Product of 1, 3-butanediol

Abstract

A product 1, 3-butanediol in which the sum of n-dodecane-converted concentrations of peaks other than methyl ethyl ketone and an acetal form of 1, 3-butanediol among peaks appearing in the range of a relative retention time of 0.80-0.99 when the relative retention time of n-dodecane is 1.00 in gas chromatography by a non-split injection method under specific conditions is 25 ppm or less.

Description

Technical Field

[0001] The present invention relates to a product 1,3-butanediol which is useful as a raw material for synthetic resins, a raw material for surfactants, a solvent, an antifreeze solution, a raw material for cosmetics, and the like. Background Art

[0002] 1,3-Butanediol is a viscous, colorless, transparent, low-odor liquid with a boiling point of 208°C and excellent chemical stability. Therefore, 1,3-Butanediol is used as a raw material for various synthetic resins and surfactants. In addition, 1,3-Butanediol is also used as a material for cosmetics, desiccant, high-boiling-point solvent, and antifreeze by effectively utilizing its excellent hygroscopic properties, low volatility, and low toxicity. In recent years, in the cosmetics industry, in particular, the demand for 1,3-Butanediol has increased significantly due to its excellent properties as a moisturizer with low toxicity and irritation.

[0003] Patent Document 1 discloses 1,3-butanediol having less odor, and discloses a method for producing 1,3-butanediol by purifying crude 1,3-butanediol by hydrogenation as a method for obtaining 1,3-butanediol having less odor.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2020-512351 Summary of the invention

[0007] Problems to be solved by the invention

[0008] Here, for example, when 1,3-butanediol is used in the field of cosmetics, it is directly applied to the skin, but the 1,3-butanediol obtained by the method described in Patent Document 1 still has the problem of not being able to sufficiently reduce skin sensitization. In addition, when 1,3-butanediol is used in the field of cosmetics, it is sometimes heated under alkaline conditions for compounding, but there is also the problem of coloring of 1,3-butanediol during mixing preparation under alkaline conditions.

[0009] In view of the above circumstances, an object of the present invention is to provide a 1,3-butanediol product that can reduce skin sensitization and is less likely to be colored under alkaline conditions.

[0010] Methods used to solve problems

[0011] The present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by suppressing the concentration of specific impurities contained in 1,3-butanediol to a certain level or less, thereby completing the present invention.

[0012] That is, the present invention is as follows. In addition, in this specification, ppm means mass ppm unless otherwise specified.

[0013] [1] A 1,3-butanediol product, wherein, in a gas chromatography analysis by a splitless injection method under the following conditions, when the relative retention time of n-dodecane is set to 1.00, the sum of the n-dodecane conversion concentrations of peaks appearing in the range of relative retention times of 0.80 to 0.99, excluding peaks of methyl ethyl ketone and acetal of 1,3-butanediol, is 25 ppm or less.

[0014] [Conditions for gas chromatography analysis]

[0015] Analytical column: Column with (50% cyanopropyl-phenyl) dimethylpolysiloxane as the stationary phase (length 30m×inner diameter 0.25mm×film thickness 0.25μm)

[0016] Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. The temperature was kept at 220°C for 12 minutes.

[0017] Sample introduction temperature: 220℃

[0018] Carrier gas: Nitrogen

[0019] Column gas flow rate: 0.5 mL / min

[0020] Detector and detection temperature: hydrogen flame ionization detector (FID), 220℃

[0021] Control mode: Constant flow

[0022] Split ratio: No split

[0023] Inlet vent purge: 60mL / min

[0024] Purge start time: 1 minute

[0025] Sample injection conditions: 0.6μL

[0026] Sample preparation: n-dodecane as an internal standard was diluted with 2-propanol to 24 ppm to prepare an internal standard solution, and then 0.5 g of product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample.

[0027] Calculation of the sum of n-dodecane conversion concentrations: When the relative retention time of n-dodecane detected under the above-mentioned gas chromatography analysis conditions is set to 1.00, the total area value (detection peak area value) of the peaks detected within the relative retention time range of 0.80 to 0.99, excluding the peaks of the acetal form of methyl ethyl ketone and 1,3-butanediol, is converted into the sum of n-dodecane conversion concentrations using the following formula (1).

[0028] The sum of the converted concentration of n-dodecane (ppm) = n-dodecane concentration (ppm) × detection peak area value / n-dodecane area value (1)

[0029] Here, the n-dodecane concentration (ppm) refers to a value calculated using the following formula (2).

[0030] n-Dodecane concentration (ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2)

[0031] [2] A product 1,3-butanediol, wherein the sum of the n-dodecane conversion concentrations of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol is 20 ppm or less in a gas chromatographic analysis by a splitless injection method under the following conditions.

[0032] [Conditions for gas chromatography analysis]

[0033] Analytical column: Column with (50% cyanopropyl-phenyl) dimethylpolysiloxane as the stationary phase (length 30m×inner diameter 0.25mm×film thickness 0.25μm)

[0034] Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. The temperature was kept at 220°C for 12 minutes.

[0035] Sample introduction temperature: 220℃

[0036] Carrier gas: Nitrogen

[0037] Column gas flow rate: 0.5 mL / min

[0038] Detector and detection temperature: hydrogen flame ionization detector (FID), 220℃

[0039] Control mode: Constant flow

[0040] Split ratio: No split

[0041] Inlet vent purge: 60mL / min

[0042] Purge start time: 1 minute

[0043] Sample injection conditions: 0.6μL

[0044] Sample preparation: n-dodecane as an internal standard was diluted with 2-propanol to 24 ppm to prepare an internal standard solution, and then 0.5 g of product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample.

[0045] Calculation of the sum of n-dodecane-converted concentrations: The total area value (detection peak area value) of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol detected under the above-mentioned gas chromatography analysis conditions was converted into the sum of n-dodecane-converted concentrations using the following formula (1).

[0046] The sum of the converted concentration of n-dodecane (ppm) = n-dodecane concentration (ppm) × detection peak area value / n-dodecane area value (1)

[0047] Here, the n-dodecane concentration (ppm) refers to a value calculated using the following formula (2).

[0048] n-Dodecane concentration (ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2)

[0049] [3] The 1,3-butanediol product according to [1] or [2] above, wherein the area ratio of the peak of 1,3-butanediol is 99.5% or more in a gas chromatography analysis under the following conditions.

[0050] [Conditions for gas chromatography analysis]

[0051] Analytical column: Column with polyethylene glycol as the stationary phase (length 30m×inner diameter 0.25mm×film thickness 0.25μm)

[0052] Heating conditions: 5°C / min from 80°C to 230°C, then maintain at 230°C for 10 minutes

[0053] Sample introduction temperature: 250℃

[0054] Carrier gas: Nitrogen

[0055] Column gas flow rate: 0.5 mL / min

[0056] Detector and detection temperature: hydrogen flame ionization detector (FID), 250℃

[0057] Control mode: Constant flow

[0058] Split ratio: 50:1

[0059] Sample injection conditions: 1μL

[0060] Effects of the Invention

[0061] According to the present invention, it is possible to provide a product 1,3-butanediol which can reduce skin sensitization and is less likely to be colored under alkaline conditions. DETAILED DESCRIPTION

[0062] Hereinafter, an embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following description, and can be implemented in various modifications within the scope of the gist thereof.

[0063] In addition, in this embodiment, 1,3-butanediol as a final product is referred to as "product 1,3-butanediol", and 1,3-butanediol as a raw material or an intermediate before the final product is referred to as "crude 1,3-butanediol".

[0064] [Product 1,3-Butanediol Production Method]

[0065] (raw material)

[0066] The crude 1,3-butanediol used as a raw material when producing the product 1,3-butanediol in the present embodiment is not particularly limited, and examples thereof include 1,3-butanediol having skin sensitization and 1,3-butanediol that is colored under alkaline conditions.

[0067] Regarding crude 1,3-butanediol as a raw material, from the viewpoint of reducing the amount of impurities contained in the product 1,3-butanediol, the area ratio of the peak of 1,3-butanediol in gas chromatography analysis 2 under specific conditions described later is preferably 99.5% or more, more preferably 99.6% or more, and even more preferably 99.7% or more.

[0068] The manufacturing method of crude 1,3-butanediol as a raw material is not particularly limited, for example, crude 1,3-butanediol can be manufactured by a known method (refer to Japanese Patent Publication No. 3-80139, Japanese Patent Publication No. 7-258129, etc.). In addition, crude 1,3-butanediol manufactured by a liquid phase hydrogen reduction method of butanediol, crude 1,3-butanediol manufactured by a hydrolysis method of 1,3-butylene oxide, or crude 1,3-butanediol manufactured by a fermentation method using microorganisms or fungi, any of these mixtures, etc. can also be used. Among them, the method of using the reaction product obtained by the liquid phase hydrogen reduction method of butanediol is preferred because it has a tendency to make the effect of the present invention more significant. In the liquid phase hydrogen reduction method of butyraldehyde, low-boiling point compounds such as acetaldehyde, n-butyraldehyde, crotonaldehyde, methyl vinyl ketone, and their condensation products or acetals with 1,3-butanediol, and acetals with ethanol, which are considered to be odor-causing substances, are produced. These are difficult to fully remove by distillation. In addition, there is the following problem: in the heating step such as distillation, acetaldehyde and n-butyraldehyde undergo a condensation reaction to produce 2-ethyl crotonaldehyde or acetals with n-butyraldehyde and 1,3-butanediol. The above-mentioned odor-causing substances include substances that are odor sources themselves and substances that become odorous substances due to changes over time, heat treatment, chemical treatment, etc.

[0069] Alternatively, crude 1,3-butanediol may be obtained by removing by-products such as ethanol, salts, and water from a reaction product obtained by liquid-phase hydrogen reduction of aldol. The method for removing these components is not limited, and methods such as distillation and adsorption may be used.

[0070] Alternatively, the fraction after removal of ethanol and the like may be subjected to one or more known purification steps, such as a step of adding an alkali metal compound (such as sodium hydroxide, potassium hydroxide, etc.) and performing a heat treatment (see Japanese Patent No. 4559625, etc.) to obtain a crude 1,3-butanediol. Alternatively, the crude 1,3-butanediol may be obtained as a commercially available product.

[0071] (Hydrogenation step)

[0072] The method for producing the product 1,3-butanediol in this embodiment includes a step of hydrogenating crude 1,3-butanediol using a catalyst (hydrogenation step). More specifically, the hydrogenation step is, for example, a step of hydrogen reduction by flowing crude 1,3-butanediol and hydrogen gas through a catalyst layer filled with a catalyst.

[0073] It is presumed that by hydrogenating crude 1,3-butanediol using a catalyst, acetals of 2-ethylcrotonaldehyde and n-butyraldehyde with 1,3-butanediol, which are coloring and skin sensitization-causing substances under alkaline conditions, are hydrogenated or hydrogenolyzed. However, the mechanism of the present invention is not limited to the above.

[0074] The hydrotreatment step can be carried out in either the gas phase or the liquid phase, preferably in the liquid phase. When implemented in the liquid phase, the reaction temperature can be set to a lower temperature than when implemented in the gas phase, so that the thermal decomposition reaction of 1,3-butanediol can be suppressed. In the hydrotreatment step, a Pd / C catalyst is preferably used as a catalyst. A Pd / C catalyst refers to a catalyst having activated carbon as a carrier and palladium dispersed and loaded thereon. The loading rate of the palladium dispersed and loaded on the activated carbon is not particularly limited, and is preferably 0.1 to 30%, more preferably 0.2 to 10%, and particularly preferably 0.4 to 1%. In addition, the shape of the Pd / C catalyst is not particularly limited, and may be in the form of powder, particles, or the like.

[0075] The reaction temperature in the hydrotreatment step is not particularly limited. When the heat treatment step described later is carried out, it is preferably 100 to 150°C, more preferably 110 to 145°C, and further preferably 125 to 135°C. When the heat treatment step described later is not carried out, it is preferably higher than 120 to 150°C, and more preferably 125 to 135°C.

[0076] When the reaction temperature in the hydrogenation treatment step is 150°C or lower, the thermal decomposition reaction of 1,3-butanediol does not proceed and the increase of high boiling point components tends to be suppressed. When the reaction temperature is 100°C or higher (more than 120°C when the heating treatment step is not performed), the hydrogenation or hydrogenolysis of the acetal of 2-ethylcrotonaldehyde and n-butyraldehyde with 1,3-butanediol tends to be promoted.

[0077] The hydrogen pressure in the hydrotreatment step is not particularly limited, but is preferably 0.4 to 1.0 MPa, more preferably 0.5 to 0.9 MPa, and further preferably 0.6 to 0.8 MPa. When the hydrogen pressure in the hydrotreatment step is 1.0 MPa or less, a thick-walled device with sufficient strength is not required as a high-pressure gas device, and thus the device cost tends to be reduced. When the hydrogen pressure is 0.4 MPa or more, the hydrogenation or hydrogenolysis of the acetal of 2-ethylcrotonaldehyde and n-butyraldehyde with 1,3-butanediol tends to be promoted.

[0078] The method for producing the product 1,3-butanediol in the present embodiment is not particularly limited as long as it includes a step of hydrogenating crude 1,3-butanediol using a catalyst (hydrogenation step), and in addition to the hydrogenation step, it may further include one or more of a step of heating crude 1,3-butanediol (heating step) and a step of removing low-boiling components from crude 1,3-butanediol (low-boiling distillation step). The order of these steps is not particularly limited, but from the viewpoint of making the effect of the present invention more significant, it is preferably implemented in the order of the heating step, the hydrogenation step, and the low-boiling distillation step.

[0079] Each step is described below.

[0080] (Heat treatment step)

[0081] The heating treatment step in the method for producing the product 1,3-butanediol of the present embodiment is a step of heating the crude 1,3-butanediol. By heating the crude 1,3-butanediol, acetaldehyde and n-butyraldehyde, which are the source substances of the associated 2-ethyl crotonaldehyde, are consumed due to condensation reactions, etc., or n-butyraldehyde, which is the source substance of the associated acetal of n-butyraldehyde and 1,3-butanediol, is consumed. Therefore, in the subsequent distillation step and other steps accompanied by heating, the amount of acetals of 2-ethyl crotonaldehyde and n-butyraldehyde and 1,3-butanediol is reduced. In addition, in the heating step, after 2-ethyl crotonaldehyde or n-butyraldehyde is associated with the acetal of 1,3-butanediol, etc., a hydrogenation treatment is performed, thereby having a tendency for the source substance to be efficiently decomposed due to hydrogenation or hydrogenolysis. However, the mechanism of the present invention is not limited to the above.

[0082] The heating time in the heat treatment step is not particularly limited, but is preferably 20 minutes to 9 hours, more preferably 1 to 6 hours, and still more preferably 1 to 3 hours. When the heating time is 20 minutes or more, there is a tendency that the consumption of acetaldehyde and n-butyraldehyde by the condensation reaction proceeds sufficiently, and when the heating time is 9 hours or less, there is a tendency that the increase in the cost required for the heat treatment can be suppressed.

[0083] The heating temperature in the heat treatment step is not particularly limited, but is preferably 80 to 200° C., more preferably 90 to 120° C., and further preferably 100 to 110° C. When the heating temperature is 80° C. or higher, the condensation reaction of acetaldehyde and n-butyraldehyde tends to proceed, and when the heating temperature is 200° C. or lower, the thermal decomposition reaction of 1,3-butanediol tends to be suppressed, and impurities tend to be reduced.

[0084] The heat treatment apparatus in the heat treatment step is not particularly limited, and examples thereof include continuous tube-type, batch tank-type, and continuous tank-type heat treatment apparatuses. From the viewpoint of stirring efficiency, a batch tank-type is particularly preferred.

[0085] (low boiling distillation step)

[0086] The step of removing low-boiling distillation in the method for producing the product 1,3-butanediol of the present embodiment is, for example, a step of removing low-boiling components from the fraction containing more 1,3-butanediol obtained by the hydrogenation treatment step. As the distillation apparatus used in the step of removing low-boiling distillation, for example, a porous plate column, a bubble column, a packed column, etc., among which a packed column with a theoretical plate number of 7 to 40 is preferred. A single distillation tower can be used, or two or more towers can be used. As the conditions for distillation, the pressure at the top of the distillation tower is preferably 1 to 20 kPa, and the temperature at the bottom of the distillation tower is preferably 100 to 160°C, more preferably 110 to 140°C. As a specific mode of the step of removing low-boiling distillation, it can be a continuous method or a batch method. For example, as a continuous method, a method of continuously supplying a fraction containing more 1,3-butanediol from the top of the distillation tower, continuously taking out a fraction containing more low-boiling components from the top of the tower, and continuously taking out a fraction containing more 1,3-butanediol from the bottom of the tower can be cited.

[0087] [Product 1,3-Butanediol]

[0088] As one of the present embodiments, a product 1,3-butanediol is provided, wherein in a gas chromatography analysis based on a splitless injection method under the following conditions, when the relative retention time of n-dodecane is set to 1.00, the sum of the n-dodecane conversion concentrations of the peaks appearing in the range of relative retention times of 0.80 to 0.99, excluding the peaks of methyl ethyl ketone and the acetal form of 1,3-butanediol, is less than 25 ppm.

[0089] [Conditions for gas chromatography analysis]

[0090] Analytical column: Column with (50% cyanopropyl-phenyl) dimethylpolysiloxane as the stationary phase (length 30m×inner diameter 0.25mm×film thickness 0.25μm)

[0091] Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. The temperature was kept at 220°C for 12 minutes.

[0092] Sample introduction temperature: 220℃

[0093] Carrier gas: Nitrogen

[0094] Column gas flow rate: 0.5 mL / min

[0095] Detector and detection temperature: hydrogen flame ionization detector (FID), 220℃

[0096] Control mode: Constant flow

[0097] Split ratio: No split

[0098] Inlet vent purge: 60mL / min

[0099] Purge start time: 1 minute

[0100] Sample injection conditions: 0.6μL

[0101] Sample preparation: n-dodecane as an internal standard was diluted with 2-propanol to 24 ppm to prepare an internal standard solution, and then 0.5 g of product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample.

[0102] Calculation of the sum of n-dodecane conversion concentrations: When the relative retention time of n-dodecane detected under the above-mentioned gas chromatography analysis conditions is set to 1.00, the total area value (detection peak area value) of the peaks detected within the relative retention time range of 0.80 to 0.99, excluding the peaks of the acetal form of methyl ethyl ketone and 1,3-butanediol, is converted into the sum of n-dodecane conversion concentrations using the following formula (1).

[0103] The sum of the converted concentration of n-dodecane (ppm) = n-dodecane concentration (ppm) × detection peak area value / n-dodecane area value (1)

[0104] Here, the n-dodecane concentration (ppm) refers to a value calculated using the following formula (2).

[0105] n-Dodecane concentration (ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2)

[0106] Here, as the analytical column, for example, DB-225 manufactured by Agilent Technologies (length 30 m×inner diameter 0.25 mm×film thickness 0.25 μm, stationary phase: (50% cyanopropyl-phenyl) dimethylpolysiloxane) can be used.

[0107] Regarding 1,3-butanediol, which is a product of one embodiment of the present invention, in order to have a tendency that the effect exerted by the present invention becomes more significant, the sum of the n-dodecane conversion concentrations of the peaks appearing in the relative retention time range of 0.80 to 0.99, excluding the peaks of methyl ethyl ketone and the acetal form of 1,3-butanediol, is 25 ppm or less, preferably 23 ppm or less, and more preferably 21 ppm or less.

[0108] In addition, as one of the present embodiments, a product 1,3-butanediol is provided, wherein the sum of the n-dodecane conversion concentrations of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol in gas chromatography analysis based on a splitless injection method under the following conditions is 20 ppm or less.

[0109] [Conditions for gas chromatography analysis]

[0110] Analytical column: Column with (50% cyanopropyl-phenyl) dimethylpolysiloxane as the stationary phase (length 30m×inner diameter 0.25mm×film thickness 0.25μm)

[0111] Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. The temperature was kept at 220°C for 12 minutes.

[0112] Sample introduction temperature: 220℃

[0113] Carrier gas: Nitrogen

[0114] Column gas flow rate: 0.5 mL / min

[0115] Detector and detection temperature: hydrogen flame ionization detector (FID), 220℃

[0116] Control mode: Constant flow

[0117] Split ratio: No split

[0118] Inlet vent purge: 60mL / min

[0119] Purge start time: 1 minute

[0120] Sample injection conditions: 0.6μL

[0121] Sample preparation: n-dodecane as an internal standard was diluted with 2-propanol to 24 ppm to prepare an internal standard solution, and then 0.5 g of product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample.

[0122] Calculation of the sum of n-dodecane-converted concentrations: The total area value (detection peak area value) of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol detected under the above-mentioned gas chromatography analysis conditions was converted into the sum of n-dodecane-converted concentrations using the following formula (1).

[0123] The sum of the converted concentration of n-dodecane (ppm) = n-dodecane concentration (ppm) × detection peak area value / n-dodecane area value (1)

[0124] Here, the n-dodecane concentration (ppm) refers to a value calculated using the following formula (2).

[0125] n-Dodecane concentration (ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2)

[0126] Here, as the analytical column, for example, DB-225 manufactured by Agilent Technologies (length 30 m×inner diameter 0.25 mm×film thickness 0.25 μm, stationary phase: (50% cyanopropyl-phenyl) dimethylpolysiloxane) can be used.

[0127] Regarding 1,3-butanediol, which is a product of one embodiment of the present invention, in order to have a tendency for the effect exerted by the present invention to become more significant, the sum of the n-dodecane conversion concentrations of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol is 20 ppm or less, preferably 16 ppm or less, and more preferably 12 ppm or less.

[0128] Regarding the product 1,3-butanediol of the present embodiment, the area ratio of the peak of 1,3-butanediol in the gas chromatography analysis under the following conditions is preferably 99.5% or more, more preferably 99.7% or more, further preferably 99.8% or more, and particularly preferably 99.9% or more, depending on the required product quality. It should be noted that the "area ratio" of a peak refers to the ratio of the area of ​​a specific peak to the sum of the areas of all peaks appearing in the chromatogram. In addition, all peaks refer to all peaks that appear when the relative retention time of the peak of 1,3-butanediol is set to 1.0 and the analysis is continued until the relative retention time is 2.2 and stopped. By making the area ratio of the above peaks within the above range, there is a tendency for the generation of odor and skin sensitization to be further reduced.

[0129] [Conditions for gas chromatography analysis]

[0130] Analytical column: Column with polyethylene glycol as the stationary phase (length 30m×inner diameter 0.25mm×film thickness 0.25μm)

[0131] Heating conditions: 5°C / min from 80°C to 230°C, then maintain at 230°C for 10 minutes

[0132] Sample introduction temperature: 250℃

[0133] Carrier gas: Nitrogen

[0134] Column gas flow rate: 0.5 mL / min

[0135] Detector and detection temperature: hydrogen flame ionization detector (FID), 250℃

[0136] Control mode: Constant flow

[0137] Split ratio: 50:1

[0138] Sample injection conditions: 1μL

[0139] Here, as the analytical column, for example, DB-WAX manufactured by Agilent Technologies (column with a stationary phase of polyethylene glycol; length 30 m×inner diameter 0.25 mm×film thickness 0.25 μm) can be used.

[0140] [Skin sensitization test]

[0141] The product 1,3-butanediol in this embodiment is 1,3-butanediol with reduced skin sensitization. Here, skin sensitization refers to an allergic reaction caused after contact with the skin. In the past, experimental animals were usually used to evaluate skin sensitization, but from the perspective of animal welfare, the 2015 OECD Guideline TG442C selected the peptide binding test (DPRA) as an in vitro chemical (in chemico) test as an alternative test. In this embodiment, skin sensitization is also evaluated by a test using DPRA. In more detail, skin sensitization is evaluated according to the method described in the examples described later.

[0142] [Coloring under alkaline conditions]

[0143] The product 1,3-butanediol in this embodiment has the advantage that it is not easy to be colored under alkaline conditions. The coloration under alkaline conditions can be evaluated by the method described in the examples described later (alkaline coloration test). Chromaticity (b ) is not particularly limited, but is, for example, preferably 4.0 or less, more preferably 3.8 or less, and particularly preferably 3.5 or less, in terms of an average value of three measurements.

[0144] Example

[0145] The present invention is further specifically described below by examples, but the present invention is not limited to the following examples. As the crude 1,3-butanediol used as the raw material, a substance obtained by hydrogenating and reducing butanediol and then performing low-boiling distillation and high-boiling distillation (distillation to remove high-boiling components contained in the crude 1,3-butanediol) was used. In addition, various analyses and evaluations were performed as follows. In the gas chromatography analysis 2 under the following conditions, the peak area ratio of the crude 1,3-butanediol used as the raw material was 99.6%.

[0146] [Gas chromatography analysis 1]

[0147] The product 1,3-butanediol obtained in Examples 1 to 3 and Comparative Example 1 was subjected to gas chromatography analysis 1 by the following method.

[0148] (Conditions of gas chromatography analysis 1)

[0149] Analytical device: 7890A gas chromatograph system manufactured by Agilent Technologies

[0150] Analytical column: DB-225 manufactured by Agilent Technologies (length 30 m×inner diameter 0.25 mm×film thickness 0.25 μm, stationary phase: (50% cyanopropyl-phenyl) dimethylpolysiloxane)

[0151] Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. The temperature was kept at 220°C for 12 minutes.

[0152] Sample introduction temperature: 220℃

[0153] Carrier gas: Nitrogen

[0154] Column gas flow rate: 0.5 mL / min

[0155] Detector and detection temperature: hydrogen flame ionization detector (FID), 220℃

[0156] Control mode: Constant flow

[0157] Split ratio: No split

[0158] Inlet vent purge: 60mL / min

[0159] Purge start time: 1 minute

[0160] Sample injection conditions: 0.6μL

[0161] Sample preparation: n-dodecane manufactured by GL Sciences was diluted to 24 ppm with 2-propanol manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. to prepare an internal standard solution. 0.5 g of product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample.

[0162] Calculation of the sum of n-dodecane conversion concentrations: When the relative retention time of n-dodecane detected under the above-mentioned measurement conditions is set to 1.00, the total area value (detected peak area value) of the peaks detected at the relative retention time of 0.80 to 0.99, excluding the peak of the acetal of methyl ethyl ketone and 1,3-butanediol, is converted into the sum of n-dodecane conversion concentrations using the following formula (1), and this is taken as the impurity concentration A. In addition, the total area value (detected peak area value) of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol is converted into the sum of n-dodecane conversion concentrations using the following formula (1), and this is taken as the impurity concentration B.

[0163] The sum of the converted concentration of n-dodecane (ppm) = n-dodecane concentration (ppm) × detection peak area value / n-dodecane area value (1)

[0164] Here, the n-dodecane concentration (ppm) refers to a value calculated using the following formula (2).

[0165] n-Dodecane concentration (ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2)

[0166] [Gas chromatography analysis 2]

[0167] The crude 1,3-butanediol used as the raw material in Examples 1 to 3 and Comparative Example 1 and the product 1,3-butanediol obtained in Examples 1 to 3 and Comparative Example 1 were subjected to gas chromatography analysis 2 according to the following method.

[0168] (Conditions of gas chromatography analysis 2)

[0169] Analytical device: 7890B gas chromatograph system manufactured by Agilent Technologies

[0170] Analytical column: DB-WAX manufactured by Agilent Technologies (column with polyethylene glycol as the stationary phase; length 30 m×inner diameter 0.25 mm×film thickness 0.25 μm)

[0171] Heating conditions: 5°C / min from 80°C to 230°C, then maintain at 230°C for 10 minutes

[0172] Sample introduction temperature: 250℃

[0173] Carrier gas: Nitrogen

[0174] Column gas flow rate: 0.5 mL / min

[0175] Detector and detection temperature: hydrogen flame ionization detector (FID), 250℃

[0176] Control mode: Constant flow

[0177] Split ratio: 50:1

[0178] Sample injection conditions: 1μL

[0179] [Skin sensitization test]

[0180] The skin sensitization of the product 1,3-butanediol obtained in Examples 1 to 3 and Comparative Example 1 was evaluated by the following method.

[0181] (Conditions of skin sensitization test)

[0182] 15 mg of a cysteine-containing peptide for DPRA manufactured by Skullam was mixed with 30 mL of a 0.05 M phosphate buffer to prepare a 0.05 M phosphate buffer solution containing 0.667 mM of the peptide (hereinafter referred to as a peptide solution). One hour after the preparation of the peptide solution, 750 μL of the peptide solution and 250 μL of acetonitrile were added to three brown sample bottles for HPLC to prepare three standard solutions. Two hours after the preparation of the standard solution, 750 μL of the peptide solution, 200 μL of acetonitrile and 50 μL of 1,3-butanediol were added to another brown sample bottle for HPLC to prepare a sample solution (sample solution 1). Furthermore, 4 hours and 6 hours after the preparation of the standard solution, sample solutions (sample solutions 2 and 3) were prepared by the same operation. The three standard solutions and sample solutions (sample solution 1, sample solution 2, sample solution 3) were measured by HPLC analysis 72±2 hours after the preparation of each solution, and the three average values ​​of the peak heights of the peptides in the standard solutions and sample solutions were calculated. The peptide reduction rate was calculated from the calculated three average values ​​using the following formula (3) as the evaluation result.

[0183] Peptide reduction rate (%) = (average of three times the peak height of the peptide in the sample solution / average of three times the peak height of the peptide in the reference solution) × 100 (3)

[0184] In this test, from the viewpoint of reproducibility, the sample solution of the product 1,3-butanediol of Comparative Example 1 as a reference and the sample solutions of the products 1,3-butanediol of Examples 1 to 3 were tested on the same day.

[0185] (Conditions of HPLC analysis in skin sensitization test)

[0186] Analysis device: Agilent 1260 InfinityII manufactured by Agilent Technologies

[0187] Detector: Agilent Technologies Agilent 1260 InfinityII UV-Vis Detector G7114A

[0188] Detection wavelength: 220nm

[0189] Analytical column: Zorbax SB-C-18 manufactured by Agilent Technologies (particle size 3.5 μm, inner diameter × length = 2.1 mm × 10 mm)

[0190] Column temperature: 30°C

[0191] Measurement time: 20 minutes

[0192] Mobile Phase:

[0193] A 0.1 volume % trifluoroacetic acid aqueous solution

[0194] B 0.085 volume % trifluoroacetic acid acetonitrile solution

[0195] gradient:

[0196] A / B=90 / 10~75 / 25(10 minutes)

[0197] A / B=75 / 25~10 / 90(1 minute)

[0198] A / B=10 / 90(2 minutes)

[0199] A / B=10 / 90~90 / 10(0.5 minutes)

[0200] A / B=90 / 10(6.5 minutes)

[0201] Mobile phase flow rate: 0.35mL / min

[0202] Sample injection conditions: 5μL

[0203] [Alkaline coloring test]

[0204] The coloration of the product 1,3-butanediol obtained in Examples 1 to 3 and Comparative Example 1 under alkaline conditions was evaluated by the following method.

[0205] (Conditions of alkaline coloring test)

[0206] 13 g of water and 2 g of potassium hydroxide were added to a 100 mL heat-resistant medium bottle and mixed, and 6 g of the product 1,3-butanediol was added. Next, the heat-resistant medium bottle was immersed in a water bath and heated at 90°C for 1 hour. After cooling to room temperature, the chromaticity (b) of the solution after the heating treatment was measured using a spectrophotometer SE2000 manufactured by Nippon Denshoku Co., Ltd. ) as the rating.

[0207] [Example 1]

[0208] (Hydrogenation step)

[0209] The crude 1,3-butanediol was heated to 8.0 h -1 , make hydrogen gas at GHSV420h -1 Hydrogen reduction (hydrogenation treatment) was performed by flowing through a catalyst layer filled with 10 mL of a 0.5% Pd / C catalyst manufactured by NECHEMCAT Co. The hydrogen pressure during the reaction was 0.7 MPa, and the reaction temperature was set to 135°C.

[0210] The obtained product 1,3-butanediol was subjected to gas chromatography analysis 1. The result showed that when the relative retention time of n-dodecane was set to 1.00, the sum of the n-dodecane conversion concentrations of the peaks other than the peaks of methyl ethyl ketone and 1,3-butanediol acetal was detected at the relative retention time of 0.80 to 0.99 was 21 ppm (impurity concentration A). In addition, the sum of the n-dodecane conversion concentrations of the peaks of 2-ethylcrotonaldehyde and the peaks of n-butyraldehyde and 1,3-butanediol acetal was 12 ppm (impurity concentration B).

[0211] The product 1,3-butanediol was subjected to gas chromatography analysis 2. As a result, the area ratio of the peak of the product 1,3-butanediol was 99.6%.

[0212] The results of the skin sensitization test for the product 1,3-butanediol showed that the peptide reduction rate was 45 relative to the result of Comparative Example 1 as 100. In addition, the results of the alkaline coloration test showed that the chromaticity (b ) is 2.8.

[0213] These results are shown in Table 1 for the product 1,3-butanediol.

[0214] [Example 2]

[0215] The procedure of Example 1 was repeated except that the reaction temperature in the hydrotreatment step was 125°C.

[0216] The obtained product 1,3-butanediol was subjected to gas chromatography analysis 1. The result showed that when the relative retention time of n-dodecane was set to 1.00, the sum of the n-dodecane conversion concentrations of the peaks other than the peaks of methyl ethyl ketone and 1,3-butanediol acetal was detected at the relative retention time of 0.80 to 0.99 was 18 ppm (impurity concentration A). In addition, the sum of the n-dodecane conversion concentrations of the peaks of 2-ethylcrotonaldehyde and the peaks of n-butyraldehyde and 1,3-butanediol acetal was 10 ppm (impurity concentration B).

[0217] The product 1,3-butanediol was subjected to gas chromatography analysis 2. As a result, the area ratio of the peak of the product 1,3-butanediol was 99.6%.

[0218] The results of the skin sensitization test for the product 1,3-butanediol showed that the peptide reduction rate was 43 relative to the result of Comparative Example 1 as 100. In addition, the results of the alkaline coloration test showed that the chromaticity (b ) is 3.2.

[0219] [Example 3]

[0220] (Heat treatment step)

[0221] The crude 1,3-butanediol was flowed through a tank heated to 100° C. to perform a heat treatment so that the residence time was 1 hour.

[0222] (Hydrogenation step)

[0223] The same procedure as in Example 1 was carried out except that the 1,3-butanediol obtained in the above-mentioned heat treatment step was used as a raw material in the hydrogenation step and the reaction temperature in the hydrogenation step was set to 100°C.

[0224] (low boiling distillation step)

[0225] The 1,3-butanediol obtained in the above-mentioned hydrogenation treatment step was subjected to low-boiling distillation at an oil bath temperature of 126° C. and a pressure of 1.6 kPa using a distillation apparatus equipped with a packed tower (inner diameter 22 mm) with a height of 500 mm and filled with 3 mm-sized Dixon packings in a manner to achieve a filling height of 415 mm. A distillate of 10% by weight relative to the amount of the feed liquid was distilled off from the top of the distillation apparatus, and a product 1,3-butanediol was obtained from the bottom of the distillation apparatus.

[0226] The obtained product 1,3-butanediol was subjected to gas chromatography analysis 1. The result showed that when the relative retention time of n-dodecane was set to 1.00, the sum of the n-dodecane conversion concentrations of the peaks other than the peaks of methyl ethyl ketone and 1,3-butanediol acetal detected at the relative retention time of 0.80 to 0.99 was 0 ppm (impurity concentration A). In addition, the sum of the n-dodecane conversion concentrations of the peaks of 2-ethylcrotonaldehyde and the peaks of n-butyraldehyde and 1,3-butanediol acetal was 0 ppm (impurity concentration B).

[0227] The product 1,3-butanediol was subjected to gas chromatography analysis 2. As a result, the area ratio of the peak of the product 1,3-butanediol was 99.7%.

[0228] The results of the skin sensitization test for the product 1,3-butanediol showed that the peptide reduction rate was 22 relative to the result of Comparative Example 1 as 100. In addition, the results of the alkaline coloration test showed that the chromaticity (b ) is 0.7.

[0229] [Comparative Example 1]

[0230] The same procedure as in Example 1 was carried out except that the catalyst in the hydrogen reduction was NiSAT340 (composition: NiO, SiO 2 , Al 2 O 3 , etc.) manufactured by Clariant.

[0231] The obtained product 1,3-butanediol was subjected to gas chromatography analysis 1. The result showed that when the relative retention time of n-dodecane was set to 1.00, the sum of the n-dodecane conversion concentrations of the peaks other than the peaks of methyl ethyl ketone and 1,3-butanediol acetal was detected at the relative retention time of 0.80 to 0.99 was 28 ppm (impurity concentration A). In addition, the sum of the n-dodecane conversion concentrations of the peaks of 2-ethylcrotonaldehyde and the peaks of n-butyraldehyde and 1,3-butanediol acetal was 27 ppm (impurity concentration B).

[0232] The product 1,3-butanediol was subjected to gas chromatography analysis 2. As a result, the area ratio of the peak of the product 1,3-butanediol was 99.6%.

[0233] The skin sensitization test was conducted on the product 1,3-butanediol, and the peptide reduction rate obtained was set as 100 for the relative comparison with the examples. In addition, the results of the alkaline coloration test were chromaticity (b ) is 19.6.

[0234] [Table 1]

[0235]

[0236] This application is based on the Japanese patent application (Japanese Patent Application No. 2022-083950) filed with the Japan Patent Office on May 23, 2022, the contents of which are incorporated herein by reference.

[0237] Industrial Applicability

[0238] The 1,3-butanediol of the present invention has industrial applicability as a raw material for synthetic resins, a raw material for surfactants, a solvent, an antifreeze solution, a raw material for cosmetics, and the like.

Claims

1. A 1,3-butanediol product, wherein, in a gas chromatography analysis by a splitless injection method under the following conditions, when the relative retention time of n-dodecane is set to 1.00, the sum of the n-dodecane conversion concentrations of peaks appearing in the range of relative retention times of 0.80 to 0.99, excluding the peaks of methyl ethyl ketone and the acetal of 1,3-butanediol, is 25 mass ppm or less, [Conditions for gas chromatography analysis] Analytical column: a column with a stationary phase of (50% cyanopropyl-phenyl) dimethylpolysiloxane (length 30 m × inner diameter 0.25 mm × film thickness 0.25 μm), Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. After keeping at 220°C for 12 minutes, Sample introduction temperature: 220℃, Carrier gas: nitrogen, Column gas flow rate: 0.5mL / min, Detector and detection temperature: hydrogen flame ionization detector (FID), 220°C, Control mode: Constant flow, Split ratio: No split, Inlet vent purge: 60mL / min, Purge start time: 1 minute, Sample injection conditions: 0.6μL, Sample preparation: n-dodecane as an internal standard was diluted with 2-propanol to 24 mass ppm to prepare an internal standard solution, and then 0.5 g of the product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample. Calculation of the sum of n-dodecane conversion concentrations: When the relative retention time of n-dodecane detected under the gas chromatography analysis conditions is set to 1.00, the total area value (detection peak area value) of the peaks detected within the relative retention time range of 0.80 to 0.99, excluding the peaks of the acetal form of methyl ethyl ketone and 1,3-butanediol, is converted into the sum of n-dodecane conversion concentrations using the following formula (1): The sum of n-dodecane conversion concentration (mass ppm) = n-dodecane concentration (mass ppm) × detection peak area value / n-dodecane area value (1), Here, the n-dodecane concentration (mass ppm) refers to a value calculated using the following formula (2): n-Dodecane concentration (mass ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2).

2. A 1,3-butanediol product, wherein the sum of the n-dodecane conversion concentrations of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol in a gas chromatographic analysis by a splitless injection method under the following conditions is 20 mass ppm or less, [Conditions for gas chromatography analysis] Analytical column: a column with a stationary phase of (50% cyanopropyl-phenyl) dimethylpolysiloxane (length 30 m × inner diameter 0.25 mm × film thickness 0.25 μm), Heating conditions: After keeping at 50°C for 5 minutes, the temperature was increased from 50°C to 135°C at a rate of 10°C / min. After keeping at 135°C for 9 minutes, the temperature was increased from 135°C to 220°C at a rate of 15°C / min. After keeping at 220°C for 12 minutes, Sample introduction temperature: 220℃, Carrier gas: nitrogen, Column gas flow rate: 0.5mL / min, Detector and detection temperature: hydrogen flame ionization detector (FID), 220°C, Control mode: Constant flow, Split ratio: No split, Inlet vent purge: 60mL / min, Purge start time: 1 minute, Sample injection conditions: 0.6μL, Sample preparation: n-dodecane as an internal standard was diluted with 2-propanol to 24 mass ppm to prepare an internal standard solution, and then 0.5 g of the product 1,3-butanediol was mixed with 0.1 g of the internal standard solution to prepare a sample. Calculation of the sum of n-dodecane conversion concentrations: The total area value (detection peak area value) of the peak of 2-ethylcrotonaldehyde and the peak of the acetal of n-butyraldehyde and 1,3-butanediol detected under the gas chromatography analysis conditions is converted into the sum of n-dodecane conversion concentrations using the following formula (1): The sum of n-dodecane conversion concentration (mass ppm) = n-dodecane concentration (mass ppm) × detection peak area value / n-dodecane area value (1), Here, the n-dodecane concentration (mass ppm) refers to a value calculated using the following formula (2): n-Dodecane concentration (mass ppm) = (mass of n-dodecane in the sample / mass of product 1,3-butanediol in the sample) × 10 6 (2).

3. The product 1,3-butanediol according to claim 1 or 2, wherein In the gas chromatography analysis under the following conditions, the area ratio of the peak of 1,3-butanediol is 99.5% or more, [Conditions for gas chromatography analysis] Analytical column: a column with polyethylene glycol as the stationary phase (length 30 m × inner diameter 0.25 mm × film thickness 0.25 μm), Heating conditions: Heating from 80°C to 230°C at 5°C / min, then maintaining at 230°C for 10 minutes. Sample introduction temperature: 250°C, Carrier gas: nitrogen, Column gas flow rate: 0.5mL / min, Detector and detection temperature: hydrogen flame ionization detector (FID), 250°C, Control mode: Constant flow, Split ratio: 50:1, Sample injection conditions: 1 μL.

Images