Phenolic compositions and polymers

Abstract

This invention provides a biomass-derived phenol composition in which moldy odor is suppressed. [Solution] A phenol composition containing biomass-derived phenol (A), wherein the peak height percentage corresponding to isobutyraldehyde in total ion chromatography by GC-MS after pretreatment by 150°C headspace method is 4.0% or less.

Description

Technical Field

[0001] The present invention relates to a phenol composition and a polymer.

Background Art

[0002] In the context of global warming and the depletion of fossil resources, the production of chemicals from renewable biomass resources has attracted attention as a new industry towards the realization of a low-carbon society. Examples of such chemicals include phenol derived from biomass.

[0003] As a technology related to phenol derived from biomass, for example, it is described in Patent Document 1. Patent Document 1 describes a phenolic resin characterized by comprising a structure derived from specific plant-derived phenols, a structure derived from other phenols, a structure derived from aldehydes, and a structure derived from saccharides.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] According to the studies of the present inventors, it has been clarified that a biomass-derived phenol composition has an odor different from that of a petroleum-derived phenol composition, that is, a moldy odor.

[0006] The present invention provides a biomass-derived phenol composition that solves the above problems and has a suppressed moldy odor.

Means for Solving the Problems

[0007] The inventors diligently conducted research to achieve the above objectives. As a result, they discovered that moldy odors can be suppressed by adjusting the isobutyraldehyde content in the biomass-derived phenol composition, thus completing the present invention.

[0008] [1] A phenol composition containing biomass-derived phenol (A), A phenol composition in which, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to isobutyraldehyde is 4.0% or less. [2] Radiocarbon derived from biomass resources, determined based on the concentration of radiocarbon in circulating carbon in the 1950s, as measured according to ASTM D6866-20. 14 The phenol composition according to [1], wherein the measured bio-conversion rate of phenol (A), which indicates the proportion of C, is 80% or more and 100% or less. [3] A phenol composition according to [1] or [2], which is solid at 23°C. [4] A phenol composition according to any one of [1] to [3], wherein, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the sum of the peak height percentage corresponding to toluene and the peak height percentage corresponding to styrene is 2.00% or less. [5] A phenol composition according to any one of [1] to [4], wherein, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the sum of the peak height percentages corresponding to acetaldehyde, n-butyraldehyde, isobutyraldehyde, and isovaleraldehyde is 0.01% or more and 5.00% or less. [6] A phenol composition according to any one of [1] to [5], wherein, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to propionic acid is 0.35% or less. [7] A phenol composition according to any one of [1] to [6], wherein the content of phenol (A) is 70% by mass or more. [8] A polymer comprising at least one structural unit derived from phenol (A) in any of the phenol compositions described in [1] to [7]. [9] The polymer described in [8] is a phenolic resin. [Effects of the Invention]

[0009] According to the present invention, a biomass-derived phenol composition with suppressed moldy odor can be provided. [Modes for carrying out the invention]

[0010] Embodiments of the present invention will be described in detail below. In this embodiment, "pure water" refers to water with an electrical conductivity of 1 MΩ·cm or higher.

[0011] [Priority Composition] The phenol composition of this embodiment is a phenol composition containing biomass-derived phenol (A), and in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to isobutyraldehyde is 4.0% or less.

[0012] According to the phenol composition of this embodiment, although the detailed mechanism is unknown, the peak height percentage corresponding to isobutyraldehyde is 4.0% or less, which allows for the suppression of moldy odor even when using biomass-derived raw materials. The peak height ratio represents the ratio occupied by the detection intensity of the peak corresponding to a certain compound when the total of the detection intensities of all detected in the total ion chromatography of GC-MS by pretreatment with the 150 °C headspace method is taken as 100%. Here, if there is a moldy odor, the user may be concerned about the mold-induced deterioration and thus may hesitate to use it. In contrast, since the phenolic composition of the present embodiment can suppress the moldy odor, it can improve the user's comfort.

[0013] In the phenolic composition of the present embodiment, from the viewpoint of further suppressing the moldy odor, the peak height ratio corresponding to the isobutyraldehyde is preferably 3.50% or less, more preferably 3.00% or less, still more preferably 2.50% or less, still more preferably 2.00% or less, still more preferably 1.50% or less, still more preferably 1.00% or less, still more preferably 0.50% or less, still more preferably 0.25% or less, still more preferably 0.15% or less, still more preferably 0.10% or less, still more preferably 0.05% or less, still more preferably 0.03% or less, still more preferably 0.01% or less. The lower limit of the peak height ratio corresponding to the isobutyraldehyde is not particularly limited, and for example, it is 0.00% or more. From the viewpoint of simplifying the purification process of the phenolic composition and improving productivity, it is preferably 0.01% or more, more preferably 0.02% or more. Here, 0.00% means that the peak height is below the detection limit, and it includes cases where the peak height ratio corresponding to isobutyraldehyde cannot be calculated. The same applies to each compound described below.

[0014] The phenolic composition of the present embodiment can be produced by the production method described below, particularly (i) generating a precursor from a plant-derived raw material compound using a first transformant, (ii) generating a phenolic composition from the precursor by phenolizing a second transformant or the precursor (4-hydroxybenzoic acid), and (iii) separating and concentrating the generated phenolic composition.

[0015] In the phenol composition of the present embodiment, the radiocarbon derived from biomass resources determined based on the concentration of radiocarbon in the recycled carbon in the 1950s, measured according to ASTM D6866-20 14 The measured bio-based ratio indicating the proportion of 14 C is preferably 80% or more and 100% or less, more preferably 85% or more and 100% or less, still more preferably 90% or more and 100% or less, and still more preferably 95% or more and 100% or less. When the measured bio-based ratio is within the above numerical range, the environmental compatibility is better from the perspective of carbon neutrality. The measured bio-based ratio indicates the amount of plant-derived carbon contained in phenol, and the larger this value is, the more the phenol composition is composed of naturally derived raw materials. Therefore, the larger the measured bio-based ratio is, the better the environmental compatibility is from the perspective of carbon neutrality.

[0016] The radiocarbon 14 C in all carbon atoms of phenol (A) in the phenol composition of the present embodiment 14 The measured bio-based ratio indicating the proportion of 14 C is calculated based on the content of radiocarbon 14 C in the sample according to the bio-based concentration test standard ASTM D6866-20 defined by the American Society for Testing and Materials (ASTM), and the measurement result and the concentration of radiocarbon 14 C in the recycled carbon in 1950. Although this test standard shows a plurality of analysis methods, among them, analysis method B (AMS method) is preferably used. For analysis method B, for example, an analytical device such as an accelerator mass spectrometer Pelletron AMS manufactured by NEC Corporation is used. 14 C content measurement, and the measurement result and the radiocarbon 14 C concentration in the recycled carbon in 1950 14 C concentration.

[0017] In the phenol composition of the present embodiment, the content of the phenol (A) is preferably 70% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, still more preferably 80% by mass or more and 100% by mass or less, and still more preferably 85% by mass or more and less than 100% by mass, when the total phenol composition is 100% by mass. When the content of the phenol (A) is within the above numerical range, the environmental compatibility is better from the perspective of carbon neutrality. Furthermore, when the content of phenol (A) is 100% by mass, the content of acetaldehyde, n-butyraldehyde, isovaleraldehyde, isobutyraldehyde, propionic acid, toluene, styrene, and other components is 0% by mass. This also includes cases where the content of other components is below the detection limit and cannot be detected by quantitative analysis.

[0018] In the phenol composition of this embodiment, it is preferable that the phenol (A) contains at least a structure derived from the benzene ring of a product of one or more transformants selected from the group consisting of transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). By containing at least the product of the phenol (A), environmental compatibility is improved from the viewpoint of carbon neutrality.

[0019] In the phenol composition of this embodiment, phenol (A) may contain the products of one or more transformants selected from the group consisting of transformant PHE7 (accession number: NITE BP-976), transformant PHE18 (accession number: NITE BP-995), transformant PHE21 (accession number: NITE BP-996), and transformant PHE31 (accession number: NITE BP-999). By containing at least the products of phenol (A), environmental compatibility is improved from the viewpoint of carbon neutrality.

[0020] In the phenol composition of this embodiment, from the viewpoint of improving the desired properties of the obtained phenol composition and simplifying the purification process to improve productivity, in total ion chromatography of GC-MS after pretreatment by the 150°C headspace method, the sum of the peak height percentage corresponding to toluene and the peak height percentage corresponding to styrene is preferably 0.00% to 2.00%, more preferably 0.01% to 1.50%, even more preferably 0.03% to 1.00%, even more preferably 0.05% to 0.50%, even more preferably 0.08% to 0.35%, even more preferably 0.10% to 0.20%, and even more preferably 0.10% to 0.15%. In this case, 0.00% includes cases where the peak height is below the detection limit and the peak height percentage corresponding to toluene or styrene cannot be calculated, and the same applies to each compound described below.

[0021] <toluene> In the phenol composition of this embodiment, from the viewpoint of improving the desired properties of the obtained phenol composition and simplifying the purification process to improve productivity, the peak height percentage corresponding to toluene in total ion chromatography of GC-MS after pretreatment by the 150°C headspace method is preferably 0.00% to 0.30%, more preferably 0.01% to 0.20%, even more preferably 0.02% to 0.15%, and even more preferably 0.03% to 0.10%.

[0022] <styrene> In the phenol composition of this embodiment, from the viewpoint of improving the desired properties of the obtained phenol composition and simplifying the purification process to improve productivity, the peak height percentage corresponding to styrene in total ion chromatography of GC-MS after pretreatment by the 150°C headspace method is preferably 0.00% to 3.00%, more preferably 0.01% to 2.00%, even more preferably 0.02% to 1.00%, even more preferably 0.03% to 0.50%, even more preferably 0.04% to 0.25%, and even more preferably 0.05% to 0.15%.

[0023] In the phenol composition of this embodiment, from the viewpoint of improving the desired properties of the obtained phenol composition and from the viewpoint of simplifying the purification process and improving productivity, in total ion chromatography of GC-MS after pretreatment by the 150°C headspace method, the sum of the peak height percentages corresponding to acetaldehyde, n-butyraldehyde, isobutyraldehyde, and isovaleraldehyde is preferably 0.01% to 5.00%, more preferably 0.02% to 4.00%, even more preferably 0.03% to 3.00%, even more preferably 0.04% to 2.50%, even more preferably 0.05% to 2.00%, even more preferably 0.10% to 1.00%, even more preferably 0.20% to 0.90%, even more preferably 0.30% to 0.80%, and even more preferably 0.40% to 0.80%.

[0024] <Acetaldehyde> In the phenol composition of this embodiment, from the viewpoint of further suppressing the burnt odor and simplifying the purification process to improve productivity, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to acetaldehyde is preferably 0.00% to 0.15%, more preferably 0.00% to 0.10%, even more preferably 0.01% to 0.08%, even more preferably 0.01% to 0.05%, and even more preferably 0.02% to 0.05%.

[0025] <n-butyraldehyde> In the phenol composition of this embodiment, from the viewpoint of improving the desired properties of the obtained phenol composition, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to n-butyraldehyde is preferably 0.00% or more and 0.05% or less, more preferably 0.00% or more and 0.03% or less, even more preferably 0.00% or more and 0.01% or less, and even more preferably 0.00% or more and less than 0.01%.

[0026] <Isovaleraldehyde> In the phenol composition of this embodiment, from the viewpoint of improving the desired properties of the obtained phenol composition, in total ion chromatography of GC-MS pretreatment by 150°C headspace method, the peak height percentage corresponding to isovaleraldehyde is preferably 1.00% or less, more preferably 0.50% or less, even more preferably 0.30% or less, even more preferably 0.20% or less, even more preferably 0.10% or less, and even more preferably 0.05% or less. The lower limit of the peak height percentage corresponding to isovaleraldehyde is not particularly limited, but for example it may be 0.00% or more, and from the viewpoint of simplifying the purification process of the phenol composition and improving productivity, it may be 0.01% or more, or 0.02% or more.

[0027] <Propionic acid> In the phenol composition of this embodiment, from the viewpoint of further suppressing acidic odor and simplifying the purification process to improve productivity, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to propionic acid is preferably 0.00% to 0.35%, more preferably 0.01% to 0.20%, even more preferably 0.02% to 0.15%, and even more preferably 0.03% to 0.13%.

[0028] <Other ingredients> In the phenol composition of this embodiment, other components besides those described above may be included, as long as they do not affect the odor. Other components may include one or more compounds selected from the group consisting of the following compounds. Monosaccharides such as fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, cellobiose, and xylobiose; and polysaccharides such as dextrin or soluble starch. Sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid, and isovaleric acid; alcohols such as ethanol and propanol; hydrocarbons such as n-paraffin, etc. Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate; urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, amino acids, and other nitrogen-containing organic compounds. Potassium monophosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, etc. Solvents such as pure water.

[0029] In the phenol composition of this embodiment, the content of the other components is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less, when the total phenol composition is considered to be 100% by mass. By keeping the content of the other components below the upper limit, the required properties of the phenol composition of this embodiment can be improved. Furthermore, the lower limit of the content of the other aforementioned components is not particularly limited, but for example, it may be 0.000% by mass or more, and may be 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, or 0.30% by mass or more, from the viewpoint of simplifying the purification process of the phenol composition and improving productivity. In this case, 0.000% by mass includes cases where the content of the other aforementioned components is below the detection limit and cannot be detected by quantitative analysis. In the phenol composition of this embodiment, if it contains multiple other components, it is sufficient that the total content of the other components is less than or equal to the upper limit and greater than or equal to the lower limit.

[0030] Methods for quantifying the content of phenol (A) and other components in this embodiment include, for example, high-performance liquid chromatography using a high-performance liquid chromatograph equipped with a UV detector (Hitachi High-Tech Science Co., Ltd., Chromaster®), ion chromatography, gas chromatography-mass spectrometry (GC / MS), and inductively coupled plasma mass spectrometry (ICP-MS).

[0031] The phenol composition of this embodiment is preferably solid at 23°C.

[0032] <Method for producing phenolic composition> Next, the method for producing the phenol composition of this embodiment will be described.

[0033] The phenol composition of this embodiment can be obtained by a manufacturing method comprising the following steps: (A), (B1) or (B2), (C), and (D). (A) A step of reacting a first transformant in a reaction intermediate solution containing sugars, a compound that can produce colismic acid by metabolism of the transformant, or at least one starting compound selected from the group consisting of colismic acid and salts thereof, to produce a precursor. (B1) A step of producing a phenol composition from a precursor using a second transformant and obtaining a reaction solution containing the phenol composition. (B2) A step of obtaining a phenol composition by phenolizing 4-hydroxybenzoic acid in the culture medium. (C) A step to remove the transformants from the reaction solution. (D) A step of separating and concentrating the phenol composition in the reaction solution.

[0034] [(A) A step of reacting a first transformant with sugars, at least one starting compound selected from the group consisting of a compound that can produce colismic acid by metabolism of the transformant, or colismic acid and salts thereof, in a reaction intermediate solution to produce a precursor.] When using the production method for the phenol composition of this embodiment, first, a step is performed to produce a precursor by reacting A) a first transformant with sugars and at least one raw material compound selected from the group consisting of a compound that can produce colismic acid by metabolism of the transformant, or colismic acid and salts thereof, in a reaction intermediate solution. The compounds used in this process and the reaction conditions are described in detail below.

[0035] (First transformant) In the method for producing the phenol composition of this embodiment, any transformant capable of producing a precursor from sugars through metabolism can be used as the first transformant. Examples of such precursors include 4-hydroxybenzoic acid. Examples of such transformants include the Corynebacterial transformant HBA-2 (accession number: NITE BP-01838) described in Japanese Patent No. 6327653 or the Corynebacterial transformant HBA-47 (accession number: NITE BP-01849) described in Japanese Patent No. 6327654.

[0036] Prior to the reaction, it is preferable to culture the first transformant under aerobic conditions. The culture temperature and culture time are not particularly limited as long as the transformant can be cultured and a sufficient amount of transformant can be obtained. For example, the culture temperature is 25°C to 38°C. For example, the culture time is 12 hours to 48 hours.

[0037] (Culture medium) The culture medium used for the aerobic culture of the first transformant prior to the reaction can be a natural or synthetic medium containing a carbon source, nitrogen source, inorganic salts, and other nutrients. As a carbon source, sugars (monosaccharides such as glucose, fructose, mannose, xylose, arabinose, and galactose; disaccharides such as sucrose, maltose, lactose, cellobiose, xylobiose, and trehalose; polysaccharides such as starch; molasses, etc.), sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin can also be used. Carbon sources can be used individually or in combination of two or more. The concentration of the carbon source in the culture medium will vary depending on the compound used, but for example, it should be between 0.1 w / v% and 20 w / v%.

[0038] As nitrogen sources, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate can be used. Additionally, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. Nitrogen sources can be used individually or in mixtures of two or more. The concentration of the nitrogen source in the culture medium will vary depending on the nitrogen compound used, but for example, it should be between 0.1 w / v% and 10 w / v%. Examples of inorganic salts include potassium monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Inorganic salts can be used individually or in mixtures of two or more. The concentration of inorganic salts in the culture medium will vary depending on the inorganic salt used, but for example, it should be between 0.01 w / v% and 1 w / v%.

[0039] Nutrients include meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, skim soybean hydrochloride hydrolysate, extracts of animals, plants, or microorganisms, and their decomposition products. The concentration of nutrients in the culture medium will vary depending on the nutrients used, but for example, it should be between 0.1 w / v% and 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the culture medium is preferably between 6 and 8.

[0040] Specific preferred culture media include Medium A [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7:182-196 (2004)] and Medium BT [Omumasaba, CA et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8:91-103 (2004)]. In these media, the sugar concentration should be within the aforementioned range.

[0041] (Raw material compound) The raw material compound is preferably a compound that can be taken up into the cells of the first transformant, and more preferably one that is readily available industrially, such as being abundant in plants. Among the raw material compounds, sugars that can produce glucose through the metabolism of the first transformant are preferred, and glucose is more preferred. Such sugars include oligosaccharides and polysaccharides having glucose units. Examples of the oligosaccharides and polysaccharides include monosaccharides such as fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, cellobiose, and xylobiose; and polysaccharides such as dextrin or soluble starch. Furthermore, using glucose is preferable from the viewpoint of improving the efficiency of precursor production and thus improving the production efficiency of the phenol composition of this embodiment. Furthermore, among the raw material compounds, examples of compounds in which the first transformant can produce colismic acid through metabolism include quinic acid and shikimic acid. Furthermore, plant-derived raw materials can be used as raw materials containing these raw material compounds, for example. As plant-derived raw materials, it is also possible to use saccharified liquids containing multiple sugars such as glucose, obtained by saccharifying non-edible agricultural waste such as molasses, straw (rice straw, barley straw, wheat straw, rye straw, oat straw, etc.), bagasse, and corn stover, as well as energy crops such as switchgrass, napier grass, and miscanthus, and wood chips and waste paper with saccharifying enzymes. In particular, glucose, chorismic acid, quinic acid, and shikimic acid are preferred as raw material compounds, and it is preferable to use plant-derived raw materials containing these compounds.

[0042] (Intermediate reaction solution) As the reaction intermediate, a natural or synthetic reaction solution containing a carbon source, a nitrogen source, and inorganic salts can be used. As a carbon source, the raw material compounds described above or molasses or saccharification solutions containing them may be used. In addition to sugars, sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin may also be used as carbon sources. Carbon sources can be used individually or in combination of two or more. The concentration of the starting compound in the reaction intermediate solution is preferably 1 w / v% to 20 w / v%, more preferably 2 w / v% to 10 w / v%, and even more preferably 2 w / v% to 5 w / v%. Furthermore, the concentration of the total carbon source, including the starting compound, in the reaction intermediate solution should be between 2 w / v% and 5 w / v%.

[0043] As nitrogen sources, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate can be used. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. Nitrogen sources can be used individually or in mixtures of two or more. The concentration of the nitrogen source in the reaction intermediate solution varies depending on the nitrogen compound used, but for example, it should be between 0.1 w / v% and 10 w / v%. Examples of inorganic salts include potassium monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Inorganic salts can be used individually or in mixtures of two or more. The concentration of inorganic salts in the reaction intermediate solution varies depending on the inorganic salt used, but for example, it should be between 0.01 w / v% and 1 w / v%.

[0044] Nutrients include meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, skim soybean hydrochloride hydrolysate, extracts of animals, plants, or microorganisms, and their decomposition products. The concentration of nutrients in the reaction intermediate solution will vary depending on the nutrients used, but for example, it should be between 0.1 w / v% and 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the reaction intermediate solution is preferably between 6 and 8.

[0045] Specific preferred reaction intermediates include the aforementioned A medium and BT medium. In these reaction intermediates, the sugar concentration should be within the aforementioned range.

[0046] (Reaction conditions) From the viewpoint of the efficiency of producing the phenol composition, the reaction temperature, i.e., the survival temperature of the first transformant, is preferably 20°C or higher, more preferably 23°C or higher, and even more preferably 25°C or higher. Also, from the same viewpoint, the survival temperature is preferably 50°C or lower, more preferably 48°C or lower, and even more preferably 47°C or lower. From the viewpoint of the efficiency of producing the phenol composition, the reaction time is preferably 7 days or less, more preferably 5 days or less, and even more preferably 3 days or less. Furthermore, the reaction time is not particularly limited as long as the reaction proceeds sufficiently, but for example, it is 1 day or more. The culture can be carried out using a batch, fed-batch, or continuous method. Of these, the batch method is preferred from the viewpoint of production efficiency of the phenol composition. The reaction may be carried out under aerobic or reducing conditions. The first transformant itself has a higher capacity to produce the phenol composition under aerobic conditions. However, under aerobic conditions, the first transformant proliferates, and the starting compound is consumed for growth, which reduces the efficiency of phenol composition production. Therefore, it is preferable to carry out the reaction under aerobic conditions and in which the first transformant does not grow. In this specification, "does not grow" includes substantially no growth or hardly any growth. For example, by using a reaction solution that is deficient in or limited one or more compounds essential for microbial growth, such as biotin, vitamins such as thiamine, or nitrogen sources, the growth of the first transformant can be avoided or suppressed.

[0047] Furthermore, under reducing conditions, the first transformant does not substantially grow, so the raw material compound is not consumed for growth, improving the efficiency of precursor production, and consequently increasing the efficiency of phenol composition production. The reduction conditions are determined by the oxidation-reduction potential of the reaction intermediate solution. The oxidation-reduction potential of the reaction solution is preferably between -500mV and -200mV, and more preferably between -500mV and -150mV. The reduction state of the reaction intermediate can be easily estimated using a resazurin indicator (which changes from blue to colorless if reduced), but it can be accurately measured using an oxidation-reduction potentiometer (for example, ORP Electrodes, manufactured by Broadley James).

[0048] The method for preparing the reaction intermediate solution under reducing conditions can be any known method without limitation. For example, instead of distilled water or the like, an aqueous solution for the reaction intermediate solution may be used as the liquid medium for the reaction intermediate solution. For example, methods for preparing culture media for obligate anaerobic microorganisms such as sulfate-reducing microorganisms (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, MP et al., p926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Manual, Volume 3, edited by the Department of Agricultural Chemistry, Faculty of Agriculture, Kyoto University, 26th printing, 1990, published by Sangyo Tosho Co., Ltd.) can be used as references to obtain an aqueous solution under the desired reducing conditions. Specifically, an aqueous solution for the reaction intermediate under reducing conditions can be obtained by removing dissolved gases by heating or reducing the pressure of distilled water or the like. In this case, by treating distilled water or the like under reduced pressure, preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less, for preferably 1 minute to 60 minutes, more preferably 5 minutes to 40 minutes, dissolved gases, especially dissolved oxygen, can be removed to create an aqueous solution for the reaction intermediate under reducing conditions.

[0049] Furthermore, an aqueous solution for the reaction intermediate under reducing conditions can be prepared by adding a suitable reducing agent (for example, thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.). Combining these methods appropriately is also an effective way to prepare aqueous solutions for reaction intermediates under reducing conditions.

[0050] When the reaction is carried out under reducing conditions, it is preferable to maintain reducing conditions for the reaction intermediate solution throughout the reaction. To maintain reducing conditions during the reaction, it is desirable to prevent oxygen contamination from outside the reaction system as much as possible. Specifically, this can be achieved by sealing the reaction system with an inert gas such as nitrogen gas or carbon dioxide gas. As a more effective way to prevent oxygen contamination, it may be necessary to add a pH-maintaining solution or various nutrient solutions to the reaction system as appropriate in order to efficiently enable the metabolic functions of the first transformant in this embodiment during the reaction. In such cases, it is effective to remove oxygen from the added solution beforehand.

[0051] [(A)' Step of removing the first transformant from the precursor] Furthermore, in the method for producing the phenol composition of this embodiment, from the viewpoint of yielding the phenol composition, the method may include a step of removing the first transformant from the precursor (A)' after the step of reacting the first transformant with sugars, a compound that can produce colismic acid by metabolism of the transformant, or at least one raw material compound selected from the group consisting of colismic acid and salts thereof, to produce a precursor, and before the step of producing a phenol composition from the precursor with the second transformant (B1) described below, or before the step of phenolizing 4-hydroxybenzoic acid in the culture medium to obtain a reaction solution containing the phenol composition (B2), the method may include a step of removing the first transformant from the precursor (A)'. (A)' In the step of removing the first transformant from the precursor, the reaction solution recovery method exemplified in the step of removing the phenol composition in the reaction solution described later in (D) can be used. By applying the reaction solution recovery method to the precursor, the first transformant can be removed from the precursor and the precursor can be recovered.

[0052] [(B1) A step of producing a phenol composition from the precursor using a second transformant and obtaining a reaction solution containing the phenol composition.] Next, (B1) a step is performed to produce a phenol composition from the precursor using a second transformant and to obtain a reaction solution containing the phenol composition. By culturing as described above, the precursor is produced in the reaction intermediate solution. By adding the second transformant to this reaction intermediate solution, a phenol composition can be produced from the precursor, and a reaction solution containing the phenol composition can be obtained. The compounds used in this process and the reaction conditions are described in detail below.

[0053] (Second transformed organism) In the method for producing the phenol composition of this embodiment, any transformant capable of producing a phenol composition from a precursor can be used as the second transformant. Examples of the precursor include 4-hydroxybenzoic acid. Examples of such transformants include the Corynebacterial transformant PHE7 (accession number: NITE BP-976) described in Japanese Patent No. 5932649, the Corynebacterial transformant PHE18 (accession number: NITE BP-995) described in Japanese Patent No. 5996434, the Corynebacterial transformant PHE21 (accession number: NITE BP-996) described in Japanese Patent No. 5932660, or the Corynebacterial transformant PHE31 (accession number: NITE BP-999) described in Japanese Patent No. 5887277.

[0054] Prior to the reaction, it is preferable to culture the second transformant under aerobic conditions. The culture temperature and culture time are not particularly limited as long as the transformant can be cultured and a sufficient amount of transformant can be obtained. For example, the culture temperature is 25°C to 38°C. For example, the culture time is 12 hours to 48 hours.

[0055] (Culture medium) For the aerobic culture of the second transformant prior to the reaction, a natural or synthetic culture medium containing a carbon source, nitrogen source, inorganic salts, and other nutrients can be used. As a carbon source, sugars (monosaccharides such as glucose, fructose, mannose, xylose, arabinose, and galactose; disaccharides such as sucrose, maltose, lactose, cellobiose, xylobiose, and trehalose; polysaccharides such as starch; molasses, etc.), sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin can also be used. Carbon sources can be used individually or in combination of two or more. The concentration of the carbon source in the culture medium will vary depending on the compound used, but for example, it should be between 0.1 w / v% and 20 w / v%.

[0056] As nitrogen sources, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate can be used. Additionally, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. Nitrogen sources can be used individually or in mixtures of two or more. The concentration of the nitrogen source in the culture medium will vary depending on the nitrogen compound used, but for example, it should be between 0.1 w / v% and 10 w / v%. Examples of inorganic salts include potassium monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Inorganic salts can be used individually or in mixtures of two or more. The concentration of inorganic salts in the culture medium varies depending on the inorganic salt used, but for example, it should be between 0.01 w / v% and 1 w / v%.

[0057] Nutrients include meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, skim soybean hydrochloride hydrolysate, extracts of animals, plants, or microorganisms, and their decomposition products. The concentration of nutrients in the culture medium will vary depending on the nutrients used, but for example, it should be between 0.1 w / v% and 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the culture medium is preferably between 6 and 8.

[0058] Specific preferred culture media include Medium A [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7:182-196 (2004)] and Medium BT [Omumasaba, CA et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8:91-103 (2004)]. In these media, the sugar concentration should be within the aforementioned range.

[0059] (Reaction solution) In addition to the reaction intermediate solution used in step (A) above, buffer solutions, inorganic salt culture media, etc., can also be used as the reaction solution. In the reaction solution, the precursor may be a salt such as a sodium salt or a potassium salt; or an ester with an alcohol having 1 to 4 carbon atoms. Among these, salts are preferred, and sodium salts are more preferred. The precursor can be used alone or as a mixture of two or more. The concentration of the precursor in the reaction solution is preferably 1 w / v% to 20 w / v%, more preferably 2 w / v% to 10 w / v%, and even more preferably 2 w / v% to 5 w / v%. By keeping the precursor concentration within the above numerical range, the production efficiency of the phenol composition is further improved.

[0060] Examples of buffer solutions include phosphate buffer, Tris buffer, and carbonate buffer. From the viewpoint of the efficiency of producing the phenol composition, the concentration of the buffer solution is preferably between 10 mM and 150 mM.

[0061] Examples of inorganic salt media include media containing one or more inorganic salts such as potassium monopotassium phosphate, potassium dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Among these, media containing magnesium sulfate are preferred. Specific examples of inorganic salt media include A medium [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7:182-196 (2004)] and BT medium [Omumasaba, CA et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8:91-103 (2004)]. The concentration of inorganic salts in the culture medium varies depending on the inorganic salt used, but it is generally sufficient to maintain a concentration between 0.01 w / v% and 1 w / v%.

[0062] The pH of the reaction solution is preferably between 6 and 8. During the reaction, it is preferable to control the pH of the reaction solution to be near neutral, especially to 7, using an aqueous ammonia solution, an aqueous sodium hydroxide solution, or the like with a pH controller (for example, Able Co., Ltd., model: DT-1023).

[0063] (Reaction conditions) From the viewpoint of the efficiency of producing the phenol composition, the reaction temperature, i.e., the survival temperature of the second transformant, is preferably 20°C or higher, more preferably 23°C or higher, and even more preferably 25°C or higher. Furthermore, from the same viewpoint, the survival temperature is preferably 50°C or lower, more preferably 48°C or lower, and even more preferably 47°C or lower. From the viewpoint of the efficiency of producing the phenol composition, the reaction time is preferably 7 days or less, more preferably 5 days or less, and even more preferably 3 days or less. Furthermore, the reaction time is not particularly limited as long as the reaction proceeds sufficiently, but for example, it is 1 day or more. The culture can be carried out using a batch, fed-batch, or continuous method. Of these, the batch method is preferred from the viewpoint of production efficiency of the phenol composition.

[0064] The reaction may be carried out under aerobic conditions, but it is preferable to carry it out under reducing conditions. Under reducing conditions, the second transformant does not grow, thus increasing the efficiency of production of the phenol composition. In this specification, "does not grow" includes substantially no growth or hardly any growth. The reduction conditions are determined by the oxidation-reduction potential of the reaction solution. From the viewpoint of the efficiency of producing the phenol composition, the oxidation-reduction potential of the reaction intermediate solution is preferably -500mV or more and -200mV or more, and more preferably -500mV or more and -150mV or less. The reducing state of the reaction solution can be easily estimated using a resazurin indicator (which changes from blue to colorless if the solution is reduced), but it can be more accurately measured using an oxidation-reduction potentiometer (for example, ORP Electrodes, manufactured by Broadley James).

[0065] The method for preparing the reaction solution under reducing conditions can be any known method without limitation. For example, instead of distilled water or other liquid media for the reaction solution, an aqueous solution for the reaction solution may be used. For example, methods for preparing culture media for obligate anaerobic microorganisms such as sulfate-reducing microorganisms (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, MP et al., p926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Manual, Volume 3, edited by the Department of Agricultural Chemistry, Faculty of Agriculture, Kyoto University, 26th printing, 1990, published by Sangyo Tosho Co., Ltd.) can be used as references to obtain an aqueous solution under the desired reducing conditions. Specifically, an aqueous solution for a reaction solution under reducing conditions can be obtained by removing dissolved gases by heating or reducing the pressure of distilled water. In this case, by treating distilled water under reduced pressure, preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less, for preferably 1 minute to 60 minutes, more preferably 5 minutes to 40 minutes, dissolved gases, especially dissolved oxygen, can be removed to create an aqueous solution for a reaction solution under reducing conditions.

[0066] Furthermore, an aqueous solution for the reaction mixture can be prepared under reducing conditions by adding a suitable reducing agent (for example, thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.). Combining these methods appropriately is also an effective way to prepare aqueous solutions for reaction under reducing conditions.

[0067] When the reaction is carried out under reducing conditions, it is preferable to maintain reducing conditions in the reaction solution throughout the reaction. In order to maintain reducing conditions during the reaction, it is desirable to prevent the introduction of oxygen from outside the reaction system as much as possible. Specifically, this can be achieved by sealing the reaction system with an inert gas such as nitrogen gas or carbon dioxide gas. As a more effective way to prevent oxygen introduction, in order to efficiently enable the metabolic functions of the second transformant in this embodiment during the reaction, it may be necessary to add a pH-maintaining solution or various nutrient solutions as appropriate. In such cases, it is effective to remove oxygen from the added solution beforehand.

[0068] [(B2) A step to obtain a reaction solution containing a phenol composition by phenolizing 4-hydroxybenzoic acid in the culture medium.] Alternatively, instead of the step of (B1) generating a phenol composition from a precursor using the second transformant and obtaining a reaction solution containing the phenol composition, the process may include the step of (B2) phenolizing 4-hydroxybenzoic acid (hereinafter also referred to as 4-HBA) in the culture medium and obtaining a reaction solution containing the phenol composition. In this embodiment, the precursor containing 4-HBA in the culture medium can be recovered as described above. However, in order to improve the purity of 4-HBA, 4-HBA is separated and concentrated from the culture medium by known methods. Such known methods include distillation, permeation vaporization, membrane permeation, organic solvent extraction, acid-base extraction, and filtration. These methods can be carried out by combining one or more of them as appropriate.

[0069] Next, the obtained 4-HBA is phenolized to obtain a phenol composition. In this embodiment, the phenol composition can be obtained by phenolizing 4-HBA using known methods. Known methods include heating 4-HBA to induce a decarboxylation reaction, and treating the 4-hydroxybenzoate obtained from 4-HBA with acid to decarboxylate it.

[0070] [(C) Step to remove the transformed product from the reaction solution] Next, (C) a step is performed to remove the transformants from the reaction solution. As described above, phenol is generated in the reaction solution by culturing or phenolization of 4-HBA, but transformants remain in the reaction solution. By removing these transformants, the reaction solution containing the phenol composition can be recovered.

[0071] One method for recovering the reaction solution is to separate the reaction solution from the transformants. If the method for producing the phenol composition includes step (B1), the first transformant may be removed from the (A)' precursor as described above, and the first and second transformants may be separated separately from the reaction solution obtained in step (B1). Alternatively, the first and second transformants may be separated simultaneously from the reaction solution obtained in step (B1) without removing the first transformant from the (A)' precursor. Furthermore, if the method for producing the phenol composition includes steps (A)' and (B2), step (C) is unnecessary because the reaction solution obtained in step (B2) does not contain transformants. For separating the transformants, known separation methods can be used. Known separation methods include, for example, collecting the supernatant by standing, membrane filtration, and centrifugation. These methods can be carried out individually or in appropriate combinations of two or more.

[0072] The membrane filtration process can be carried out under general filtration conditions. From the viewpoint of improving the efficiency of phenol composition production, the membrane pore size is preferably 0.01 μm or larger, more preferably 0.03 μm or larger, even more preferably 0.05 μm or larger, even more preferably 0.07 μm or larger, even more preferably 0.10 μm or larger, even more preferably 0.15 μm or larger, and even more preferably 0.20 μm or larger. Also, from the same viewpoint, it is preferably 3 μm or smaller, more preferably 2 μm or smaller, and even more preferably 1 μm or smaller. As for methods of measuring the membrane pore size, general measurement methods such as mercury intrusion method, bubble point test, and bacterial filtration method can be used, but it is preferable to use the value obtained by the bubble point test. Examples of membrane materials used in membrane filtration include polymer membranes, ceramic membranes, and stainless steel membranes.

[0073] For centrifugal separation, general-purpose equipment such as separation plate type, cylindrical type, and decanter type can be used. From the viewpoint of improving the efficiency of phenol composition production, the lower limit of the temperature during centrifugal separation is preferably 0°C or higher, more preferably 1°C or higher, and even more preferably 3°C or higher. Similarly, from the same viewpoint, the upper limit of the temperature during centrifugal separation is preferably 70°C or lower, more preferably 50°C or lower, even more preferably 30°C or lower, even more preferably 10°C or lower, and even more preferably 5°C or lower.

[0074] Furthermore, while the relative centrifugal force and time can be set as appropriate, the lower limit of the relative centrifugal force is preferably 3000g or more, more preferably 5000g or more, even more preferably 7000g or more, even more preferably 10000g or more, and even more preferably 15000g or more, from the viewpoint of improving the polymerizability of the phenol composition. Furthermore, the upper limit of the relative centrifugal force is preferably 50000g or less, more preferably 25000g or less, and even more preferably 20000g or less, from the viewpoint of improving the production efficiency of the phenol composition. Similarly, the lower limit of the time is preferably 0.2 minutes or more, more preferably 0.5 minutes or more, even more preferably 1 minute or more, and even more preferably 5 minutes or more, from the viewpoint of improving the color tone of the polymer obtained using the phenol composition. The upper limit of the time is preferably 75 minutes or less, more preferably 60 minutes or less, even more preferably 30 minutes or less, even more preferably 15 minutes or less, and even more preferably 10 minutes or less, from the viewpoint of improving the production efficiency of the phenol composition.

[0075] [(D) Step of separating and concentrating the phenol composition in the reaction solution] Finally, (D) a step of separating and concentrating the phenol composition in the reaction solution is performed. In this embodiment, the phenol composition in the reaction solution can be recovered as described above, but in order to increase the phenol concentration in the phenol composition and further remove isobutyraldehyde, thereby suppressing the musty odor of the phenol composition, the phenol composition is separated and concentrated by known methods. Such known methods include distillation, permeation vaporization, membrane permeation, and organic solvent extraction. These methods can be performed individually or in appropriate combinations of two or more.

[0076] Any known distillation method can be used. Known distillation methods are not particularly limited, but include atmospheric pressure distillation using a distillation column, reduced pressure distillation using an evaporator, steam distillation, and thin-film distillation.

[0077] The permeation vaporization method is a method of obtaining a phenol composition in a gaseous state by using a permeation vaporization membrane and allowing the material to permeate through the membrane. The permeation vaporization membrane has the function of preferentially allowing phenol to permeate over water. Therefore, the phenol composition in the reaction solution moves from the supply side space to the permeation side space, preferentially permeating through the permeation vaporization membrane, rather than moving over water. As a result, the phenol composition obtained in the permeation side space has a higher phenol concentration than that of the reaction solution. In this way, by using the permeation vaporization method, it is possible to obtain a phenol composition in a gaseous state from the reaction solution and to make the phenol concentration in the obtained phenol composition higher than that of the reaction solution.

[0078] The shape of the permeable vaporization membrane is not particularly limited, and dense membranes such as bag-shaped, flat-membrane, hollow-fiber, tubular, and spiral types can be used.

[0079] The average thickness of such a permeation vaporization membrane is not particularly limited, but is preferably about 10 to 500 μm, and more preferably about 20 to 400 μm. By setting the average thickness of the permeation vaporization membrane within the above range, the supply side space and the permeation side space can be reliably separated, and the vaporized phenol composition can be obtained more reliably from the reaction solution.

[0080] Furthermore, the material of the permeation vaporization membrane is not particularly limited, but examples include inorganic membranes such as DDR-type zeolite membranes, polymer membranes such as polyimide, polyamide, polysulfone, polyethersulfone, and polyamideimide, or composite membranes thereof. Among these, inorganic membranes are preferred, and DDR-type zeolite membranes are more preferred. This makes it possible to improve the separation performance of phenol while also improving the mechanical properties of the permeation vaporization membrane.

[0081] <Application> The phenol composition of this embodiment can be used in the same applications as phenol compositions synthesized by conventional petrochemical processes using fossil resources as raw materials. Specifically, applications of the phenol composition of this embodiment include bisphenol A precursors, polymer raw materials, industrial chemicals, and fibers. Of these, it is preferable to use them for polymer applications. That is, a polymer using the phenol composition of this embodiment is a polymer that contains at least one structural unit derived from phenol(A) in the phenol composition of this embodiment.

[0082] The polymer in this embodiment may be any polymer that requires phenol for synthesis. Preferably, the polymer in this embodiment is a phenolic resin.

[0083] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope of achieving the objectives of the present invention are included. [Examples]

[0084] Embodiments of the present invention will be described in detail based on examples and comparative examples. It should be noted that the present invention is not limited to these examples.

[0085] <Examples, Comparative Examples> (Example 1) In a test tube containing 10 ml of liquid medium A containing 50 μg / ml kanamycin [(NH2)2CO2 2 g, (NH4)2SO4 7 g, KH2PO4 0.5 g, K2HPO4 0.5 g, MgSO4·7H2O 0.5 g, 0.06% (w / v) FeSO4·7H2O + 0.042% (w / v) MnSO4·2H2O 1 ml, 0.02% (w / v) biotin solution 1 ml, 0.01% (w / v) thiamin solution 2 ml, yeast extract 2 g, vitamin assay casamino acid 7 g, glucose 40 g dissolved in 1 L of distilled water], further dissolved 2% by mass of calcium carbonate, the Corynebacterial transformant HBA-47 described in Patent No. 6327654 (Accession number: NITE) was added. BP-01849) was inoculated into a platinum loop and cultured aerobically with shaking at 33°C and 200 rpm. 20 ml of the resulting pre-culture was inoculated into 500 ml of liquid medium A (which does not contain (NH2)2CO) to prepare the culture medium. The resulting culture solution was incubated in a 1 liter jar fermenter (Able Co., Ltd.) for 22 hours (33°C, 900 rpm, aeration rate 1 vol / vol / min). During this time, the pH was maintained at 7.0 by automatic addition of 5N NaOH. Adekanol LG-126 (0.2% "vol / vol"; ADEKA Corporation) was added to the medium as an antifoaming agent. Next, the cells that had grown in the medium were collected by centrifugation. Subsequently, the cells were resuspended in 220 ml of modified BT medium containing 400 mM glucose [(NH4)2SO4 7 g, KH2PO4 0.5 g, K2HPO4 0.5 g, MgSO4·7H2O 0.5 g dissolved in 1 L of distilled water] to a final cell concentration of 5% (wt / vol; wet weight). The production reaction was carried out in a 1 liter jar fermenter for 24 hours (33°C, 900 rpm, aeration rate 1 vol / vol / min). The pH was maintained at 7.3 by automatic addition of 5N NaOH. Glucose in the reaction solution was replenished as needed before it was depleted. Then, HBA-47 was separated from the test solution by vacuum filtration using a 0.22 μm pore size membrane filter (Merck Millipore, Steritop 0.22 μm × 33 mm) to obtain the test solution (4-hydroxybenzoic acid (4-HBA): 37 g / L).Next, the solvent (water) of the obtained test solution was evaporated using an evaporator (60°C, 20 hPa) to obtain a 5-fold concentrated solution. 25% sulfuric acid was added to the concentrate to lower the pH from 8 to 3, thereby precipitating the solute. The precipitated solid was filtered and dried to obtain solid 4-HBA. The purity of the 4-HBA obtained by HPLC was 90%. Next, the obtained 4-HBA was placed in a round-bottom flask and heated under total reflux at 240°C for 30 minutes to decarboxylate and phenolize it. Under heating at 240°C, vacuum simple distillation at 200 hPa was performed, and the phenol composition was obtained by distillation.

[0086] (Example 2) The procedure was the same as in Example 1 up to decarboxylation and phenolization. Next, the components distilled off by vacuum simple distillation at 240°C and 400 hPa were separated, and then the phenol composition was obtained by vacuum simple distillation at 240°C and 200 hPa.

[0087] (Example 3) The phenol composition obtained in Example 2 was subjected to simple distillation under reduced pressure at 150°C and 100 hPa to separate the distillate components, and then the phenol composition was obtained by simple distillation under reduced pressure at 170°C and 100 hPa.

[0088] (Example 4) In a test tube containing 10 ml of liquid medium A containing 50 μg / ml kanamycin [(NH2)2CO2 2 g, (NH4)2SO4 7 g, KH2PO4 0.5 g, K2HPO4 0.5 g, MgSO4·7H2O 0.5 g, 0.06% (w / v) FeSO4·7H2O + 0.042% (w / v) MnSO4·2H2O 1 ml, 0.02% (w / v) biotin solution 1 ml, 0.01% (w / v) thiamin solution 2 ml, yeast extract 2 g, vitamin assay casamino acid 7 g, glucose 40 g dissolved in 1 L of distilled water], further dissolved 2% by mass of calcium carbonate, the Corynebacterial transformant HBA-47 described in Patent No. 6327654 (Accession number: NITE) was added. BP-01849) was inoculated onto a platinum loop and cultured aerobically with shaking at 33°C for 24 hours at 200 rpm.

[0089] Next, the HBA-47 was separated from the test solution by vacuum filtration using a membrane filter with a pore size of 0.22 μm (Merck Millipore, Steritop 0.22 μm × 33 mm), thereby obtaining the test solution. Subsequently, the Corynebacterial transformant PHE21 (accession number: NITE BP-996), prepared by the method described in Example 1 and paragraph

[0135] of Japanese Patent No. 5932660, was added to the test solution to obtain a bacterial suspension at a final cell concentration of 10%. This bacterial suspension was placed in a 100 ml medium bottle, and under reducing conditions (oxidation-reduction potential: -450 mV), sodium-4-hydroxybenzoate was added as a substrate to a concentration of 250 mM. The reaction was carried out in a water bath maintained at 33°C with stirring. During this time, the pH of the reaction solution was controlled using a pH controller (Able Co., Ltd., model: DT-1023) with 2.5 N aqueous ammonia to ensure that the pH of the reaction solution did not fall below 7.0.

[0090] The resulting reaction mixture was centrifuged (4°C, 15000g, 10 minutes) to obtain a supernatant containing a phenol composition synthesized from glucose (phenol concentration: 0.8% by mass).

[0091] This solution was subjected to vacuum distillation at 80 kPa and a reflux ratio of 7.8 in a continuous distillation column equipped with ordered packing (MC500S, Matsui Machine Co., Ltd.). The heating temperature at the bottom of the column was 121°C. A phenol aqueous solution concentrated to 4.3% by mass was recovered from the side cut of the continuous distillation column. Subsequently, it was concentrated to 22% by mass by dehydration using permeation vaporization (60°C, 50 Torr) with a DDR-type zeolite membrane. This concentrate was allowed to stand at room temperature to separate into a phenol phase and an aqueous phase, and the phenol phase was recovered (phenol concentration: 72% by mass). This phenol phase was further concentrated to 99% by mass by removing water using an evaporator (60°C / 20 hPa) to obtain a phenol composition.

[0092] (Example 5) The phenol composition obtained in Example 4 was distilled using an evaporator (150°C / 20hPa) to obtain the phenol composition by distillation.

[0093] (Comparative Example 1) This refers to the phenol composition separated by vacuum simple distillation (150°C, 100 hPa) in Example 3.

[0094] <GC / MSによるトータルイオンクロマトグラフィー> For each example and comparative example of phenol composition, total ion chromatography by GC-MS was performed using a headspace method with a gas chromatograph-mass spectrometer (Shimadzu Corporation, GC-MS QP2020) and a headspace sampler HS-20Trap, followed by headspace pretreatment. The peak height percentages for phenol, acetaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde, toluene, styrene, propionic acid, and isovaleric acid were calculated. The results are shown in Table 1. Peak height percentage refers to the proportion of the detection intensity of a peak corresponding to a particular compound, relative to the total detection intensity of all detection in total ion chromatography of GC-MS after pretreatment using the 150°C headspace method, with the sum of all detection intensities being set to 100%.

[0095] The GC / MS analysis conditions are as follows: (Analysis conditions) • Column: Rtx-5ms, inner diameter 0.32mm, length 60m, liquid phase film thickness 1.0μm (manufactured by Shimadzu GLC Co., Ltd.) Oven temperature: 150℃ • Carrier gas: Helium • Carrier gas linear velocity: 40 cm / second • Ionization method: 70eV EI mode • GC section: Temperature 230°C, split injection method (split ratio 10:1) MS section: Ion source temperature 200°C, interface temperature 230°C, measurement mode Scan Scan range: m / z 25-500 • Samples: Each sample is enclosed in a 20mL headspace vial at a dose of 0.1g. • HS section: 150℃ 30min loop mode

[0096] <Sensory evaluation> Sensory evaluations regarding odor were performed on the phenol compositions of each example and comparative example according to the following criteria. The results are shown in Table 1. A: No musty smell was detected. B: A faint musty smell was detected. C: A musty smell was detected, but it was not particularly unpleasant. D: A musty smell was detected, which was unpleasant.

[0097] [Table 1]

[0098] The phenol composition in the example had suppressed moldy odor. This indicates that the moldy odor of the phenol composition can be suppressed by controlling the peak height ratio of isobutyraldehyde in the phenol composition of this embodiment.

[0099] Corynebacterium glutamicum PHE7 has been deposited with the Patent Microbial Depository Center of the National Institute of Technology and Evaluation, located at 2-5-8 Kazusa-Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (Date of domestic deposit: August 31, 2010; Date of international deposit under the Budapest Convention: August 12, 2011; Accession number: NITE BP-976).

[0100] Corynebacterium glutamicum PHE18 has been deposited with the Patent Microbial Depository Center of the National Institute of Technology and Evaluation, located at 2-5-8 Kazusa-Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (Date of domestic deposit: October 21, 2010; Date of international deposit under the Budapest Convention: September 28, 2011; Accession number: NITE BP-995).

[0101] Corynebacterium glutamicum PHE21 has been deposited with the Patent Microbial Depository Center of the National Institute of Technology and Evaluation, located at 2-5-8 Kazusa-Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (Date of domestic deposit: October 21, 2010; Date of international deposit under the Budapest Convention: September 28, 2011; Accession number: NITE BP-996).

[0102] Corynebacterium glutamicum PHE31 has been deposited with the Patent Microbial Depository Center of the National Institute of Technology and Evaluation, located at 2-5-8 Kazusa-Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (Date of domestic deposit: November 2, 2010; Date of international deposit under the Budapest Convention: September 28, 2011; Accession number: NITE BP-999).

[0103] Corynebacterium glutamicum HBA-2 has been deposited with the Patent Microbial Depository Center of the National Institute of Technology and Evaluation (NITE), located at 2-5-8 Kazusa-Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (Date of domestic deposit: March 27, 2014; Date of international deposit under the Budapest Convention: February 23, 2015; Accession number: NITE BP-01838).

[0104] Corynebacterium glutamicum HBA-47 has been deposited with the Patent Microbial Depository Center of the National Institute of Technology and Evaluation, located at 2-5-8 Kazusa-Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (Date of international deposit under the Budapest Convention: April 25, 2014, accession number: NITE BP-01849). These stocks are internationally deposited under the Budapest Convention and are publicly available under the conditions set forth in 37 CFR 1.808.

Claims

1. A phenol composition containing biomass-derived phenol (A), A phenol composition in which, in total ion chromatography by GC-MS after pretreatment using the 150°C headspace method, the peak height percentage corresponding to isobutyraldehyde is 4.0% or less.

2. Radioactive carbon from biomass resources, determined based on the concentration of radioactive carbon in circulating carbon in the 1950s, as measured according to ASTM D6866-20. １４ The phenol composition according to claim 1, wherein the measured bioconversion rate of phenol (A), which indicates the proportion of C, is 80% or more and 100% or less.

3. The phenol composition according to claim 1 or 2, which is solid at 23°C.

4. The phenol composition according to claim 1 or 2, wherein, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the sum of the peak height percentage corresponding to toluene and the peak height percentage corresponding to styrene is 2.00% or less.

5. The phenol composition according to claim 1 or 2, wherein, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the sum of the peak height percentages corresponding to acetaldehyde, n-butyraldehyde, isobutyraldehyde, and isovaleraldehyde is 0.01% or more and 5.00% or less.

6. The phenol composition according to claim 1 or 2, wherein, in total ion chromatography by GC-MS pretreatment using the 150°C headspace method, the peak height percentage corresponding to propionic acid is 0.35% or less.

7. The phenol composition according to claim 1 or 2, wherein the content of phenol (A) is 70% by mass or more.

8. A polymer comprising at least one structural unit derived from phenol (A) in the phenol composition according to claim 1 or 2.

9. The polymer according to claim 8, which is a phenolic resin.

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