Method for producing 2,5-dimethylfuran, method for producing para-xylene, method for producing terephthalic acid, method for producing polyester, para-xylene, terephthalic acid, polyester composition, fiber material, resin material, film material, fiber product, resin product, and film product

Abstract

A method for producing 2,5-dimethylfuran according to one embodiment of the present invention includes a step for reacting a furan compound having a specific structure with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst. In this method for producing 2,5-dimethylfuran, the hydrogenation catalyst includes at least one type selected from among a first component group and at least one type selected from among a second component group. The first component group includes chromium, molybdenum, manganese, rhenium, ruthenium, rhodium, iridium, nickel, palladium, platinum, copper, zinc, and the like. The second component group includes aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, carbon, and the like.

Description

Methods for producing 2,5-dimethylfuran, method for producing paraxylene, method for producing terephthalic acid, and method for producing polyester, and methods for producing paraxylene, terephthalic acid, polyester compositions, fiber materials, resin materials, film materials, fiber products, resin products, and film products

[0001] The present invention relates to a method for producing 2,5-dimethylfuran, a method for producing paraxylene, a method for producing terephthalic acid, and a method for producing polyester, and to paraxylene, terephthalic acid, a polyester composition, a fiber material, a resin material, a film material, a fiber product, a resin product, and a film product.

[0002] In order to solve the global warming caused by the increase in greenhouse gases such as carbon dioxide and the associated climate change issues, efforts to achieve carbon neutrality towards a decarbonized society are accelerating. For this reason, it is extremely important to produce bulk chemicals that were originally derived from petroleum in a sustainable manner from biomass, and vigorous research and development is being carried out worldwide.

[0003] Terephthalic acid is a raw material for polyester, which is used to make synthetic fibers, films, plastic bottles, etc., and due to its wide range of uses, there is a very high demand for biomass-derived products.

[0004] In recent years, methods for producing terephthalic acid using paraxylene produced from biomass as a synthetic starting material have been investigated. A representative example of this method is a route proposed in which paraxylene is produced by the Diels-Alder reaction of 2,5-dimethylfuran with ethylene, followed by an oxidation step to produce terephthalic acid. This 2,5-dimethylfuran can be produced by chemical conversion of sugars that can be derived from biomass resources. Therefore, paraxylene and terephthalic acid can each be replaced with biomass-derived products.

[0005] In the process of converting sugars to 2,5-dimethylfuran, a route has been proposed in which 5-chloromethylfurfural is obtained by a dehydration reaction under acidic conditions with hydrochloric acid, followed by hydrogen reduction (see, for example, Patent Document 1). Another route has also been proposed in which 5-hydroxymethylfurfural is obtained and then hydrogen reduced.

[0006] On the other hand, 5-hydroxymethylfurfural is known to have low thermal stability and poor handling properties. Non-Patent Document 1 proposes a method of converting 5-hydroxymethylfurfural into an acetal compound as a method for improving the thermal stability of 5-hydroxymethylfurfural and suppressing side reactions such as polymerization and ring-opening reactions. Non-Patent Document 2 also proposes a method of converting the acetal compound into 2,5-dimethylfuran by contacting it with a solid catalyst containing an iron-ruthenium alloy under hydrogen gas pressure.

[0007] International Publication No. 2015 / 023918

[0008] Nakajima, K. et al. Angew. Chem. Int. Ed. 2018, Vol. 57, p. 8235 Vlachos, D. G. et al. Green Chem. 2023, Vol. 25, p. 9363

[0009] The method for producing 2,5-dimethylfuran described in Patent Document 1 requires harsh production conditions that require the use of a large amount of hydrochloric acid, and the chlorine atom contained in 5-chloromethylfurfural is eliminated. For this reason, the production method described in Patent Document 1 is undesirable from the viewpoint of atom economy.

[0010] Furthermore, the method for producing 2,5-dimethylfuran described in Non-Patent Document 2 uses a special alloy catalyst containing iron as a metal component, which has problems such as being easily deactivated by air or moisture and being difficult to obtain on an industrial scale due to its low versatility. Therefore, there is a need for a production method that gives 2,5-dimethylfuran in high yield under mild conditions using a catalyst that is easy to handle, highly versatile, can be easily separated and recovered from the solution after the reaction, and is reusable.

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to enable efficient production of 2,5-dimethylfuran using an iron-free hydrogenation catalyst, to enable production of paraxylene using the obtained 2,5-dimethylfuran as a raw material, to enable production of terephthalic acid using the obtained paraxylene as a raw material, and to enable production of polyester using the obtained terephthalic acid as a raw material.

[0012] In order to solve the above-mentioned problems and achieve the object, the present invention employs any of the following means.

[0013] That is, the method for producing 2,5-dimethylfuran according to the present invention is a method for producing 2,5-dimethylfuran, comprising: [1] a step of reacting a furan compound represented by general formula (I) with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst contains at least one selected from the group of first components shown below and at least one selected from the group of second components shown below:

[0014] [In general formula (I), R 1 represents -CHOH, an alkyl group having 1 to 5 carbon atoms, -CHOC(O)R 4 , -C(O)OR 5 R is any one of the groups represented by 2 and R 3 are each an alkyl group having 1 to 5 carbon atoms, which may be different from each other, and may be bonded to each other to form a ring structure. 4 is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. 5is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. (First component group) chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, and cadmium. (Second component group) magnesium aluminate, calcium aluminate, magnesium silicate, calcium silicate, aluminosilicate, boron oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, zinc oxide, chromium oxide, hydroxyapatite, silicon carbide, magnesium carbonate, calcium carbonate, barium carbonate, carbon, graphite, diamond, silicon nitride, aluminum nitride, boron nitride, aluminosilicophosphate, aluminophosphate, magnesium phosphate, calcium phosphate, strontium phosphate, pyrophosphate, chlorapatite, fluorapatite, calcium sulfate, and barium sulfate.

[0015] The method for producing 2,5-dimethylfuran according to the present invention is [2] the method according to the above [1], characterized in that the non-aqueous solvent is at least one selected from the group consisting of hydrocarbons, alcohols, ethers, and esters.

[0016] The method for producing paraxylene according to the present invention is characterized in that it comprises the following steps (A) and (B): [3] Step (A): A step of producing 2,5-dimethylfuran by the method for producing 2,5-dimethylfuran according to the above [1] or [2] Step (B): A step of producing paraxylene using the 2,5-dimethylfuran obtained by the step (A) as a raw material.

[0017] The method for producing terephthalic acid according to the present invention is characterized by including [4] a step of producing terephthalic acid using paraxylene obtained by the method for producing paraxylene described in [3] above as a raw material.

[0018] The method for producing a polyester according to the present invention is characterized by including [5] a step of producing a polyester using terephthalic acid obtained by the method for producing terephthalic acid according to the above [4] as a raw material.

[0019] Furthermore, the paraxylene according to the present invention is characterized in that it contains [6] 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, toluene, 2-methylfuran, and 2-methyltetrahydrofuran as components, and the total content of the components is 0.001 ppm or more and 500 ppm or less.

[0020] The terephthalic acid according to the present invention is characterized in that it contains, as components, [7] 2,5-furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, benzoic acid, 2-furancarboxylic acid, and tetrahydrofuran-2-carboxylic acid, and the total content of the components is 0.001 ppm or more and 500 ppm or less.

[0021] The polyester composition of the present invention is characterized in that it is obtained by the polyester production method described in [8] above [5].

[0022] [9] The polyester composition according to the present invention is characterized in that it is obtained using the terephthalic acid described in [7] above as a raw material.

[0023]

[10] A fiber material according to the present invention is characterized in that it is made using the polyester composition described in [8] or [9] above.

[0024]

[11] A resin material according to the present invention is characterized in that it is made using the polyester composition described in [8] or [9] above.

[0025]

[12] A film material according to the present invention is characterized in that it is made using the polyester composition described in [8] or [9] above.

[0026]

[13] The textile product according to the present invention is characterized in that it is made using the textile material described in

[10] above.

[0027] The textile product according to the present invention is characterized in that it is a clothing product, an industrial material, a construction material, or a daily material in the invention described in

[14] above

[13] .

[0028]

[15] The resin product according to the present invention is characterized in that it is made using the resin material described in

[11] above.

[0029] The resin product according to the present invention is characterized in that, in the invention described in

[15] above, the resin product is an electric / electronic device part, an automobile part, a machine part, or a housing material.

[0030]

[17] The film product according to the present invention is characterized in that it is made using the film material described in

[12] above.

[0031] Furthermore, the film product according to the present invention is

[18] the invention described in the above

[17] , characterized in that it is a release film for manufacturing multilayer ceramic capacitors, a film for dry film resists, a release film for polarizing plates, an optical release film, a process release film, or a film for packaging materials.

[0032] According to the present invention, 2,5-dimethylfuran can be efficiently produced, and the obtained 2,5-dimethylfuran can be used to produce paraxylene, terephthalic acid, and polyester.

[0033] Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that are implemented within the scope of the present invention.

[0034] (1) Raw Material Compound In the method for producing 2,5-dimethylfuran according to an embodiment of the present invention (hereinafter sometimes abbreviated as the method for producing 2,5-dimethylfuran of the present invention), a furan compound represented by the following general formula (I) (hereinafter sometimes simply referred to as a furan compound) is used as a raw material compound.

[0035]

[0036] In general formula (I), R 1 represents -CHOH, an alkyl group having 1 to 5 carbon atoms, -CHOC(O)R 4 , -C(O)OR 5 R is any one of the groups represented by 2 and R 3 are each an alkyl group having 1 to 5 carbon atoms, which may be different from each other, and may be bonded to each other to form a ring structure. 4 is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In this specification, for example, an alkyl group having 1 to 5 carbon atoms means an alkyl group having 1 to 5 carbon atoms. The same applies to other substituents that specify the number of carbon atoms.

[0037] R in general formula (I) 1 Examples include -CHOH, a methyl group, and -CHOC(O)R 4 , or —C(O)OR 5 is preferred. 2 and R 3 is preferably a methyl group, an ethyl group, an ethylene group, a trimethylene group, or a dimethyltrimethylene group. 4 R is preferably a methyl group or a phenyl group. 5 Among the furan compounds represented by general formula (I), R 1 ~R 5 Specific examples of furan compounds having a group in which R is preferred include furan compounds represented by any of the following formulas (I-1) to (I-30). 1 As R, —CHOH is more preferable. 1 Specific examples of furan compounds in which R is a group represented by -CHOH include dimethyl acetal, diethyl acetal, ethylene acetal, trimethylene acetal, and dimethyl trimethylene acetal of 5-hydroxymethylfurfural, which are represented by the following formulas (I-1) to (I-5). 2 and R31 A trimethylene group is more preferred as R 1 is a group represented by —CHOH, and R 2 and R 3 The furan compound in which is a trimethylene group is a trimethylene acetal of 5-hydroxymethylfurfural represented by the following formula (I-4).

[0038]

[0039] The present furan compound may be a commercially available product, a product synthesized by a known technique, or a product synthesized by a new method. Specifically, for example, the furan compounds represented by the above formulas (I-1) to (I-5) can be synthesized by the method described in Experimental Example 7 of Japanese Patent No. 6900801. Furthermore, the present furan compound may be derived from either a petroleum-based raw material or a biomass-derived product.

[0040] In particular, in the method for producing 2,5-dimethylfuran of the present invention, the furan compound is preferably derived from biomass. Also, the furan compound is preferably recovered as an unreacted component from the reaction product in the method for producing 2,5-dimethylfuran of the present invention, separated and purified as necessary, and reused.

[0041] (2) Hydrogenation Catalyst In the method for producing 2,5-dimethylfuran of the present invention, the hydrogenation catalyst contains at least one selected from the group of first components shown below and at least one selected from the group of second components shown below.

[0042] The group of first components is the group consisting of chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, and cadmium. Among these, the hydrogenation catalyst preferably contains at least one selected from the group consisting of chromium, molybdenum, manganese, rhenium, ruthenium, rhodium, iridium, nickel, palladium, platinum, copper, and zinc, because these elements have high hydrogenation catalytic ability and good reaction selectivity.

[0043] This first component may be in a metallic state or a cationic state, as long as it exhibits hydrogenation ability. Among these, the metallic state may be preferable because it has stronger hydrogenation ability and is more stable under a reducing atmosphere. The first component may be used alone or in combination with two or more types contained in a solid catalyst. When two or more first components are used, there are no particular limitations on the combination, mixing ratio, or form, and the first component may be used in the form of a mixture of individual metals, or in the form of an alloy or intermetallic compound.

[0044] The second component group is the group consisting of magnesium aluminate, calcium aluminate, magnesium silicate, calcium silicate, aluminosilicate, boron oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, zinc oxide, chromium oxide, hydroxyapatite, silicon carbide, magnesium carbonate, calcium carbonate, barium carbonate, carbon, graphite, diamond, silicon nitride, aluminum nitride, boron nitride, aluminosilicophosphate, aluminophosphate, magnesium phosphate, calcium phosphate, strontium phosphate, pyrophosphate, chlorapatite, fluorapatite, calcium sulfate, and barium sulfate. Among these, the hydrogenation catalyst preferably contains at least one selected from the group consisting of carbon, aluminum oxide, silicon oxide, titanium oxide, and zirconium oxide, due to its high hydrogenation catalytic ability.

[0045] The second component may be used singly or in combination of two or more. When two or more second components are used in combination, the combination, mixing ratio, and form are not particularly limited, and the second component may be used in the form of a mixture of individual compounds, a composite compound, or a double salt.

[0046] The hydrogenation catalyst may contain an additional component in addition to the first and second components described above in order to improve the hydrogenation catalytic ability and selectivity. Examples of the additional component include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, gallium, silicon, germanium, tin, lead, antimony, bismuth, tellurium, fluorine, chlorine, bromine, and iodine. One type of the additional component may be used alone, or two or more types may be used in combination.

[0047] (3) Non-aqueous Solvent A non-aqueous solvent is used as the solvent for the hydrodeoxygenation reaction in the method for producing 2,5-dimethylfuran of the present invention. By using a non-aqueous solvent, side reactions can be suppressed and the target product can be obtained efficiently. Specifically, the non-aqueous solvent is preferably at least one selected from the group consisting of hydrocarbons, alcohols, ethers, and esters. Examples of hydrocarbons include saturated aliphatic hydrocarbons such as pentane, neopentane, hexane, cyclohexane, heptane, methylcyclohexane, octane, isooctane, nonane, decane, decalin, dodecane, and isododecane, and aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, tetrahydronaphthalene, and methylnaphthalene. Examples of alcohols include monoalcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, t-butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol, and diols such as ethylene glycol, propanediol, butanediol, pentanediol, and neopentyl glycol. Examples of ethers include diethyl ether, tetrahydrofuran, dimethoxyethane, methyl t-butyl ether, tetrahydropyran, dipropyl ether, diisopropyl ether, methyltetrahydropyran, and cyclopentyl methyl ether. Examples of esters include methyl acetate, ethyl acetate, methyl propionate, propyl acetate, ethyl propionate, methyl butanoate, and butyl acetate.

[0048] (4) Reaction Conditions The method for producing 2,5-dimethylfuran of the present invention comprises a step of reacting a furan compound represented by the above general formula (I) with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst. The reaction that preferably proceeds here is as shown in the following formula (1), in which the target compound, 2,5-dimethylfuran, is obtained by hydrodeoxygenation, and water, an alcohol, and / or a diol are by-produced. The reaction conditions, such as the amount of feed to the reactor and the reaction temperature, are appropriately adjusted depending on the type and loading of the hydrogenation catalyst.

[0049]

[0050] In the method for producing 2,5-dimethylfuran of the present invention, the reaction temperature is not particularly limited, but is preferably 20°C or higher, more preferably 50°C or higher, and even more preferably 90°C or higher. The upper limit of this reaction temperature is preferably 500°C or lower, more preferably 400°C or lower, and even more preferably 300°C or lower. The higher the reaction temperature, the more likely it is that raw material consumption per the same amount of catalyst will be accelerated. On the other hand, if the reaction temperature is too high, the selectivity of the product will tend to decrease.

[0051] In the method for producing 2,5-dimethylfuran of the present invention, there is no limitation on the hydrogen pressure in the reactor, but the hydrogen pressure in the reactor is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, and even more preferably 0.4 MPa or more, in terms of gauge pressure. The upper limit of the hydrogen pressure in the reactor is preferably 20 MPa or less, more preferably 10 MPa or less, and even more preferably 5 MPa or less. The higher the hydrogen pressure in the reactor, the more promoted the supply of hydrogen to the hydrogenation catalyst, thereby improving the reaction rate. On the other hand, performing the reaction at a high hydrogen pressure requires reaction equipment with high pressure resistance, and product selectivity tends to decrease.

[0052] In the method for producing 2,5-dimethylfuran of the present invention, there is no limitation on the amount of the furan compound used relative to the non-aqueous solvent, but the concentration of the furan compound (raw material compound) relative to the non-aqueous solvent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. If the concentration of the raw material compound is too low, a large amount of non-aqueous solvent will be used, which will require a reaction vessel that is too large, and as a result, production efficiency will tend to decrease.

[0053] (5) Separation and Purification 2,5-dimethylfuran obtained by the method for producing 2,5-dimethylfuran of the present invention can be separated and purified by known methods depending on the content of 2,5-dimethylfuran and the types of impurities.

[0054] In the method for producing 2,5-dimethylfuran of the present invention, if the reaction product contains an unreacted furan compound as a raw material compound, as described above, the 2,5-dimethylfuran and the raw material compound are separated and recovered, and further purified as necessary. This preferably results in the target compound, 2,5-dimethylfuran, and the unreacted furan compound, and the unreacted furan compound is reused as a raw material compound for 2,5-dimethylfuran. Furthermore, if an alcohol or diol is contained in the reaction product as a by-product of the hydrodeoxygenation reaction or due to hydrolysis of the raw material compound, this is separated and recovered, and further purified as necessary. This preferably results in the target compound, 2,5-dimethylfuran, and the alcohol or diol, and the alcohol or diol is reused in the synthesis of the raw material compound, furan compound.

[0055] (6) Conversion of 2,5-dimethylfuran The method for producing paraxylene according to an embodiment of the present invention (hereinafter sometimes abbreviated as the method for producing paraxylene of the present invention) comprises the following steps (A) and (B): Step (A): A step for producing 2,5-dimethylfuran by the method for producing 2,5-dimethylfuran of the present invention; Step (B): A step for producing paraxylene using the 2,5-dimethylfuran obtained by the above step (A) as a raw material.

[0056] Step (A) is as described above in relation to the method for producing 2,5-dimethylfuran of the present invention.

[0057] In step (B), a known method can be used to produce paraxylene using 2,5-dimethylfuran as a raw material. Specific examples include the method described in Example 2 of Japanese Patent No. 6047162. This method allows paraxylene to be produced using 2,5-dimethylfuran obtained by the method for producing 2,5-dimethylfuran of the present invention.

[0058] The method for producing paraxylene of the present invention may further include a step of separating and purifying paraxylene after step (B). The method for separating and purifying paraxylene is not particularly limited, and any method known in the technical field related to the separation and purification of paraxylene can be directly applied as the method for separating and purifying paraxylene.

[0059] The paraxylene according to an embodiment of the present invention (hereinafter sometimes abbreviated as the paraxylene of the present invention) contains 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, toluene, 2-methylfuran, and 2-methyltetrahydrofuran as components. For example, 2,5-dimethylfuran is a compound represented by the following formula (II-1). 2,5-dimethyltetrahydrofuran is a compound represented by the following formula (II-2). Toluene is a compound represented by the following formula (II-3). 2-Methylfuran is a compound represented by the following formula (II-4). 2-Methyltetrahydrofuran is a compound represented by the following formula (II-5). In the paraxylene of the present invention, the total content of these components is preferably 0.001 ppm or more and 500 ppm or less, more preferably 0.001 ppm or more and 400 ppm or less, and even more preferably 0.001 ppm or more and 300 ppm or less. The lower the total content of these components (the above-mentioned compounds) contained in the paraxylene of the present invention, the more likely it is that impurities will be mixed into terephthalic acid produced by oxidizing the paraxylene, and the higher the purity of the terephthalic acid. On the other hand, reducing the total content of the above-mentioned components tends to involve an increase in the size of the purification equipment used.

[0060]

[0061] A method for producing terephthalic acid according to an embodiment of the present invention (hereinafter sometimes abbreviated as the method for producing terephthalic acid of the present invention) includes a step of producing terephthalic acid using paraxylene obtained by the method for producing paraxylene of the present invention as a raw material. As a method for producing terephthalic acid using paraxylene as a raw material, a known method can be used. Specific examples include the method described in the examples of JP 2017-095391 A. This allows terephthalic acid, which will be described later, to be produced using paraxylene obtained by the method for producing paraxylene of the present invention as a raw material.

[0062] The method for producing terephthalic acid of the present invention may further include a step of separating and purifying terephthalic acid. The method for separating and purifying terephthalic acid is not particularly limited, and examples of such a method include the method described in Examples of JP 2017-095391 A.

[0063] Terephthalic acid according to an embodiment of the present invention (hereinafter sometimes abbreviated as "terephthalic acid of the present invention") contains 2,5-furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, benzoic acid, 2-furancarboxylic acid, and tetrahydrofuran-2-carboxylic acid as components. For example, 2,5-furandicarboxylic acid is a compound represented by the following formula (III-1). Tetrahydrofuran-2,5-dicarboxylic acid is a compound represented by the following formula (III-2). Benzoic acid is a compound represented by the following formula (III-3). 2-furancarboxylic acid is a compound represented by the following formula (III-4). Tetrahydrofuran-2-carboxylic acid is a compound represented by the following formula (III-5). In the terephthalic acid of the present invention, the total content of these components is preferably 0.001 ppm or more and 500 ppm or less, more preferably 0.001 ppm or more and 400 ppm or less, and even more preferably 0.001 ppm or more and 300 ppm or less. The lower the total content of these components (the above-mentioned compounds) contained in the terephthalic acid of the present invention, the less discoloration of the polymer produced by condensation polymerization of the terephthalic acid and glycol, and the more controllable the color tone. On the other hand, reducing the total content of the above-mentioned components tends to involve an increase in the size of the purification equipment used.

[0064]

[0065] The polyester production method according to an embodiment of the present invention (hereinafter sometimes abbreviated as the polyester production method of the present invention) includes a step of producing a polyester using terephthalic acid obtained by the above-described terephthalic acid production method of the present invention as a raw material. Known methods can be used to produce a polyester using terephthalic acid as a raw material. Specific examples of such methods include those described in Example 1 of JP-A-2004-231831, Example 1 of JP-A-2016-60759, or the production examples of WO 2023 / 146235. This allows the polyester composition described below to be produced using terephthalic acid obtained by the terephthalic acid production method of the present invention as a raw material.

[0066] The polyester composition according to the embodiment of the present invention (hereinafter sometimes abbreviated as the polyester composition of the present invention) is obtained by the above-described method for producing a polyester of the present invention. That is, the polyester composition of the present invention can be produced using the above-described terephthalic acid of the present invention as a raw material. Examples of polyesters contained in the polyester composition of the present invention include polyethylene terephthalate, polybutylene terephthalate, and polybutylene adipate terephthalate.

[0067] A fiber material according to an embodiment of the present invention (hereinafter sometimes abbreviated as the fiber material of the present invention) is made using the polyester composition of the present invention described above. For example, the fiber material of the present invention can be obtained by spinning using the polyester composition of the present invention described above. Known methods can be used as a method for spinning using the polyester composition. Specific examples of such methods include the method described in Example 1 of JP-A-2023-170756. This allows a fiber material to be obtained using the polyester composition of the present invention.

[0068] The fiber material of the present invention can be used as a raw material for various fiber products. That is, a fiber product according to an embodiment of the present invention (hereinafter sometimes abbreviated as the fiber product of the present invention) is made using the fiber material of the present invention described above. The fiber product of the present invention is not particularly limited, and examples thereof include clothing, industrial materials, construction materials, and household goods. Examples of such clothing include shirts, pants, blouses, skirts, blousons, parkas, coats, jackets, fleece, sweaters, cardigans, sportswear, outdoor wear, innerwear, formal wear, accessories, and workwear. Examples of such industrial materials include belts, ropes, filters, nonwoven fabrics, tire cords, rubber hose / belt reinforcing threads, and nets. Examples of such construction materials include wallpaper, moisture-permeable waterproof sheets, soundproofing materials, heat insulating materials, sound-absorbing materials, and roof underlayment materials. Examples of such household goods include wrapping materials, bags, signboard materials, and printing substrates. The fiber product of the present invention may be any of these clothing, industrial materials, construction materials, and household goods.

[0069] A resin material according to an embodiment of the present invention (hereinafter sometimes abbreviated as the resin material of the present invention) is obtained using the polyester composition of the present invention described above. For example, the resin material of the present invention can be obtained by melt-kneading the polyester composition of the present invention described above with other components depending on the purpose. Known methods can be used as a method for melt-kneading the polyester composition. Specific examples of such methods include the method described in Example 1 of JP-A No. 2024-3891. In this way, a resin material can be obtained using the polyester composition of the present invention.

[0070] The resin material of the present invention can be molded and used as a raw material for various resin products. That is, a resin product according to an embodiment of the present invention (hereinafter sometimes abbreviated as a resin product of the present invention) is made using the above-mentioned resin material of the present invention.

[0071] The resin product of the present invention is not particularly limited, and examples thereof include electrical and electronic equipment parts, automobile parts, mechanical parts, and housing materials. Examples of such electrical and electronic equipment parts include circuit breakers, electromagnetic switches, focus cases, flyback transformers, fusing units for copiers and printers, housings for general household electrical appliances and office automation equipment, variable capacitor cases, terminal boards, transformers, printed wiring boards, terminal blocks, coil bobbins, connectors, relays, disk drive chassis, transformers, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases, and resistors. Examples of such automobile parts include automotive ignition system parts, automotive connectors, and various automotive electrical components. Examples of such mechanical parts include computer-related parts, audio parts, lighting parts, telecommunication equipment-related parts, telephone equipment-related parts, air conditioner parts, home appliance parts, copier parts, facsimile parts, and optical equipment parts. Examples of such housing materials include roofing materials, exterior wall materials, and flooring materials.

[0072] A film material according to an embodiment of the present invention (hereinafter sometimes abbreviated as the film material of the present invention) is made using the polyester composition of the present invention described above. For example, the film material of the present invention can be obtained by forming a film using the polyester composition described above. Known methods can be used to form a film using the polyester composition. Specific examples of such methods include the method described in Example 1 of JP-A-2024-123912. In this way, a film material can be obtained using the polyester composition of the present invention.

[0073] The film material of the present invention can be used as a raw material for various film products. That is, the film product according to the embodiment of the present invention (hereinafter sometimes abbreviated as the film product of the present invention) is made using the above-mentioned film material of the present invention.

[0074] The film product of the present invention is not particularly limited, but examples of the film product of the present invention include those selected from release films for manufacturing multilayer ceramic capacitors, films for dry film resists, release films for polarizing plates, optical release films, process release films, and films for packaging materials.

[0075] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0076] [Analysis of Reaction Products] The conversion rate of the raw furan compound before and after the reaction was calculated as follows by analyzing the reaction solution by gas chromatography (GC-2010 manufactured by Shimadzu Corporation, column: DB-5 manufactured by Agilent Technologies): Conversion rate of the raw furan compound = {1 - [amount of furan compound in the solution after the reaction (mol)] / [amount of furan compound in the raw material (mol)]} × 100 (%)

[0077] The yield of 2,5-dimethylfuran was calculated by analyzing the reaction solution by gas chromatography (Shimadzu GC-2030, column: Agilent Technologies DB-WAX) as follows: Yield of 2,5-dimethylfuran = [amount (mol) of 2,5-dimethylfuran in the solution after reaction] / [amount (mol) of the raw material furan compound] x 100 (%)

[0078] Example 1 In Example 1, 0.1 g of a furan compound (furan compound represented by the above formula (I-4)) prepared by the method described in a known literature (ChemCatChem. 2022, 14, e202200191.) was dissolved in 10 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and a hydrodeoxygenation reaction was carried out at 200°C for 3 hours in the presence of 0.2 g of Ru / C (Ru 5%) (manufactured by N.E. CHEMCAT) by injecting hydrogen gas at 0.9 MPa (gauge pressure) in an autoclave. The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 27%. Furthermore, 2,5-hexanedione was obtained in a yield of 4%, and 1,3-propanediol was obtained in a yield of 65%.

[0079] Comparative Example 1 Effect of Non-Aqueous Solvent In Comparative Example 1, a hydrodeoxygenation reaction was carried out in the same manner as in Example 1, except that the solvent was changed from tetrahydrofuran to water. As a result, 2,5-dimethylfuran was obtained in a yield of 2%. 2,5-hexanedione was obtained in an 8% yield, and 1,3-propanediol was obtained in a 61% yield.

[0080] In Comparative Example 1, in which an aqueous solvent was used as the solvent, the yield of 2,5-dimethylfuran was significantly reduced and the yield of 2,5-hexanedione formed by hydrolysis of 2,5-dimethylfuran was increased compared to Example 1, in which tetrahydrofuran was used as the non-aqueous solvent. This demonstrated the advantages of using a non-aqueous solvent as the solvent for the raw material compounds in the production of 2,5-dimethylfuran.

[0081] Example 2 In Example 2, 0.1 g of a furan compound (the furan compound represented by the above formula (I-4)) prepared by the method described in a known literature (ChemCatChem. 2022, 14, e202200191.) was dissolved in 10 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Hydrogen gas was injected at 2 MPa (gauge pressure) in an autoclave in the presence of 16 mg of Pd / C (Pd 5%) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and a hydrodeoxygenation reaction was carried out at 200°C for 2 hours. The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 9%. Furthermore, 2,5-hexanedione was not produced, and 1,3-propanediol was obtained in a yield of 72%.

[0082] Example 3 In Example 3, a hydrodeoxygenation reaction was carried out in the same manner as in Example 2, except that the catalyst was changed to Pt / C (Pt 5%) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 21%. Furthermore, 2,5-hexanedione was not produced, and 1,3-propanediol was obtained in a yield of 73%.

[0083] Example 4 In Example 4, a hydrodeoxygenation reaction was carried out in the same manner as in Example 2, except that the catalyst was changed to Rh / C (Pt 5%) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and analyzed by gas chromatography. As a result, 2,5-dimethylfuran was obtained in a yield of 60%. Furthermore, 2,5-hexanedione was not produced, and 1,3-propanediol was obtained in a yield of 92%.

[0084] In Example 5, a hydrodeoxygenation reaction was carried out in the same manner as in Example 4, except that the reaction temperature was set as shown in Table 1 below. The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and then analyzed by gas chromatography. The results are shown in Table 1.

[0085]

[0086] In Example 6, a hydrodeoxygenation reaction was carried out in the same manner as in Example 4, except that the hydrogen pressure was set as shown in Table 2 below. The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and then analyzed by gas chromatography. The results are shown in Table 2.

[0087]

[0088] In Example 7, a hydrodeoxygenation reaction was carried out in the same manner as in Example 4, except that the nonaqueous solvent was changed as shown in Table 3 below. The reaction solution obtained by this hydrodeoxygenation reaction was cooled to room temperature, diluted with tetrahydrofuran, and then analyzed by gas chromatography. The results are shown in Table 3.

[0089]

[0090] The present invention makes it possible to efficiently produce 2,5-dimethylfuran, which is useful as a polymer raw material, etc. In particular, when a biomass-derived furan compound is used, 100% biomass-derived 2,5-dimethylfuran can be obtained. By combining the obtained 100% biomass-derived 2,5-dimethylfuran with biomass-derived ethylene, 100% biomass-derived paraxylene can be obtained. By combining such 100% biomass-derived paraxylene with biomass-derived glycol, 100% biomass-derived polyester can be obtained. Furthermore, terephthalic acid can be obtained using the paraxylene as a raw material, and a polyester composition can be obtained using the terephthalic acid as a raw material. Fiber materials, resin materials, and film materials can be obtained using the polyester composition. Consequently, fiber products, resin products, and film products can be obtained.

Claims

1. A method for producing 2,5-dimethylfuran, comprising a step of reacting a furan compound represented by general formula (I) with hydrogen in a non-aqueous solvent in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst comprises at least one selected from the group of first components shown below and at least one selected from the group of second components shown below: [In general formula (I), R 1 represents -CHOH, an alkyl group having 1 to 5 carbon atoms, -CHOC(O)R 4 , -C(O)OR 5 R is any one of the groups represented by 2 and R 3 are each an alkyl group having 1 to 5 carbon atoms, which may be different from each other, and may be bonded to each other to form a ring structure. 4 is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. (First component group) chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, and cadmium. (Second component group) magnesium aluminate, calcium aluminate, magnesium silicate, calcium silicate, aluminosilicate, boron oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, hafnium oxide, lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, zinc oxide, chromium oxide, hydroxyapatite, silicon carbide, magnesium carbonate, calcium carbonate, barium carbonate, carbon, graphite, diamond, silicon nitride, aluminum nitride, boron nitride, aluminosilicophosphate, aluminophosphate, magnesium phosphate, calcium phosphate, strontium phosphate, pyrophosphate, chlorapatite, fluorapatite, calcium sulfate, and barium sulfate.

2. The method for producing 2,5-dimethylfuran according to claim 1, wherein the non-aqueous solvent is at least one selected from the group consisting of hydrocarbons, alcohols, ethers, and esters.

3. A method for producing paraxylene, comprising the following steps (A) and (B): Step (A): A step of producing 2,5-dimethylfuran by the method for producing 2,5-dimethylfuran according to claim 1. Step (B): A step of producing paraxylene using the 2,5-dimethylfuran obtained by step (A) as a raw material.

4. A method for producing terephthalic acid, comprising the step of producing terephthalic acid using paraxylene obtained by the method for producing paraxylene according to claim 3 as a raw material.

5. A method for producing polyester, comprising the step of producing polyester using terephthalic acid obtained by the method for producing terephthalic acid according to claim 4 as a raw material.

6. Paraxylene containing 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, toluene, 2-methylfuran, and 2-methyltetrahydrofuran as components, with the total content of the above components being 0.001 ppm or more and 500 ppm or less.

7. Terephthalic acid containing 2,5-furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, benzoic acid, 2-furancarboxylic acid, and tetrahydrofuran-2-carboxylic acid as components, in which the total content of the components is 0.001 ppm or more and 500 ppm or less.

8. A polyester composition obtained by the polyester production method according to claim 5.

9. A polyester composition obtained using the terephthalic acid according to claim 7 as a raw material.

10. A fiber material made using the polyester composition according to claim 8 or 9.

11. A resin material made using the polyester composition according to claim 8 or 9.

12. A film material made using the polyester composition according to claim 8 or 9.

13. A textile product made using the textile material according to claim 10.

14. The textile product according to claim 13, which is a clothing product, an industrial material, a construction material, or a material for daily life.

15. A resin product made using the resin material described in claim 11.

16. The resin product according to claim 15, which is an electric / electronic device part, an automobile part, a machine part, or a housing material.

17. A film product made using the film material according to claim 12.

18. The film product according to claim 17, which is a release film for manufacturing multilayer ceramic capacitors, a film for dry film resists, a release film for polarizing plates, an optical release film, a process release film, or a film for packaging materials.

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