydroxyisocaproyl-CoA dehydratase HadI gene derived from Clostridium difficile as 2-hydroxyisocaproyl-CoA dehydratase activating enzyme, 6- trans-2-enoyl-CoA reductase (GenBank: AE017248) gene derived from Treponema denticola as hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase, and the trans-2-enoyl-CoA reductase (GenBank: AE017248) gene derived from Nocardia iowensis as 6-hydroxyhexanoate 1-reductase.
• the carboxylic acid reductase (GenBank: AAR91681.1) gene and the 6-hydroxyhexanoate dehydrogenase (GenBank: AAN37489.1) gene from Rhodococcus as 6-hydroxyhexanal 1-reductase were added to pCOLADuet-1 (Novagen) with HadB, Plasmid C was created in which the HadC and HadI genes were introduced into MCS1 and the other genes were introduced into MCS2.
• Gene in this section refers to an open reading frame containing a stop codon that encodes each enzyme, and each gene has a sequence containing a T7 promoter and a ribosome binding site upstream, and a sequence containing a T7 terminator downstream.
• Each is introduced into a plasmid in such a manner as to Each gene can be expressed in large amounts in the host strain Escherichia coli such that T7 RNA polymerase is expressed by appropriate expression induction.
• Plasmids A, B, and C were sequentially transformed into chemically competent cells, BL21 Star (DE3) (Invitrogen), by the heat shock method, and selected on LB plates containing appropriate antibiotics.
• BL21 Star (DE3) strain containing all plasmids A, B, and C was obtained.
• Example 4 Preparation of 1,6-hexanediol composition 4 (1,6-HD composition 4)
• Autoclaved medium carbon source: glucose, glycerin, nitrogen source: enzyme extract, inorganic salts: potassium phosphate, potassium hydroxide, vitamin B12, antibiotics: carbenicillin, kanamycin, chloramphenicol, pH: 7.0
• glucose and glycerin are raw materials derived from biomass resources
• the optical density of Escherichia coli at 600 nm is 0.3 to 0.6
• the final concentration of isopropyl- ⁇ -thiogalactopyranoside is 0.5 mM
• the final concentration of iron (II) sulfate is 10 ⁇ M.
• the cells were added in the same manner as above and cultured for 3 hours at 30°C to express the enzyme of the 1,6-HD pathway. After expression, an appropriate amount of carbon source (glucose, glycerin) was added, and the inside of the culture vessel was placed under a nitrogen atmosphere to create anaerobic conditions. Cultivation was performed under these conditions at 30°C for 48 hours to produce 1,6-hexanediol.
• the culture solution was centrifuged at 4°C for 20 minutes, the supernatant was collected, and the filtrate was filtered using a membrane filter with an appropriate pore size of 0.2 to 0.4 ⁇ m, and the 1,6-hexanediol composition was obtained as a filtrate. I got something.
• step (a) cation exchange was performed in a batch manner. The temperature of contact with the cation exchange resin was set at 40° C., and DIAION SK1BH manufactured by Mitsubishi Chemical Corporation was added as a cation exchange resin to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, filtration was performed to obtain 1,6-hexanediol composition A as a filtrate.
• anion exchange was performed in a batch manner. The temperature of contact with the anion exchange resin was set at 40° C., and DIAION SA10AOH manufactured by Mitsubishi Chemical Corporation was added as an anion exchange resin to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, filtration was performed to obtain 1,6-hexanediol composition B as a filtrate.
• a thin film distiller was used as the apparatus for step (c).
• the jacket temperature was set at 70°C, the 1,6-hexanediol-containing composition was continuously introduced, and water was distilled off from the top.
• the dehydrated 1,6-hexanediol composition C was continuously extracted from the bottom as bottoms.
• the water concentration in this 1,6-hexanediol composition C was 0.020 mass % (200 mass ppm).
• An Aldershaw 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 top temperature was controlled at a constant temperature of 240°C. Continuous distillation is carried out from the top of the column and continuous extraction is carried out from the bottom of the column to remove low boiling point components in 1,6-hexanediol composition C.
• the 1,6-hexanediol composition D from which the components had been removed was taken out.
• a 1,6-hexanediol composition E was obtained by removing components with a higher boiling point than 1,6-hexanediol from the top of the tower (top distillate). Potassium acetate was added to 1,6-hexanediol composition E so that the potassium metal element concentration was 110 mass ppm in ICP-MS analysis, and sodium acetate was added so that the sodium metal element concentration was 190 mass ppm. ,6-hexanediol composition 4 (1,6-HD composition 4) was prepared.
• Example 5 Preparation of 1,6-hexanediol composition 5 (1,6-HD composition 5)
• 1,6-hexanediol manufactured by Ube Industries, Ltd. whose alkali metal element content was 0.02 mass ppm sodium and acid value 0 mg KOH/g by ICP-MS analysis, was heated and melted at 80°C, and potassium was 500 mass ppm. Potassium acetate was added so as to give a concentration of ppm, and 1000 ppm by mass of acetic acid was further added, and the mixture was cooled to obtain 1,6-hexanediol composition 5.
• the acid value of 1,6-hexanediol composition 5 was 0.95 mgKOH/g.
• polyester (A-1)) 1048.5 parts by mass of 1,6-hexanediol composition 1 and 2093.4 parts by mass of dodecanedioic acid (manufactured by INVISTA) were placed in a reaction vessel equipped with a stirring bar, a temperature sensor, and a rectifying tube, and the mixture was heated with dry nitrogen.
• the dehydration condensation reaction was carried out under atmospheric pressure while stirring the water flowing into the container and distilling off the water produced at 190 to 210° C. from the system.
• polyester A-1 having 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.
• Synthesis of polyesters A-2 to 9 Regarding 1,6-HD compositions 2 to 9, polyesters A-2 to A-9 were synthesized in the same manner. The reaction using 1,6-HD compositions 7 and 8 did not proceed well, so the reaction was discontinued.
• 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 ppm by mass. It has been found that polymers obtained by reacting the 1,6-hexanediol composition (eg, polyester, polyurethane obtained by reacting the polyester) have good hydrolysis resistance.
• the number average molecular weight (Mn) of polyester is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device HLC-8320GPC manufactured by Tosoh Corporation
• Detector RI (differential refractometer)
• Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Solvent Tetrahydrofuran Flow rate 0.1ml/min Standard; Monodispersed polystyrene sample; 0.2% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l) Standard sample: A calibration curve was created using the following standard polystyrene.
• the number average molecular weight (Mn) of polyurethane is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series.
• “TSKgel G5000” (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 Book “TSKgel G2000" (7.8mm I.D.

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