Classifications

• • 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
  • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
• • 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
  • 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
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
• • 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
  • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
• • 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
  • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
  • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
• • 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
  • 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
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
  • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
• • 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
  • C08G18/65—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
  • C08G18/70—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
  • 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
  • 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 a method for producing a 1,6-hexanediol composition, a 1,6-hexanediol composition, and a polymer.
• 1,6-hexanediol (1,6-HD) compositions are useful intermediates for the production of polymers such as polyesters and polyurethanes.
• 1,6-hexanediol compositions have traditionally been produced by esterifying and then hydrogenating a mixture of carboxylic acids such as adipic acid, 6-hydroxycaproic acid, and glutaric acid, which are produced by oxidizing cyclohexane, a petrochemical product. It is produced by distillation and purification.
• Patent Documents 1 and 2 disclose a method for producing a 1,6-hexanediol composition using an enzyme, including genetic information of the enzyme, a metabolic pathway, and a method for producing the composition using purification.
• Patent Documents 1 and 2 disclose an environmentally friendly method for producing a 1,6-hexanediol composition derived from biomass resources, impurities contained in the 1,6-hexanediol composition are , and the reactivity of polymers such as polyester and polyurethane using the 1,6-hexanediol was not mentioned.
• the present inventors produced a 1,6-hexanediol composition according to the description in Japanese Patent No. 6,680,671, and then purified it using a known method.
• the present invention solves the above problems and provides an environmentally friendly manufacturing method for a 1,6-hexanediol composition derived from biomass resources with excellent reactivity, and a 1,6-hexanediol with excellent reactivity obtained by the manufacturing method.
• the object of the present invention is to provide a polymer such as polyester or polyurethane which has excellent reactivity and is obtained by reacting a composition and the 1,6-hexanediol composition.
• a 1,6-hexanediol composition derived from biomass resources contains a compound having two or more secondary hydroxyl groups in one molecule, 6-hydroxyhexanal and/or its derivatives.
• the present invention was completed based on the discovery that the reactivity could be improved by reducing the amount to a specific amount or less.
• the 1,6-hexanediol composition comprises 1,6-hexanediol and 1,6-hexane One or both of the diol derivatives, a compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and/or its derivative (B), the 1,6-hexanediol
• the content of the compound (A) having two or more secondary hydroxyl groups in one molecule based on the total amount of the composition is 100 mass ppm or less, and 6-hydroxy based on the total amount of the 1,6-hexanediol composition.
• step (1) is a step of producing the 1,6-hexanediol composition at a temperature of 70° C. or lower.
• step (1) is a step of producing the 1,6-hexanediol composition at a temperature of 50° C. or lower.
• step (1) is a step of producing the 1,6-hexanediol composition using a microorganism.
• the 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition according to any one of [1] to [4] contains 1,6-hexanediol and 1,6-hexanediol.
• hexanediol derivatives a compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and/or its derivative (B), and the 1,6-
• the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule based on the total amount of the hexanediol composition is 100 mass ppm or less, and 6% based on the total amount of the 1,6-hexanediol composition.
• the method for producing a 1,6-hexanediol composition of the present invention is environmentally friendly, such as reducing carbon dioxide emissions, since the 1,6-hexanediol composition is produced from raw materials derived from biomass resources. This is the manufacturing method. Further, the 1,6-hexanediol composition of the present invention has a total content of 100 mass ppm or less of the compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and/or its derivatives ( Since the total content of B) is 1500 mass ppm or less, the reactivity is excellent.
• the method for producing a 1,6-hexanediol composition of the present invention can produce a 1,6-hexanediol composition with excellent reactivity in an environmentally friendly manner.
• the polymers of the present invention polyester, etc.
• the polyurethane of the present invention has good tensile strength and elongation.
• 1,6-hexanediol composition (also referred to as the 1,6-hexanediol composition of the present invention) obtained by the method for producing a 1,6-hexanediol composition of the present invention will be described.
• the 1,6-hexanediol composition (sometimes simply referred to as the "composition") of the present invention includes either one or both of 1,6-hexanediol and 1,6-hexanediol derivatives in one molecule.
• This is a composition containing a compound (A) having two or more hydroxyl groups, and 6-hydroxyhexanal and/or a derivative thereof (B).
• a secondary hydroxyl group means a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a secondary carbon atom.
• a compound (A) having two or more secondary hydroxyl groups in one molecule may be simply referred to as "component (A)," and the same applies to component (B).
• 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 total content of either or both of 1,6-hexanediol and 1,6-hexanediol derivatives is preferably 96.00 to 99.99% based on the total amount of the composition. % by mass, more preferably 98.00 to 99.99% by mass, even more preferably 99.50 to 99.99% by mass.
• the effects of the present invention can be more favorably achieved by keeping the total content of component (A) and the total content of component (B) within the above range, and keeping the purity of the 1,6-hexanediol composition within the above range.
• the total content of either or both of 1,6-hexanediol and 1,6-hexanediol derivatives is a value measured by gas chromatography mass spectrometry (GC/MS).
• Component (A) is not particularly limited as long as it is a compound having two or more secondary hydroxyl groups in one molecule, such as 2,3-butylene glycol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, and galactitol.
• 1,4-cyclohexane has a large influence on the reactivity of the 1,6-hexanediol composition and the reactivity of the polymer such as polyester obtained by reacting the 1,6-hexanediol composition.
• Diol or glucose may also be used.
• the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule is 100 mass ppm or less, preferably 50 mass ppm or less, more preferably 10 mass ppm or less, even more preferably 5 mass ppm or less, and particularly preferably 0 mass ppm (excluding). be.
• the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule is a value measured by gas chromatography mass spectrometry (GC/MS).
• Component (B) is not particularly limited as long as it is one or both of 6-hydroxyhexanal and 6-hydroxyhexanal derivatives.
• the derivative of 6-hydroxyhexanal is not particularly limited as long as it is a derivative of 6-hydroxyhexanal (a compound represented by the following formula (1)), and includes cyclized products, aldol condensates, glycerin reactants, hexanediol ( HDO) reactants, and specific examples include compounds represented by the following formulas (2) to (7). These may be used alone or in combination of two or more.
• component (B) 6 - It may be hydroxyhexanal.
• the total content of 6-hydroxyhexanal and/or its derivative (B) (preferably the content of 6-hydroxyhexanal) with respect to the total amount of the 1,6-hexanediol composition of the present invention is 1500 mass ppm or less However, it is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, even more preferably 200 mass ppm or less, particularly preferably 0 mass ppm (excluding). This tends to result in good reactivity of the composition of the present invention, good reactivity of polymers (such as polyester) using the composition of the present invention as a reaction raw material, and good tensile strength and elongation of polyurethane. .
• the coloring and odor of the composition and the polymer using the composition as a reaction raw material can also be reduced.
• the total content of 6-hydroxyhexanal and/or its derivative (B) is a value measured by gas chromatography mass spectrometry (GC/MS).
• the composition of the present invention has excellent reactivity. Furthermore, polymers such as polyester using the composition of the present invention as a reaction raw material also have excellent reactivity. Although the reason why such effects are exhibited is not clear, it is presumed as follows.
• composition of the present invention contains a large amount of component (A)
• polymers such as polyester using the composition of the present invention as a reaction raw material may have secondary hydroxyl groups at the ends. This results in a decrease in the reactivity of polymers such as polyester.
• component (B) chain interruption or branching will occur during a polymerization reaction using the composition of the present invention as a reaction raw material.
• polyurethane using the composition of the present invention as a reaction raw material has good tensile strength and elongation. This is because when synthesizing a polyol (reaction raw material for polyurethane) from the composition of the present invention, the production of a polyol having a secondary hydroxyl group end can be suppressed to a small amount. Therefore, it is presumed that this is because the molecular weight does not decrease during polyurethanization, and the amount of hydroxyl groups at the polyester ends increases, so branching occurs during polyurethanization, and the cohesive force of the polyurethane decreases.
• the 1,6-hexanediol composition of the present invention preferably further contains an alkali metal element.
• 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 prevent the original action of the catalyst from being excessively reduced by the alkali metal. It does not have any adverse effect on the synthesis of polymers such as.
• the 1,6-hexanediol composition of the present invention further contains an alkali metal element, and if the alkali metal element is contained in a specific amount, good hydrolysis resistance can be imparted to the polymer. Furthermore, the 1,6-hexanediol composition of the present invention is used as a reaction raw material to synthesize polymers such as polyester and polyurethane without any adverse effect, and the polymers obtained by reacting the 1,6-hexanediol composition (e.g. polyester, polyurethane with ester bonds) have good hydrolysis resistance.
• the 1,6-hexanediol composition of the present invention is used as a reaction raw material to synthesize polymers such as polyester and polyurethane without any adverse effect, and the polymers obtained by reacting the 1,6-hexanediol composition (e.g. polyester, polyurethane with ester bonds) have good hydrolysis resistance.
• the total content of alkali metal elements is preferably 0.1 to 1000 ppm by mass based on the total amount of the 1,6-hexanediol composition of the present invention.
• 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 total content of alkali metal elements (preferably the total content of one or both of sodium metal elements and potassium metal elements) with respect to the total amount of the 1,6-hexanediol composition of the present invention is 0.1 to 1000 mass ppm, preferably 0.1 to 800 ppm by mass, more preferably 0.1 to 600 ppm by mass.
• the total content of alkali metals is 0.1 mass ppm or more, better reactivity, hydrolysis resistance, and tensile strength and elongation can be obtained, and when the total content is 1000 mass ppm or less, when synthesizing the polymer, For example, better reactivity tends to be obtained when polyester or polyurethane is synthesized using a 1,6-hexanediol composition as a raw material.
• the total content of alkali metals is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).
• the 1,6-hexanediol composition of the present invention may further contain glycerin, and the content of glycerin based on the total amount of the composition is preferably 2000 mass ppm or less, more preferably 1500 mass ppm or less, and even more preferably It is not more than 1000 ppm by weight, particularly preferably not more than 500 ppm by weight, and most preferably not more than 0 ppm by weight.
• the content of glycerin is 2000 mass ppm or less, it is possible to suppress excessive incorporation of glycerin into the polymer when reacting the 1,6-hexanediol composition to synthesize a polymer such as polyester.
• the content of glycerin is a value measured by gas chromatography mass spectrometry (GC/MS).
• the 1,6-hexanediol composition of the present invention may be produced such that the total content of component (A) and the total content of component (B) are within the above ranges.
• the 1,6-hexanediol composition of the present invention when the content of alkali metal is low, for example, a metal salt of an acid such as acetic acid, phosphoric acid, nitric acid and an alkali metal is added to remove the alkali metal.
• the total content may be within the above range.
• the 1,6-hexanediol composition of the present invention is a 1,6-hexanediol composition obtained by the following environmentally friendly production method (method for producing a 1,6-hexanediol composition of the present invention).
• a hexanediol composition (1,6-hexanediol composition derived from biomass resources) can be suitably used.
• the method for producing the 1,6-hexanediol composition of the present invention comprises a step of producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and/or its derivatives obtained from raw materials derived from biomass resources. 1), and a step (2) of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and/or distillation.
• Step (1) is a step of producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and/or its derivatives obtained from raw materials derived from biomass resources.
• producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and/or its derivatives obtained from raw materials derived from biomass resources means producing 6-hydroxycaproic acid and/or its derivatives from raw materials derived from biomass resources. It means producing a 1,6-hexanediol composition via / or a derivative thereof.
• 6-Hydroxycaproic acid and/or its derivatives may be used as long as it passes through 6-hydroxycaproic acid and/or its derivatives.
• 6-hydroxycaproic acid is transferred from raw materials derived from biomass resources in the cells of microorganisms. It may be a step of converting 6-hydroxycaproic acid and/or its derivatives into a 1,6-hexanediol composition via microorganisms and a raw material derived from biomass resources and containing the compound. This may be a step in which the culture solution is used as it is and converted into a 1,6-hexanediol composition by microorganisms, and the culture solution is purified and the compound is converted into 1,6-hexane diol composition by microorganisms in a different reaction tank. It may also be a step of converting into a diol composition.
• the derivative of 6-hydroxycaproic acid is not particularly limited as long as it is a derivative of 6-hydroxycaproic acid, for example, 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxycaproic acid
• examples include ester compounds such as cyclized products, condensates of 6-hydroxycaproic acids, and condensates of 6-hydroxycaproic acids and 1,6-hexanediol. These may be used alone or in combination of two or more.
• 6-hydroxy-hexanoyl-CoA which is a thioester of 6-hydroxycaproic acid
• CoA means coenzyme A.
• 6-hydroxycaproic acid and/or its derivatives 6-hydroxycaproic acid and 6-hydroxy-hexanoyl-CoA are preferable, and 6-hydroxycaproic acid is more preferable.
• the step (1) is a step of producing a 1,6-hexanediol composition at a temperature of 70°C or lower, and a step of producing a 1,6-hexanediol composition at a temperature of 50°C or lower. It is more preferable that there be.
• the lower limit of the temperature is not particularly limited, but is preferably 20°C or higher.
• the step (1) may be carried out using, for example, a microorganism capable of producing (biosynthesizing) 1,6-hexanediol.
• a microorganism capable of producing 1,6-hexanediol include microorganisms described in JP-A No. 2020-114227 and Japanese Patent No. 6,680,671. These may be used alone or in combination of two or more. Those skilled in the art can easily produce or obtain microorganisms capable of producing 1,6-hexanediol based on known techniques such as the above publications.
• 3-oxopropionate and 3-hydroxypropanal are produced by metabolic pathways within microorganisms.
• 3-phospho-glycerides are converted from sugars (pentose, hexose) through glycolytic metabolic pathways such as the pentose phosphate pathway (PP pathway) in microorganisms.
• Cellaldehyde is produced.
• 3-phospho-glyceraldehyde is produced from glycerin by metabolic pathways within microorganisms.
• 3-hydroxypropanal is produced from 3-phospho-glyceraldehyde through a reaction catalyzed by multiple enzymes possessed by microorganisms.
• 3-hydroxypropanal is produced from glycerin in one reaction by diol dehydratase and/or glycerol dehydratase.
• 3-phosphoglycerol is produced from sugars (pentose, hexose) through glycolytic metabolic pathways such as the Embden-Meyerhoff pathway (EM pathway) in microorganisms.
• the acid, 2-phosphoglyceric acid is produced.
• Glyceric acid is produced from 3-phosphoglyceric acid and 2-phosphoglyceric acid using the enzymes listed in Table 1 of Japanese Patent No. 6,680,671, or the reverse reaction of glyceric acid kinase.
• 3-oxopropionate is produced from glyceric acid by diol dehydratase and/or glycerol dehydratase. Furthermore, it can also be produced in one reaction from oxaloacetate, a metabolic intermediate of the TCA cycle, by keto acid decarboxylase. Oxaloacetate can also be produced from sugar by phosphoenolpyruvate carboxylase and pyruvate carboxylase without going through the TCA cycle.
• microorganisms capable of producing 1,6-hexanediol from 3-oxopropionate and 3-hydroxypropanal, which are produced by metabolic pathways within microorganisms, 1,6 -Hexanediol is produced.
• Preferred examples of microorganisms capable of producing 1,6-hexanediol from 3-oxopropionate and 3-hydroxypropanal that is, microorganisms capable of producing 1,6-hexanediol include the following microorganisms: can be mentioned.
• Microorganisms having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are not particularly limited as long as they have genes encoding the 10 enzymes of the 1,6-hexanediol pathway, and include, for example, prokaryotes, e.g. Examples include nuclear organisms. Furthermore, as a microorganism having genes encoding the 10 enzymes of the 1,6-hexanediol pathway, all of the genes (enzymes) have genes encoding the 10 enzymes of the 1,6-hexanediol pathway. and/or may be a genetically modified microorganism into which a portion has been introduced.
• the microorganism to be used has only eight of the ten enzymes, genes encoding the remaining two enzymes may be introduced into the microorganism. Furthermore, if the microorganism to be used has only some of the ten enzymes, a single microorganism or a plurality of microorganisms having genes encoding the remaining enzymes may be used in combination. Furthermore, it is preferable that the microorganism has a gene encoding diol dehydratase and/or glycerol dehydratase. Here, the gene can be introduced by a known method.
• prokaryotes examples include bacteria and the like.
• eukaryotes examples include yeast, filamentous fungi, and the like.
• bacteria examples include bacteria belonging to the family Enterobacteriaceae, coryneform bacteria, bacteria of the genus Bacillus, acetic acid bacteria, actinomycetes, and lactic acid bacteria.
• bacteria belonging to the Enterobacteriaceae family include the genus Escherichia, the genus Enterobacter, the genus Pantoea, the genus Klebsiella, the genus Serratia, the genus Erwinia, and the genus Erwinia.
• NCBI National Center for Biotechnology Information
• Bacteria belonging to the genus Escherichia include, but are not particularly limited to, bacteria classified into the genus Escherichia according to classifications known to microbiology experts.
• Escherichia bacteria include the book by Neidhardt et al. (Backmann, B. J. 1996. Derivations and Genotypes of some mutant derivatives of Escherichia coli K-12, p. 2460-2488. Table 1.
• Neidhardt ed.
• Escherichia coli and Salmonella Cellular and Molecular Biology/Second Edition American Society for Microbiology Press, Washington, D.C.
• Escherichia bacteria include Escherichia coli.
• Escherichia coli examples include Escherichia coli K-12 strains such as W3110 strain (ATCC 27325) and MG1655 strain (ATCC 47076); Escherichia coli K5 strain (ATCC 23506); and Escherichia coli strains such as BL21 (DE3) strain. coli B strain; and derivative strains thereof.
• Enterobacter bacteria examples include Enterobacter agglomerans and Enterobacter aerogenes.
• Pantoea genus bacteria include Pantoea ananatis, Pantoea stewartii, Pantoea agglomerans, and Pantoea citre. a) is mentioned.
• Erwinia bacteria examples include Erwinia amylovora and Erwinia carotovora.
• bacteria belonging to the genus Klebsiella examples include Klebsiella planticola.
• coryneform bacteria examples include bacteria belonging to the genus Corynebacterium, genus Brevibacterium, genus Microbacterium, and the like.
• coryneform bacteria include the following species. Corynebacterium acetoacidophilum Corynebacterium acetoglutamicum Corynebacterium alkanolyticum Corynebacterium callunae Corynebacterium crenatum Corynebacterium glutamicum Corynebacterium lilium Corynebacterium melassecola Corynebacterium thermoaminogenes (Corynebacterium efficiens) Corynebacterium herculis Brevibacterium divaricatum (Corynebacterium glutamicum) Brevibacterium flavum (Corynebacterium glutamicum) Brevibacterium immariophilum Brevibacterium lactofermentum (Corynebacterium glutamicum) Brevibacterium roseum Brevibacterium saccharolyticum Brevibacterium thiogenitalis Corynebacterium ammoniagenes (Corynebacterium stationis) Brevibacterium album Brevibacterium cerinum
• coryneform bacteria include the following strains. Corynebacterium acetoacidophilum ATCC 13870 Corynebacterium acetoglutamicum ATCC 15806 Corynebacterium alkanolyticum ATCC 21511 Corynebacterium callunae ATCC 15991 Corynebacterium crenatum AS1.542 Corynebacterium glutamicum ATCC 13020, ATCC 13032, ATCC 13060, ATCC 13869, FERM BP-734 Corynebacterium lilium ATCC 15990 Corynebacterium melassecola ATCC 17965 Corynebacterium efficiens (Corynebacterium thermoaminogenes) AJ12340 (FERM BP-1539) Corynebacterium herculis ATCC 13868 Brevibacterium divaricatum (Corynebacterium glutamicum) ATCC 14020 Brevibacterium flavum (Corynebacterium glutamicum) ATCC
• bacteria of the genus Corynebacterium include bacteria that were previously classified as the genus Brevibacterium but have now been integrated into the genus Corynebacterium (Int. J. Syst. Bacteriol., 41, 255 (1991)). included.
• Corynebacterium stationis includes bacteria that were previously classified as Corynebacterium ammoniagenes, but were reclassified as Corynebacterium stationis through 16S rRNA base sequence analysis (Int. J . Syst. Evol. Microbiol., 60, 874-879 (2010)).
• Bacillus bacteria examples include Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus licheniformis. illus licheniformis), Bacillus megaterium , Bacillus brevis, Bacillus polymixa, and Bacillus stearothermophilus.
• Bacillus subtilis examples include Bacillus subtilis 168 Marburg strain (ATCC 6051) and Bacillus subtilis PY79 strain (Plasmid, 1984, 12, 1-9).
• Bacillus amyloliquefaciens include Bacillus amyloliquefaciens T strain (ATCC 23842) and Bacillus amyloliquefaciens N strain (ATCC 23845).
• acetic acid bacteria examples include the genus Gluconobacter, the genus Acetobacter, the genus Gluconacetobacter, the genus Acidicaldus, the genus Acidiphilium, and the genus Acidisphaera.
• Genus Acidisphaera Genus Acidocella, Genus Acidomonas, Genus Asaia, Genus Belnapia, Genus Craurococcus, Genus Granulibacter, Genus Kozachia ( Genus Kozakia, Lee Leahibacter, Muricoccus, Neoasaia, Oleomonas, Paracraurococcus, Rhodopila, Roseococcus occus), Rubritepida genus , the genus Saccharibacter, the genus Stella, the genus Swaminathania, the genus Teichococcus, the genus Zavarzinia, and the like.
• acetic acid bacteria include Gluconobacter oxydans, Acetobacter xylinum, Acidomonas methanolicus, and Asaia botanicals. Gorensis, Asaia crungsapensis, Bernapia ⁇ Moavensis, Gluconacetobacter xylinus, Granulibacter bethesdensis, Kozakia variensis, Oleomonas sag aranensis), etc.
• Actinomyces include, for example, the genus Actinomyces, the genus Mycobacterium, the genus Nocardia, the genus Streptomyces, the genus Actinoplanes, and the genus Rhodococcus. us) genus etc. Examples include bacteria belonging to .
• actinobacteria include Streptomyces coelicolor, Streptomyces griseus, Streptomyces avermitilis, and Streptomyces avermitilis.
• Examples include Rhodococcus zopfii. .
• lactic acid bacteria examples include the genus Lacticaseibacillus, the genus Lactobacillus, the genus Ligilactobacillus, the genus Limosilactobacillus, and the genus Ligilactobacillus.
• Genus Liquorilactobacillus, Lactiplantibacillus examples include bacteria belonging to the genus Lactiplantibacillus, Streptococcus, Lactococcus, Enterococcus, and the like.
• lactic acid bacteria include, for example, Lacticaseibacillus casei, Lactobacillus gasseri, and Lactobacillus acidophilus. us), Lactobacillus helveticus, Lactobacillus del Brookie subspecies. bulgaricus (Lactobacillus delbrueckii subsp. bulgaricus), Lactobacillus delbrueckii subsp. Lactobacillus delbrueckii subsp.
• Lactococcus johnsonii Lactobacillus johnsonii, Ligilactobacillus salivarius us salivarius
• Limosilactobacillus fermentum Limosilactobacillus fermentum
• Licolilactobacillus mari Liquorilactobacillus mali
• Lactiplantibacillus plantarum Streptococcus thermophilus
• Lactococcus ⁇ Lactis subspecies lactis (Lactococcus lactis subsp. lactis), Lactococcus lactis subsp. cremoris (Lactococcus lactis subsp.
• Bacteria other than the above-mentioned bacteria include, for example, the genus Pseudomonas, the genus Agrobacterium, the genus Alicyclobacillus, the genus Arthrobacter, the genus Azotobacter, and the genus Chromatium ( Genus Chromatium , Methylobacterium spp., Rhodobacter spp., Rhodopseudomonas spp., Rhodospirillum spp., Zymomonas spp., Achromobacter spp.
• romobacter genus, Aerobacter genus, Genus Alcaligenes, Genus Arthrobacter, Genus Erwinia, Genus Microbacterium, Genus Micrococcus, Genus Protaminobacter, Genus Proteus (P roteus) genus
• examples include bacteria belonging to the genus Sartina, the genus Xanthomonas, the genus Aeromonas, the genus Flavobacterium, the genus Rhizobium, and the like.
• yeast examples include Saccharomyces genus, Candida genus, Pichia genus, Schizosaccharomyces genus, Kluyveromyces genus, Rhodotorul spp. a) Genus, Cryptococcus ), Torulopsis, Hansenula, Issatchenkia, Kluyveromyces, Yarrowia, and the like.
• yeast examples include Saccharomyces cerevisiae, Candida utilis, Pichia pastoris, and Hansenula pol. ymorpha), Schizosaccharomyces pombe etc.
• filamentous fungi examples include Aspergillus genus, Paecilomyces genus, Penicillium genus, Neurospora genus, Trichoderma genus, Fusarium genus, Chrysospo Examples include bacteria belonging to the genus Chrysosporium.
• filamentous fungi include Aspergillus oryzae, Paecilomyces saturatus, Paecilomyces divari icatus), Penicillium camemberti (P. camemberti), and the like.
• strains can be purchased, for example, from the American Type Culture Collection, 12301 Parklawn Drive, Rockville, Maryland 20852 P.O. Box 1549, Manassas, VA 20108 , United States of America). That is, each strain is assigned a corresponding registration number, and can be distributed using this registration number (see http://www.atcc.org/). The accession number corresponding to each strain is listed in the American Type Culture Collection catalog. Furthermore, these strains can be obtained, for example, from the depository institutions where each strain has been deposited.
• microorganisms may be used alone or in combination of two or more.
• prokaryotes are preferred, bacteria are more preferred, microorganisms belonging to the family Enterobacteriaceae are even more preferred, microorganisms belonging to the genus Escherichia are particularly preferred, and Escherichia coli is most preferred.
• prokaryotes having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are preferred, bacteria having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are more preferred; - Microorganisms belonging to the family Enterobacteriaceae having genes encoding 10 enzymes of the hexanediol pathway are more preferred, and microorganisms belonging to the genus Escherichia having genes encoding 10 enzymes of the 1,6-hexanediol pathway are particularly preferred; Escherichia coli having genes encoding the 10 enzymes of the 1,6-hexanediol pathway is most preferred.
• the 4,6-dihydroxy-2-oxo-hexanoate aldolase is a 2,4-dihydroxy-2-oxo-hexanoate aldolase encoded by the HpaI gene of Escherichia coli.
• Hept-2-ene-1,7-dioic acid aldolase and the 4,6-dihydroxy-2-oxo-hexanoate 4-dehydratase is a 2-oxo- Hept-4-ene-1,7-dioic acid hydratase, and the 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase is NADP of Arabidopsis thaliana with GenBank accession number CAC01710.1.
• 6-hydroxy-2-oxohexanoic acid 2-reductase is D-2-hydroxy acid dehydrogenase encoded by the panE gene of Lactococcus lactis, and the 2,6- Dihydroxy-hexanoic acid CoA-transferase and the 6-hydroxyhexanoyl-CoA-transferase are glutaconic acid-CoA-transferases encoded by the HadA gene of Clostridium difficile, and the 2,6-dihydroxy-hexanoyl-CoA-transferase
• the dehydratase is 2-hydroxyisocaproyl-CoA dehydratase expressed in Clostridium difficile
• the 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase is Treponema denticola GenBank accession number AE017248.
• trans-2-enoyl CoA reductase of Nocardia iowensis and/or the 6-hydroxyhexanoate 1-reductase is ATP/NADPH-CAR of Nocardia iowensis GenBank accession number AAR91681.1;
• the 1-reductase is 6-hydroxyhexanoate dehydrogenase of Rhodococcus GenBank Accession No. AAN37489.1.
• the microorganism By using the microorganism, (a) converting C 3 aldehydes and pyruvate to C 6 ⁇ -hydroxyketone intermediates via aldol addition; and then (b) converting the It is possible to carry out a step of converting the C 6 ⁇ -hydroxyketone intermediate to 1,6-hexanediol or a solvate thereof.
• the transformation comprises reduction of an enoyl or enoate, reduction of a ketone, reduction of an aldehyde, dehydration, formation of a thioester, reduction of a thioester, or a combination thereof.
• the method further includes a step of preparing an acid.
• the C3 aldehyde is also obtained via a series of enzymatic steps, where the enzymatic steps preferably include dehydration of the diol.
• 3-oxopropionate and 3-hydroxypropanal which are produced by the metabolic pathway within the microorganism, can be produced as shown in FIGS. 2 and 5 of Japanese Patent No. 6,680,671.
• 1,6-hexanediol is produced through the 2A, 2B, 2C, 2D, 2E, 2F, 2G, 4F3, 5R, and 5S routes.
• 6-hydroxy-hexanoyl-CoA is produced by the enzymatic reaction of the pathway up to 2G, and then 6-hydroxycaproic acid is produced by the enzymatic reaction of 4F3.
• 6-hydroxyhexanal is produced by the 5R enzymatic reaction, and 1,6-hexanediol is then produced by the 5S enzymatic reaction.
• a 1,6-hexanediol composition is produced from 6-hydroxycaproic acid and/or its derivatives obtained from raw materials derived from biomass resources. can.
• the raw materials derived from the biomass resources are not particularly limited, and include xylose, xylulose, ribulose, arabinose, lyxose, pentose such as ribose, allose, altrose, glucose, mannose, gulose, idose, talose, galactose, fructose, Monosaccharides such as hexoses such as psicose, sorbose or tagatose, disaccharides such as lactose, cellobiose, sucrose and maltose, polysaccharides such as starch, cellulose, agarose and dextran, alcohols such as sorbitol, ethanol and glycerin, peptone Carbon sources used in medium components such as , tryptone, and casamino acids; Nitrogen sources used in medium components such as peptone, tryptone, casamino acids, organic nitrogen compounds such as yeast extract, meat extract, and corn steep liquor.
• carbon sources used in culture medium components are preferred, and monosaccharides and alcohols are more preferred.
• monosaccharide hexose is more preferable, and glucose is particularly preferable.
• alcohol glycerin is more preferred. Therefore, glucose and glycerin are most preferred as raw materials derived from biomass resources.
• the medium is not particularly limited as long as it contains raw materials derived from the biomass resources, and may be a normal medium containing a carbon source, a nitrogen source, inorganic ions, and, if necessary, an organic nutrient source, as appropriate depending on the microorganism used. Can be prepared. Among these, it is preferable that the carbon source is contained as a raw material derived from biomass resources.
• Carbon sources other than the above-mentioned components are not particularly limited as long as they can be used by microorganisms, and include organic acids such as fumaric acid, citric acid, acetic acid, and propionic acid, salts thereof, and carbohydrates such as paraffin. These may be used alone or in combination of two or more.
• nitrogen sources other than the above components include ammonium salts of inorganic salts such as ammonium sulfate and ammonium chloride, ammonium salts of organic acids such as ammonium fumarate and ammonium citrate, and nitrates such as sodium nitrate and potassium nitrate. These may be used alone or in combination of two or more.
• the medium may contain nutrient sources used in ordinary mediums, such as trace metal salts, vitamins, and hormones. These may be used alone or in combination of two or more. Among these, it is preferable to include sodium and/or potassium as the trace metal salt.
• culture is carried out for about 4 to 140 hours while controlling the pH and temperature appropriately within the range of pH 3 to 11 and temperature of 20 to 70°C (more preferably 20 to 50°C). That's fine.
• Cultivation may be carried out under either aerobic or anaerobic conditions, which may be appropriately selected depending on the microorganism used, but aerobic conditions are preferred.
• a 1,6-hexanediol composition can be produced by culturing the microorganism in a medium containing raw materials derived from biomass resources. Since the 1,6-hexanediol composition exists together with microorganisms in the medium, the microorganisms may be removed from the medium if necessary.
• the method for removing microorganisms is not particularly limited, and may be performed by, for example, centrifugation and/or membrane separation.
• Centrifugation is not particularly limited, and for example, continuous centrifugation using a continuous centrifuge may be used.
• continuous centrifuges include squirrel cage centrifuges, disk centrifuges, nozzle centrifuges, and the like. These may be used alone or in combination of two or more.
• the membrane used for membrane separation is not particularly limited, and examples include membranes with a pore size of 10.0 ⁇ m or less, and specific examples include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes, etc. Can be mentioned. These may be used alone or in combination of two or more.
• the shape of the membrane is not particularly limited, and may be any shape such as a flat membrane, hollow fiber membrane, spiral membrane, tubular membrane, or pleated membrane.
• the type of filtration is not particularly limited either, and either a dead-end type or a tangential flow type can be applied, but a tangential flow type is preferred.
• Step (2) is a step of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and/or distillation.
• step (2) impurities contained in the 1,6-hexanediol composition obtained in step (1), for example, the culture medium containing the 1,6-hexanediol composition after removal of microorganisms, are removed by ionization.
• step (2) is a process in which the 1,6-hexanediol composition obtained in step (1) is purified by ion exchange and distillation.
• the process is a step of:
• the ion exchange is preferably cation exchange and anion exchange, and it is more preferable to perform cation exchange and anion exchange in this order.
• the distillation is preferably performed to remove water, components with a lower boiling point than 1,6-hexanediol, and components with a higher boiling point than 1,6-hexanediol. It is more preferable to remove components with a lower boiling point than 6-hexanediol and remove components with a higher boiling point than 1,6-hexanediol in this order.
• the 1,6-hexanediol composition obtained in step (1) to be subjected to step (2) is not particularly limited as long as it is the 1,6-hexanediol composition obtained in step (1).
• the liquid is obtained by removing microorganisms from the medium containing the 1,6-hexanediol composition obtained in step (1). More preferably, it is a liquid obtained by subjecting a medium containing a diol composition to centrifugation and membrane separation treatment to remove microorganisms.
• step (2) An example of step (2) will be described in detail below.
• a 1,6-hexanediol composition is obtained through the following steps (a) and (b) in this order.
• Examples of the components removed by contact with the cation exchange resin in step (a) include metal cations and ammonium ions.
• Examples of the components removed by contact with the anion exchange resin in step (b) include chloride ions, sulfate ions, phosphate ions, and organic acids.
• the organic acids mentioned here include the compound (A) having two or more secondary hydroxyl groups in one molecule having an acid group.
• the treatment with an ion exchange resin is not particularly limited, it is preferable to carry out the treatment by a batch method or a column method.
• step (a) cations are removed by bringing the 1,6-hexanediol composition into contact with a cation exchange resin.
• the cation exchange resin to be used includes, for example, strongly acidic and weakly acidic resins, but is not particularly limited. Further, examples include styrene type, acrylic type, hydrogel type, etc., but are not particularly limited. Further, examples include gel type, porous type, and high porous type, but these are not particularly limited.
• the form of the resin includes, for example, powder, spherical, fibrous, film, etc., but is not particularly limited.
• anions are removed by bringing the 1,6-hexanediol composition into contact with an anion exchange resin.
• the anion exchange resin to be used includes, for example, strongly basic and weakly basic resins, but is not particularly limited. Further, examples include styrene type, acrylic type, hydrogel type, etc., but are not particularly limited. Further, examples include gel type, porous type, and high porous type, but these are not particularly limited.
• the form of the resin includes, for example, powder, spherical, fibrous, film, etc., but is not particularly limited.
• the said description demonstrated the method of performing the said process (a) and the said process (b) in this order
• 1,6-hexanediol composition for example, 1,6-hexanediol composition B
• Examples of the component having a lower boiling point than 1,6-hexanediol in step (d) include 1,3-propanediol, a compound (A) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal. and/or its derivative (B).
• the component having a higher boiling point than 1,6-hexanediol in the step (e) for example, glycerin, a compound (A) having two or more secondary hydroxyl groups in one molecule, 6-hydroxyhexanal and/or its derivatives. (B) etc.
• distillation method is not particularly limited, it is preferable to remove by continuous or batch distillation.
• the 1,6-hexanediol composition obtained in the above ion exchange step for example, 1,6-hexanediol composition B
• the pressure is reduced. Water is removed from 1,6-hexanediol composition B by:
• Examples of the equipment used include, but are not particularly limited to, continuous distillation columns, multi-effect cans, thin film evaporators, evaporators, batch distillers, atomization separation equipment, etc.
• the step (d) is a step carried out for both the purpose of sufficiently removing low-boiling point components in order to obtain high-purity 1,6-hexanediol and removing trace amounts of coloring-causing components. be.
• components having a boiling point lower than 1,6-hexanediol such as the coloring component itself and the hydrogenated product of the coloring component, are particularly removed or reduced.
• the distillation in step (d) can be performed using known means and equipment, such as atmospheric distillation, reduced pressure distillation, and pressure distillation.
• the removal device include a continuous distillation column, a multi-effect tank, a thin film evaporator, an evaporator, a batch distiller, and an atomization separation device, but are not particularly limited.
• the operating conditions used in step (d) may be appropriately set taking into consideration the composition of the 1,6-hexanediol composition C, the purity to be finally obtained, etc., and are not particularly limited.
• steps (e) Step of removing components with a higher boiling point than 1,6-hexanediol>
• steps (e) components having a boiling point higher than 1,6-hexanediol are removed from 1,6-hexanediol composition D obtained in step (d).
• step (e) in particular, components having a boiling point higher than 1,6-hexanediol, which are specific to the fermentation method, such as nitrogen-containing components derived from amino acids and proteins, sugars and their decomposition products, are removed.
• step (e) examples include, but are not particularly limited to, continuous distillation columns, multi-effect cans, thin film evaporators, evaporators, batch distillers, atomization separation equipment, etc.
• the operating conditions used in step (e) may be appropriately set taking into account the composition of the 1,6-hexanediol composition D, the purity to be finally obtained, etc., and are not particularly limited.
• Step (f) Step of obtaining a higher purity 1,6-hexanediol composition>
• step (f) the 1,6-hexanediol composition E obtained through steps (c), (d), and (e) is purified to obtain higher purity 1,6-hexanediol. Obtain a composition.
• Examples of devices for obtaining a higher purity 1,6-hexanediol composition include continuous distillation columns, multi-effect cans, thin film evaporators, evaporators, batch distillers, atomization separation devices, etc. It is not limited.
• step (f) are not particularly limited, and may be appropriately set taking into account the composition of the liquid to be purified, the purity to be finally obtained, etc.
• the 1,6-hexanediol composition of the present invention can be obtained by performing the step (e) and, if necessary, the step (f).
• the method for producing a 1,6-hexanediol composition of the present invention may include step (1) and step (2), and in addition to step (1) and step (2), step (1), It may include steps other than step (2).
• step (2) the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule and the total content of 6-hydroxyhexanal and/or its derivative (B) are within the above range. However, the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule and the total content of 6-hydroxyhexanal and/or its derivative (B) are more preferably within the above range. You may perform step (2) repeatedly so that. By repeating step (2), the total content of the compound (A) having two or more secondary hydroxyl groups in one molecule and the total content of 6-hydroxyhexanal and/or its derivative (B) are further reduced. becomes possible.
• the polymer of the present invention is a polymer obtained by reacting the 1,6-hexanediol composition of the present invention.
• the polymer is not particularly limited as long as it is a polymer having a structural unit derived from the 1,6-hexanediol composition of the present invention, and includes oligomers.
• Examples of the polymer of the present invention include polyester, polyurethane, polycarbonate, polyether, epoxy polymers made from the above-mentioned epoxy group-containing 1,6-hexanediol derivatives, and the above-mentioned (meth)acryloyl group-containing 1,6-hexanediol derivatives. Examples include acrylic polymers made from .
• polyester, polyurethane, polycarbonate, and polyether are preferred, polyester, polyurethane, and polyether are more preferred, and polyester and polyurethane are even more preferred.
• the polymer of the present invention has at least a structural unit derived from the 1,6-hexanediol composition of the present invention, and optionally contains a structural unit derived from glycerin contained in the 1,6-hexanediol composition.
• 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 structural units derived from component (A) in one molecule in 100% by mass of the polymer of the present invention is preferably 50 mass ppm or less, more preferably 10 mass ppm or less, still more preferably 5 mass ppm or less, Particularly preferably, it is 0 mass ppm (not included). Thereby, there is a tendency for more favorable effects to be obtained.
• the total content of structural units derived from component (B) in 100% by mass of the polymer of the present invention is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, still more preferably 200 mass ppm or less, and particularly preferably 0 Mass ppm (excluding). Thereby, there is a tendency for more favorable effects to be obtained.
• 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 total content of alkali metals is 0.05 mass ppm or more, better reactivity, hydrolysis resistance, and tensile strength and elongation can be obtained, and when it is 500 mass ppm or less, it can be used when synthesizing a polymer. There is a tendency for reactivity to be further improved.
• the content of glycerin-derived structural units in 100% by mass of the polymer of the present invention is preferably 1500 mass ppm or less, more preferably 1000 mass ppm or less, even more preferably 500 mass ppm or less, particularly preferably 0 mass ppm (including No). Thereby, there is a tendency for more favorable effects to be obtained.
• the polymer may be modified. Modification is not particularly limited, and includes, for example, the modification described for 1,6-hexanediol derivatives. 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 obtained by reacting the 1,6-hexanediol composition of the present invention.
• 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 optionally contains a structural unit derived from glycerin contained in the 1,6-hexanediol composition.
• the polyester of the present invention may be 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 acid
• 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. Among these, aliphatic carboxylic acids are preferred, and adipic 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 monoalcohols such as phenol, cresol, and bisphenol-A.
• aliphatic monoalcohols such as ethanol, butanol, and 2-ethylhexanol
• aliphatic polyols such as ethylene glycol, neopentyl glycol, and trimethylolpropane
• aromatic monoalcohols such as phenol, cresol, and bisphenol-A.
• examples thereof include polyhydric phenols; ethylene
• the content of the 1,6-hexanediol composition of the present invention in 100% by mass of alcohol, which is a reaction raw material for polyester, 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 (or polyester polyol as the case may be) 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 the structural unit 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 structural units derived from the compound (A) having two or more secondary hydroxyl groups in one molecule in 100% by mass of the polyester of the present invention is preferably 70 mass ppm or less, more preferably 35 mass ppm or less, More preferably it is 7 mass ppm or less, particularly preferably 0 mass ppm (excluding). Thereby, there is a tendency for more favorable effects to be obtained.
• the total content of structural units derived from 6-hydroxyhexanal and/or its derivative (B) in 100% by mass of the polyester of the present invention is preferably 700 mass ppm or less, more preferably 350 mass ppm or less, and still more preferably 140 mass ppm or less. It is less than or equal to ppm by mass, particularly preferably 0 ppm by mass (excluding). Thereby, there is a tendency for more favorable effects to be obtained.
• the total content of alkali metal elements is preferably 0.05 to 500 ppm, more preferably 0. 0.05 to 400 mass ppm, more preferably 0.05 to 300 mass ppm.
• the polyester of the present invention can be used as a raw material. There is a tendency for reactivity to be further improved when synthesizing urethane.
• the content of structural units derived from glycerin in 100% by mass of the polyester of the present invention is preferably 1400 mass ppm or less, more preferably 1050 mass ppm or less, still more preferably 700 mass ppm or less, particularly preferably 0 mass ppm (including No). Thereby, there is a tendency for more favorable effects to be obtained.
• 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 Contains a structural unit derived from glycerin contained in the composition.
• 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 structural units derived from the compound (A) having two or more secondary hydroxyl groups in one molecule in 100% by mass of the polyurethane of the present invention is preferably 63 mass ppm or less, more preferably 32 mass ppm or less, More preferably it is 6 mass ppm or less, particularly preferably 0 mass ppm (excluding). Thereby, there is a tendency for more favorable effects to be obtained.
• the total content of structural units derived from 6-hydroxyhexanal and/or its derivative (B) in 100% by mass of the polyurethane of the present invention is preferably 945 mass ppm or less, more preferably 630 mass ppm or less, and even more preferably 315 mass ppm or less. It is less than or equal to ppm by mass, particularly preferably 0 ppm by mass (excluding). Thereby, there is a tendency for more favorable effects to be obtained.
• 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 total content of alkali metals is 0.05 mass ppm or more, better reactivity, hydrolysis resistance, and tensile strength and elongation tend to be obtained.
• the content of structural units derived from glycerin in 100% by mass of the polyurethane of the present invention is preferably 1260 mass ppm or less, more preferably 945 mass ppm or less, still more preferably 630 mass ppm or less, particularly preferably 0 mass ppm (including No). It is. Thereby, tensile strength and elongation tend to be more suitably obtained.
• 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.
• 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 of BL21 Star (DE3) (Invitrogen) by the heat shock method, and selected on LB plates containing appropriate antibiotics. As a result, a BL21 Star (DE3) strain containing all plasmids A, B, and C was obtained.
• Example 1 Preparation of 1,6-hexanediol composition 1 (1,6-HD composition 1)
• 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 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.
• the analysis results of the obtained 1,6-HD Composition 1 are shown below.
• the detection limits for glycerin, glucose, 1,4-cyclohexanediol, 6-hydroxyhexanal, potassium metal, and sodium metal elements were 5.0 mass ppm and 5.0 mass ppm, respectively. They were mass ppm, 0.3 mass ppm, 10.0 mass ppm, 3.0 mass ppb, and 3.0 mass ppb.
• the determination of potassium metal element and sodium metal element was performed by ICP-MS analysis, and other analyzes were performed by HPLC analysis and GC analysis.
• Glycerin 800 mass ppm Glucose: below detection limit 1,4-cyclohexanediol: below detection limit 6-hydroxyhexanal: 500 ppm by mass Potassium metal element: 2 mass ppm Sodium metal element: 2 mass ppm
• HPLC analysis details /equipment Shimadzu HPLC device (system controller: SCL-10A, liquid feeding unit: LC-10AD, column oven: CTO-10A, autosampler: SIL-10AD, low pressure gradient unit: FCV-10AL, Online degasser: DGU-14A) ⁇ Column: TSKgel OApak-A ⁇ Guard column: TSKgel OApak-P ⁇ Column temperature: 40°C ⁇ Eluent (iso): 0.75mM sulfuric acid ⁇ Flow rate: 0.8mL/min ⁇ Injection volume: 10.0 ⁇ L ⁇ Detector: RI (RID-10A) GC analysis details /equipment: Agilent GC-MS (GC7890B
• the obtained polyester was evaluated by the following method, and the analysis results are shown below.
• Reaction time Reaction time until acid value reaches 0.2 (3-level evaluation) Less than 6 hours: ⁇ , 6 hours or more and less than 8 hours: ⁇ , 8 hours or more: ⁇
• Odor Put 1000g of polyester polyol in a 1kg metal can and leave it in a dryer at 100°C for 3 hours to completely dissolve. Sensory evaluation of the strength of the odor when the lid is opened: ⁇ : Almost no odor.'' ⁇ : Slight odor” “ ⁇ : Strong odor” “ ⁇ : Quite strong odor”
• the obtained polyurethane was evaluated by the following method, and the analysis results are shown below.
• Reaction time Time until NCO% becomes 0.1% or less after TDI injection Less than 6 hours: ⁇ , 6 hours or more and less than 8 hours: ⁇ , 8 hours or more and less than 10 hours: ⁇ , 10 hours or more: ⁇
• Hydrolysis resistance (evaluated by retention rate of breaking strength from initial value and breaking elongation after hydrolysis resistance test): “ ⁇ : Retention rate of breaking strength is 80% or more, and breaking elongation is 100% or more.” “ ⁇ : Retention rate of breaking strength is 70% or more and less than 80%, and breaking elongation is 100% or more.” “ ⁇ : Retention rate of breaking strength is 50% or more and less than 70%, and breaking elongation is 100% or more” “ ⁇ : Retention rate of breaking strength is less than 50%, or breaking elongation is less than 100%”
• Example 2 Preparation of 1,6-hexanediol composition 2 (1,6-HD composition 2)
• the 1,6-hexanediol composition obtained by the biomethod was purified repeatedly to obtain a 1,6-hexanediol composition with a glycerin content of 150 mass ppm and a 6-hydroxyhexanal content of 100 mass ppm.
• Hexanediol composition 2 was obtained.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Example 3 Preparation of 1,6-hexanediol composition 3 (1,6-HD composition 3)
• the 1,6-hexanediol composition obtained by the biomethod was purified repeatedly, and the 1,6-hexanediol composition was purified so that the glycerin content was 5 mass ppm and the 6-hydroxyhexanal content was 10 mass ppm.
• Hexanediol composition 3 was obtained.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Example 4 Preparation of 1,6-hexanediol composition 4 (1,6-HD composition 4)
• Potassium acetate was added to the 1,6-HD composition 3 obtained in Example 3 so that the potassium metal element concentration was 300 mass ppm, and sodium acetate was added so that the sodium metal element concentration was 200 mass ppm.
• a 1,6-hexanediol composition 4 (1,6-HD composition 4) was prepared.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Polyester evaluation Reaction time ⁇ Number of colors: ⁇ 1 Odor: ⁇ Polyurethane evaluation Reaction time: ⁇ Breaking strength of film: ⁇ Breaking elongation of film: ⁇ Hydrolysis resistance: ⁇
• Example 5 Preparation of 1,6-hexanediol composition 5 (1,6-HD composition 5)
• 1,6-hexanediol composition 5 (1,6-HD composition 5) in which glycerin was added to 1,6-HD composition 3 obtained in Example 3 so that the glycerin content was 150 mass ppm was added.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Example 6 Preparation of 1,6-hexanediol composition 6 (1,6-HD composition 6)
• 1,6-hexanediol composition 6 (1,6-HD composition 6) in which glycerin was added to 1,6-HD composition 3 obtained in Example 3 so that the glycerin content was 1500 mass ppm was added.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Polyester evaluation Reaction time ⁇ Number of colors: ⁇ 1 Odor: ⁇ Polyurethane evaluation Reaction time: ⁇ Breaking strength of film: ⁇ Breaking elongation of film: ⁇ Hydrolysis resistance: ⁇
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Polyester evaluation Reaction time ⁇ Number of colors: ⁇ 1 Odor: ⁇ Polyurethane evaluation Reaction time: ⁇ Breaking strength of film: ⁇ Breaking elongation of film: ⁇ Hydrolysis resistance: ⁇
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• polyester resin The synthesis and evaluation of polyester resin and the synthesis and evaluation of polyurethane resin were performed in the same manner as in Example 1.
• Polyester evaluation Reaction time ⁇ Number of colors: ⁇ 1 Odor: ⁇ Polyurethane evaluation Reaction time: ⁇ Breaking strength of film: ⁇ Breaking elongation of film: ⁇ Hydrolysis resistance: ⁇
• the method for producing the 1,6-hexanediol composition of the present invention is to produce 1,6-hexane from 6-hydroxycaproic acid and/or its derivatives obtained from raw materials derived from biomass resources.
• the 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition of the present invention has excellent reactivity
• the 1,6-hexanediol composition obtained by using the 1,6-hexanediol composition as a reaction raw material Polyester was also found to have excellent reactivity. It was also found that polyurethane using the 1,6-hexanediol composition of the present invention as a reaction raw material has good tensile strength and elongation.
• 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 Columns: TSKgel4000HXL, TSKgel3000HXL, TSKgel2000HXL, and TSKgel1000HXL manufactured by Tosoh Corporation were used by connecting them in series.
• Detector; RI differential refractometer
• Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Solvent Tetrahydrofuran (THF) Flow rate 0.1 ml/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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Zoology (AREA)
• General Chemical & Material Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Biotechnology (AREA)
• Biochemistry (AREA)
• Bioinformatics & Cheminformatics (AREA)
• General Engineering & Computer Science (AREA)
• Microbiology (AREA)
• Genetics & Genomics (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyesters Or Polycarbonates (AREA)
• Polyurethanes Or Polyureas (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=89617835

Family Applications (1)

Country Status (6)

Cited By (2)

Citations (6)

Family Cites Families (2)

• 2023
  • 2023-07-13 US US18/992,306 patent/US20260009053A1/en active Pending
  • 2023-07-13 EP EP23842903.9A patent/EP4559891A1/en not_active Withdrawn
  • 2023-07-13 CN CN202380049536.XA patent/CN119384404A/zh not_active Withdrawn
  • 2023-07-13 JP JP2023563851A patent/JP7468810B1/ja active Active
  • 2023-07-13 KR KR1020257000164A patent/KR20250040624A/ko active Pending
  • 2023-07-13 WO PCT/JP2023/025826 patent/WO2024018980A1/ja not_active Ceased

Patent Citations (8)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events