Method for producing polyphenol derivative, polyphenol derivative, and resin composition material containing polyphenol derivative

Abstract

A method for producing a polyphenol derivative, a polyphenol derivative produced by the method, and a polyphenol derivative-containing resin composition material containing the polyphenol derivative. The method for producing a polyphenol derivative comprises the steps of reacting a composition containing a polyphenol and an aromatic compound having ortho-para-directing groups in a solvent.

Description

Technical Field

[0001] The present invention relates to a method for producing a polyphenol derivative, a polyphenol derivative, and a resin composition material containing the polyphenol derivative. Background Art

[0002] From the perspective of reducing greenhouse gases, the use of carbon-neutral plant-derived substances in plastic materials is expected. Plant-derived substances mainly include sugar-derived cellulose, hemicellulose, and polyphenols such as lignin. Among them, polyphenols such as lignin are expected to be effectively used as plastic materials because they have aromatic rings, aliphatic hydroxyl groups and aromatic hydroxyl groups. However, there are two problems (a) and (b), and thus the use of polyphenols such as lignin as plastic materials has hardly been found: (a) a simple and economical separation and purification method for polyphenols such as lignin has not been established; and (b) polyphenols such as lignin are not easily biodegradable, are almost insoluble in solvents, and have a high softening point, so they are not easy to handle. Not only that, they also lack reactivity with existing plastic materials. Therefore, in order to make polyphenols such as lignin suitable as plastic materials, the following technical research is being carried out: appropriate separation and purification, modification, and then the use of the modified polyphenols such as lignin.

[0003] Separation of polyphenols such as lignin from biomass residues has been previously exemplified by separation of polyphenols such as lignin from black liquor, which is a residue of the pulp industry. However, black liquor contains many impurities such as inorganic salts, and therefore is used for fuel and other purposes with low industrial value. Recently, the following efforts have been known: as in Patent Document 1, modification such as reacting PEG (polyethylene glycol) with lignin contained in black liquor is performed to separate the lignin, thereby increasing the industrial value.

[0004] In addition, regarding the utilization of separated lignin, for example, Patent Document 2 discloses a technology involving a modified lignin in which a benzoxazine skeleton is introduced into lignin without reducing the molecular weight of the lignin to impart reactivity, and a molding material in which the mechanical strength of a molded product is improved by containing the modified lignin.

[0005] In addition, Patent Document 3 discloses: a technology in which lignin is reacted with phenols in the presence of a catalyst to perform phenolization, and then heated with an alkali to obtain an alkalized lignin, and then an aldehyde is added thereto to increase the reactivity of the lignin in the form of hydroxymethylated lignin; and a technology in which the lignin with increased reactivity is used in an adhesive composition.

[0006] Patent Document 4 discloses a phenol-modified lignin resin having improved curability and resin strength by a production method in which lignin, phenols, and aldehydes are reacted in the presence of an acid.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application No. 2015-519452

[0010] Patent Document 2: Japanese Patent No. 5671430

[0011] Patent Document 3: Japanese Patent Application No. 2016-540058

[0012] Patent Document 4: International Publication No. 2015 / 147165 Summary of the invention

[0013] Problems to be solved by the invention

[0014] In the case of intending to achieve greenhouse gas emission reduction as described above by using polyphenols such as lignin as plastic materials, there are the following issues: it is necessary to meet the four conditions of (i) cheap, (ii) able to be prepared in large quantities, (iii) easy to mix with resin, and (iv) easy to react with resin. However, although sulfite lignin, sulfate lignin, and alkali lignin obtained from black liquor discharged from the pulp industry, which are considered to be the current lignin raw materials, can meet the conditions of (i) and (ii), sulfite lignin is difficult to achieve (iv) due to its high sulfur concentration, and (iii) is also unsatisfactory due to its water solubility. In addition, sulfate lignin and alkali lignin are also unable to achieve (iii) and (iv) due to their high molecular weight. Recently, an organic solvent-type lignin that can be dissolved in an organic solvent has been reported (PEG lignin in Patent Document 1 is also an example thereof). Although it is believed that it can overcome the above-mentioned issues, there are problems in solving (i) and (ii).

[0015] Therefore, the object of the present invention is to provide a method for inexpensively producing a polyphenol derivative, a lignin derivative capable of providing a molded product having improved reactivity with existing plastic materials, good compatibility with resins, and improved physical properties such as flexural strength, and a resin composition material containing the lignin derivative.

[0016] Means of solving problems

[0017] As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, it has been found that by allowing an aromatic compound having ortho-para-directing groups to react with a composition containing polyphenols such as biomass in a solvent, the polyphenols can be separated as polyphenol derivatives and light components derived from the polyphenols can be reduced and their molecular weight can be lowered in one reaction, thereby solving the above-mentioned problems.

[0018] That is, the present invention is as follows.

[0019] [1] A method for producing a polyphenol derivative, comprising: reacting a composition containing a polyphenol with an aromatic compound having ortho-para-directing groups in a solvent.

[0020] [2] A lignin derivative having a weight average molecular weight of less than 5000 and a content of less than 0.7% by mass of the lignin derivative having a molecular weight LogM of 2.15 to 2.20.

[0021] [3] A resin composition material containing a lignin derivative, comprising a lignin derivative produced by the method for producing a polyphenol derivative or the lignin derivative described above.

[0022] Effects of the Invention

[0023] According to the present invention, a method for inexpensively producing a polyphenol derivative, a lignin derivative capable of improving reactivity with existing plastic materials, having good compatibility with resins, and capable of providing a molded product having improved physical properties such as flexural strength can be provided, and a resin composition material containing the lignin derivative can be provided. DETAILED DESCRIPTION

[0024] [Method for producing polyphenol derivatives]

[0025] The method for producing a polyphenol derivative of the present invention comprises the step of reacting a composition containing a polyphenol with an aromatic compound having an ortho-para-directing group in a solvent.

[0026] Here, in the present invention, the "polyphenol derivative" refers to a reaction product derived from polyphenol obtained by reacting the polyphenol contained in the polyphenol-containing composition with an aromatic compound.

[0027] Examples of the polyphenol in the polyphenol-containing composition of the present invention include lignite, lignin, tannin, catechin, anthocyanin, rutin, isoflavone, lignan, curcumin, and chlorogenic acid.

[0028] In particular, in the method for producing a polyphenol derivative of the present invention, the polyphenol contained in the polyphenol-containing composition is preferably lignin from the viewpoint of usefulness as a plastic material. Therefore, the polyphenol derivative is preferably a lignin derivative.

[0029] In the present specification, the polyphenol contained in the polyphenol-containing composition is specifically described by taking as an example the case where the polyphenol is lignin and the polyphenol derivative is a lignin derivative, but the method for producing the polyphenol derivative of the present invention is not limited to these lignin and lignin derivatives.

[0030] Here, lignin refers to a polymer compound obtained by polymerizing three types of lignin monomers, which are p-hydroxycinnamyl alcohols, and has a basic skeleton represented by the following formula (2).

[0031] [Chemistry 1]

[0032]

[0033] In the above formula (2), R as a substituent 3 and R 4 represents a hydrogen atom or a methoxy group. 3 and R 4 When both sides are hydrogen atoms, it is called a p-hydroxyphenyl nucleus (H-type skeleton). 3 and R 4 When either of the two atoms is a hydrogen atom, it is called a guaiacyl core (G-type skeleton). 3 and R 4 When neither of the two atoms is a hydrogen atom, it is called a syringyl nucleus (S-type skeleton).

[0034] It should be noted that in the above formula (2), X represents a bond to a carbon atom, and Y represents a bond to a hydrogen atom or a carbon atom.

[0035] Although the basic skeleton of lignin is similar to R 3 and R 4 The bonded carbon atom becomes a highly reactive reaction point (hereinafter, sometimes simply referred to as a "reaction point"). 3 and R 4 When it is a methoxy group, the carbon atom lacks reactivity. Therefore, in order to make lignin react, it is desirable that R 3 and R 4 A hydrogen atom.

[0036] In addition, lignin contains not only the above-mentioned aromatic sites but also aliphatic sites, and the hydroxyl groups present in the aliphatic sites lack oxidative stability (aliphatic hydroxyl groups will be converted into aldehydes and carboxylic acids due to oxidation). Therefore, when the number of hydroxyl groups present in the aliphatic sites is as small as possible, the reactivity with existing plastic materials is good.

[0037] In addition, the lignin derivative can be miscible by lowering its softening point without significantly reducing its molecular weight, thereby improving its reactivity with existing plastic materials.

[0038] That is, for lignin derivatives, if they can be made into substances with highly reactive H-type skeletons, G-type skeletons, or substances with a large amount of these two skeletons, and with few aliphatic hydroxyl groups, and preferably with a low softening point without significantly reducing the molecular weight, then a lignin derivative that is highly reactive and suitable as a plastic material can be obtained.

[0039] Therefore, in the production method of the present invention, a composition containing polyphenols is mixed with an aromatic compound in a solvent, and the substituent R in the basic skeleton of lignin represented by the above formula (2) in the composition containing polyphenols is substituted. 3 and R 4 The substitution reaction transferred to the aromatic compound gives a lignin derivative suitable for the above-mentioned plastic materials.

[0040] Reaction Process

[0041] <Composition containing polyphenol>

[0042] In the method for producing a polyphenol derivative of the present invention, as the polyphenol-containing composition used as a raw material, at least one of biomass and biomass residues may be used.

[0043] Examples of the biomass residue include biomass residue derived from plant-based biomass such as woody biomass and herbaceous biomass.

[0044] In addition, examples of biomass residues include saccharification residues and fermentation residues of lignocellulosic biomass (second-generation ethanol saccharification residues and second-generation ethanol fermentation residues), black liquor (sulfite lignin, sulfate lignin, alkali lignin, etc.), and tannins, and any one or more of these can be used. Among them, any one or more of second-generation ethanol saccharification residues and second-generation ethanol fermentation residues can be used as the composition containing polyphenol from the viewpoint of easy availability, quality of the polyphenol derivative, and economic efficiency.

[0045] (Lignocellulosic biomass)

[0046] Examples of non-food plant biomass include woody biomass and herbaceous biomass. Examples of woody biomass include coniferous trees and broad-leaved trees such as cedar, cypress, hinoki, cherry, eucalyptus, beech, and bamboo.

[0047] Examples of herbaceous biomass include trunks / empty shells of oil palm, fibers and seeds of oil palm fruits, bagasse (the residue of sugarcane and high biomass sugarcane), sugarcane tops (the top and leaves of sugarcane), energy sugarcane, rice straw, wheat straw, cobs / stems / residues of corn (corn stover, corn cobs, corn husks), sorghum (including sweet sorghum) residues, skins and shells of Jatropha curcas, cashew nut shells, switchgrass, sedge, high biomass yield crops, energy crops, and the like.

[0048] Among them, from the viewpoint of easy availability and suitability with the production method used in the present invention, herbaceous biomass is preferred, and empty shells of oil palm, wheat straw, cobs / stems / residues of corn (corn stalks, corn cobs, corn husks), bagasse, sugarcane tails, energy sugarcane, and residues after useful components are extracted from them are more preferred, and cobs / stems / residues of corn (corn stalks, corn cobs, corn husks), bagasse, sugarcane tails, energy sugarcane are more preferred. It should be noted that the above useful components include, for example, hemicellulose, sugar, minerals, water, etc.

[0049] Bagasse contains about 5 to 30% by mass of lignin. In addition, the lignin in bagasse includes all of the H nucleus, G nucleus, and S nucleus as a basic skeleton.

[0050] Plant-based biomass may be crushed and used, and may be in any form of a block, crumbs, powder, or a hydrate containing water.

[0051] Sugarcane bagasse, corn stover, etc. are subjected to an organic solvent method, a pressurized hot water method, a steam explosion method, an ammonia treatment method, an ammonia explosion method, an acid treatment method, an alkali treatment method, an oxidative decomposition method, a pyrolysis method, a microwave heating method, etc., preferably an acid treatment, an ammonia explosion method, a steam explosion method, etc., and after hemicellulose is separated to the solution side, cellulose is converted into glucose using an enzyme and also separated to the solution side, or cellulose is saccharified together with hemicellulose without separating it and then separated to the solution side, and the remaining solid is the second generation ethanol saccharification residue. Alternatively, sugars are not separated, but are fermented to ethanol and separated to the solution side, and the remaining solid is the second generation ethanol fermentation residue.

[0052] The second generation ethanol saccharification residue contains lignin as the main component, decomposed organic matter, catalyst, enzyme, ash, cellulose, etc. In addition, the second generation ethanol fermentation residue contains lignin as the main component, decomposed organic matter, catalyst, enzyme, yeast, ash, cellulose, etc.

[0053] A more specific embodiment of the manufacturing method of the present invention is shown in the examples described below, but for example, it is as follows. Any one or more of the second-generation ethanol saccharification residue and the second-generation ethanol fermentation residue are used as raw materials, and a solvent and an aromatic compound are added. After continuous heating for about 2 to 4 hours, since the heated liquid contains insoluble matter, it is hot filtered using No. 2 filter paper. The filtered solids are unreacted products and inorganic impurities. The filtrate is distilled under reduced pressure to remove the solvent and unreacted aromatic compounds. For aromatic compounds that are not completely removed during distillation, they are removed by repeated vacuum drying, or by dissolving in acetone as needed and reprecipitating with water as a poor solvent. The separated solid is a modified lignin derivative. If the aromatic compounds remaining during distillation do not become a problem in subsequent reactions, they can also be used directly as plastic materials.

[0054] In addition, as for the composition containing polyphenol used as a raw material, lignin separated by treating non-edible plant biomass with an organic solvent method, a pressurized hot water method, a steam explosion method, an ammonia treatment method, an ammonia explosion method, an acid treatment method, an alkali treatment method, an oxidative decomposition method, a pyrolysis method, a microwave heating method, etc. can also be used. Specifically, for example, the following lignin can be used, that is, after treating with an organic solvent or a solvent containing an organic solvent and water at a high temperature, lignin contained in the non-edible plant biomass is dissolved in the solvent, and the solution containing lignin is filtered to remove cellulose and the like, and then the solution is concentrated and dried to separate lignin.

[0055] <Aromatic compounds>

[0056] The aromatic compound having an ortho-para directing group (hereinafter, sometimes simply referred to as an "aromatic compound") may be any aromatic compound having one or more ortho-para directing groups.

[0057] The ortho-para-directing group is an electron-donating substituent, and examples thereof include hydroxyl, methoxy, aliphatic hydrocarbon, amino, halogen and other functional groups, and hydroxyl is preferred. That is, the aromatic compound is preferably a phenol compound.

[0058] In the aromatic compound, at least one of the 2-position, 4-position and 6-position as the substituent relative to the ortho-para-position directing group is a hydrogen atom, and preferably, the compound represented by the following formula (A) is used.

[0059] [Chemistry 2]

[0060]

[0061] In the above formula (A), W is an ortho-para-positioning group, R 1 and R 2 Each independently represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 15 carbon atoms, and R1 and R 2 Optional same or different.

[0062] The alkyl group having 1 to 15 carbon atoms may be linear or branched. The alkyl group having 1 to 15 carbon atoms is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and further preferably a linear alkyl group having 1 to 3 carbon atoms.

[0063] Examples of the aromatic compound represented by the above formula (A) include phenol, anisole, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, tert-butylbenzene, aniline, methylaniline, N,N-dimethylaniline, chlorobenzene, m-cresol, p-cresol, o-cresol, m-methoxyphenol, m-xylene, 1,3-diethylbenzene, 3-methylaniline, 3-methyl-N-methylaniline, 3-methyl-N,N-dimethylaniline, m-dichlorobenzene, m-chlorotoluene, 3,5-dimethylphenol, 3,5-dimethylanisole, mesitylene, 3,5-dimethylaniline, 3,5-dimethyl-N-methylaniline, 3,5-dimethyl-N,N-dimethylaniline, 3-chloro-m-xylene, and 3,5-dichlorotoluene.

[0064] [Phenol compounds]

[0065] As described above, the aromatic compound is preferably a phenol compound in which the ortho-para-directing groups are hydroxyl groups.

[0066] The phenol compound is preferably a phenol compound in which at least one of the 2-position, 4-position and 6-position as a substituent with respect to the hydroxyl group is a hydrogen atom.

[0067] The phenol compound having hydrogen atoms at the 2-, 4- and 6-positions (i.e., the ortho and para positions) is particularly suitable as a site for receiving a substituent resulting from a substitution reaction with lignin due to its group orientation. The reason for this is that by mixing the composition containing polyphenols with the phenol compound in a solvent, R in the basic skeleton of lignin represented by the above formula (2) in the composition containing polyphenols is 3 and R 4 The substituent of is transferred to the 2-position, 4-position or 6-position of the phenol compound. 3 or R 4 Alternatively, both of them become hydrogen atoms, thereby obtaining the above-mentioned lignin derivative with increased reaction points.

[0068] Therefore, through this substitution reaction, the S-type skeleton in lignin is reduced and the G-type skeleton and H-type skeleton are increased, thereby improving reactivity. In addition, as mentioned above, the molecular chain of lignin is changed through this substitution reaction, thereby reducing the molecular weight and improving the miscibility of lignin derivatives.

[0069] The phenol compounds may be used alone or in combination of two or more.

[0070] The phenol compound is preferably a compound represented by the following formula (1) wherein W in the above formula (A) is a hydroxyl group. With this phenol compound, the above substituent is attached to at least three sites, so that the substitution reaction can proceed well.

[0071] [Chemistry 3]

[0072]

[0073] In the above formula (1), R 1 and R 2 With R in the above formula (A) 1 and R 2 Synonymous.

[0074] Examples of the phenol compound represented by the above formula (1) include 3-alkylphenols such as phenol, resorcinol, pyrogallol, meta-cresol, 3-ethylphenol, and 3-propylphenol; 5-alkylresorcinols such as 5-methylresorcinol, 5-ethylresorcinol, and 5-propylresorcinol; and 3,5-dialkylphenols such as 3,5-dimethylphenol, 3-methyl-5-ethyl-phenol, and 3,5-diethylphenol.

[0075] In addition, since the acidity of the compound can be increased by making the phenol compound have a plurality of hydroxyl groups, and the reaction can be expected to proceed without a catalyst, R 1 and R 2 A phenol compound in which at least one of the phenols is a hydroxyl group. Specific examples of such phenol compounds include resorcinol, phloroglucinol, and 5-alkylresorcinol (5-methylresorcinol, 5-ethylresorcinol, etc.).

[0076] <Solvent>

[0077] The reaction of the composition containing polyphenol and the aromatic compound is carried out in a solvent.

[0078] The polyphenol in the composition containing polyphenol reacts with the aromatic compound. When no solvent is used in the reaction, the reaction is advanced, but the amount of the aromatic compound used is increased compared to the case of using a solvent. In addition, by using a solvent, the solubility of the polyphenol is improved, the above reaction is preferably advanced, and even if the amount of the aromatic compound used is small, there is no possibility of an extreme decrease in yield, and a certain yield or more can be achieved, which is also preferred from the viewpoint of economic efficiency.

[0079] As the solvent, from the viewpoint of improving the solubility of polyphenols such as lignin in the raw material, it is preferred to include a polar solvent. In addition, from the viewpoint of the solubility and economy of polyphenols such as lignin in the raw material, it is preferred to include any one or more of alcohols, ketones, ethers, aromatics and water. Regarding these solvents, specifically, any one or more of organic solvents such as methanol, ethanol, alcohols such as isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, ethers such as tetrahydrofuran, aromatics, and water.

[0080] The organic solvent preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms, from the viewpoints of preventing the softening point from becoming too high and being in an appropriate range, solubility of polyphenols such as lignin, and economic efficiency.

[0081] Among the above solvents, from the viewpoint of low softening point, high yield and economy of polyphenol derivatives such as lignin derivatives, it is preferred to use any one or more of ethanol, acetone and water, more preferably any one or more of ethanol and water, and further preferably ethanol or a combination of ethanol and water. In particular, by using water and an organic solvent as a solvent, a high yield can be expected.

[0082] When an organic solvent and water are used together, the mass ratio [organic solvent: water] is preferably 95:5 to 5:95, more preferably 95:5 to 20:80, further preferably 95:5 to 30:70, further preferably 95:5 to 40:60, further preferably 95:5 to 50:50, and further preferably 90:10 to 50:50, from the viewpoint of low softening point, high yield and economy of polyphenol derivatives such as lignin derivatives.

[0083] In addition, relative to the total amount of aromatic compounds and solvents, 4 to 95% by mass of aromatic compounds can be used. If the usage of the above-mentioned aromatic compounds exceeds 95% by mass, there is a tendency for molecular weight to decrease and strength to decrease, and economic efficiency decreases. In addition, if the usage of the above-mentioned aromatic compounds is more than 4% by mass, the softening point of polyphenol derivatives such as lignin derivatives will not become too high, and the compatibility with the resin will become good, and the yield will not decrease. Further, if the usage of the above-mentioned aromatic compounds is more than 4% by mass, it can be expected that the reaction of the composition containing polyphenols and the aromatic compounds with ortho-para-positioning groups in the solvent will be effectively promoted. About the usage of the above-mentioned aromatic compounds, from the viewpoint of economic efficiency, it is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass.

[0084] <Mass ratio [aromatic compounds / lignin]>

[0085] In the production method of the present invention, the mass ratio of the aromatic compound to the polyphenol such as lignin in the polyphenol-containing composition [aromatic compound / polyphenol such as lignin] may be generally about 0.1 to 15. The mass ratio is preferably 0.1 to 10, more preferably 0.1 to 5, further preferably 0.1 to 4, further preferably 0.1 to 3, further preferably 0.1 to 2, further preferably 0.1 to 1, further preferably 0.1 to 0.7, further preferably 0.1 to 0.5 from the viewpoint of economic efficiency and good progress of the substitution reaction.

[0086] <Acid Catalyst>

[0087] In the production method of the present invention, the reaction of the composition containing polyphenols and the aromatic compound is preferably carried out under the following conditions, that is, the reaction is carried out in the absence of a catalyst, or in the presence of an acid catalyst in an amount of preferably greater than 0 and less than 5.0% by mass, and further in the presence of 0.1 to 3.0% by mass of an acid catalyst relative to the total amount of polyphenols such as lignin and the aromatic compound in the composition containing polyphenols.

[0088] As described above, the aromatic compound used in the reaction can be used to promote the reaction under the condition of no catalyst. By promoting the reaction under the condition of no catalyst, for example, the post-treatment (purification process) after the reaction process can be omitted, and it can be expected that the physical properties such as the bending strength of the molded product obtained by using the obtained polyphenol derivative as a plastic material can be improved.

[0089] Examples of the acid catalyst include inorganic acids such as phosphoric acid, phosphoric acid esters, hydrochloric acid, sulfuric acid, and sulfuric acid esters, and organic acids such as acetic acid, formic acid, oxalic acid, and p-toluenesulfonic acid. The acid catalysts may be used alone or in combination of two or more.

[0090] When an acid catalyst is used in the above reaction, the amount of the acid catalyst used is usually greater than 0 relative to the total amount of polyphenols such as lignin and aromatic compounds in the composition containing polyphenols, and the upper limit is not particularly limited, but from the viewpoint of being able to exert the effect well by adding the acid catalyst and the impurities remaining in the polyphenol derivative, the reaction is usually carried out in the presence of 0.01 to 5.0% by mass of the acid catalyst, preferably 0.1 to 3.0% by mass, more preferably 0.2 to 3.0% by mass, and further preferably 0.2 to 2.6% by mass. If the amount of the acid catalyst used is within the above range, the above reaction can be carried out well. When the amount of the acid catalyst used exceeds the above range, the hydrolysis of cellulose, hemicellulose, etc. contained in the biomass and biomass residues of the composition containing polyphenols is promoted, and the concentration of sulfate groups increases, impurities increase, and there is a possibility that the cost of purification increases.

[0091] <Reaction Temperature and Time>

[0092] The reaction temperature is not particularly limited as long as it is usually 100° C. or higher, but is usually about 140° C. or higher and 350° C. or lower, preferably 140° C. or higher and 300° C. or lower, more preferably 140° C. or higher and 270° C. or lower, further preferably 140° C. or higher and 250° C. or lower, further preferably 150 to 230° C., further preferably 180 to 230° C. If it is higher than 140° C., the lignin derivative can be dissolved to advance the reaction, and if it is 300° C. or lower, the advancement of the reverse reaction can be prevented.

[0093] The reaction time is generally about 0.1 to 15 hours, but from the viewpoint of being able to sufficiently advance the reaction and modify the polyphenol, it is preferably 0.5 hours or more, more preferably 1 hour or more, and from the viewpoint of being unable to expect the reaction to advance even if the reaction time is too long, the upper limit is preferably 10 hours or less, more preferably 1 hour or more and 8 hours or less, and further preferably 2 hours or more and 8 hours or less.

[0094] <Reaction Pressure>

[0095] Reaction pressure is usually not particularly limited if it is more than 0.05MPa, but is usually expected to be more than 0.1MPa and about 30MPa or less. However, the preferred range of the pressure of the reaction system is affected by the amount and temperature of the solvent, so it is appropriately set. In addition, the reaction can be carried out under ambient atmosphere. It should be noted that, in order to suppress the polymerization caused by the oxidation reaction, it is particularly preferred to react under an atmosphere in which nitrogen purge is carried out and oxygen is reduced.

[0096] The reaction method in the reaction is not particularly limited, but can be static or stirring treatment. For example, a general batch reactor, a semi-batch reactor, etc. can be used. In addition, a method of processing while extruding a slurry containing biomass, biomass residue and solvent with a screw or a pump can also be applied.

[0097] 《Refining process》

[0098] The polyphenol derivative of the present invention is produced by performing the above-mentioned reaction process. Therefore, the lignin derivative produced by the method for producing the polyphenol derivative after the reaction process can be used directly as a plastic material, but a purification process can also be performed after the reaction process. For example, the method for producing the polyphenol derivative preferably further comprises a solid-liquid separation process in addition to the above-mentioned reaction process.

[0099] <Solid-Liquid Separation>

[0100] After the above reaction, the polyphenol derivative is dissolved in the solvent and the aromatic compound, but the unreacted product and the inorganic residue are present in the liquid in the form of solids. They are preferably removed by filtration (hot filtration). For example, the reaction solution is placed in a pressurized (hot) filter equipped with filter paper such as NO.5C or NO.2, and pressure filtered at about 20 to 100°C, about 20 to 70°C, usually about 20 to 50°C, at about 0.1 to 0.99 MPa, usually about 0.1 to 0.4 MPa. The filtered solid can be diluted and / or washed with an appropriate solvent and filtered. In this filtration, the polyphenol derivative is contained in the filtrate. In addition, for example, the reaction liquid can be diluted and / or washed with any one or more of low-boiling general solvents such as water, acetone, methyl ethyl ketone and other ketones, methanol, ethanol, isopropyl alcohol and other alcohols, tetrahydrofuran and other ethers, and solid-liquid separation is performed. In this solid-liquid separation, the polyphenol derivative is contained in the solution.

[0101] The method for performing solid-liquid separation is not particularly limited, and examples thereof include filtration, filter press, centrifugal separation, dehydrator and the like.

[0102] <Distillation>

[0103] Distillation can be performed, for example, by subjecting a solution containing the above-mentioned polyphenol derivative to reduced pressure distillation at a temperature of about 40 to 200° C., usually about 50 to 150° C., and a reduced pressure condition of about 3 to 20 kPa, usually about 5 to 10 kPa, to remove the solvent and the aromatic compound. In this distillation, the polyphenol derivative is obtained in the form of a solid. In addition, for example, when other diluent solvents are used, reduced pressure distillation can be performed at an appropriate temperature considering the boiling point of the solvent to remove the low-boiling general-purpose solvent, and then the aromatic compound can be removed by the same method as above. In this distillation, the polyphenol derivative is obtained in the form of a solid.

[0104] <Decompression and drying>

[0105] The polyphenol derivative obtained by distillation can be heated to 50 to 200° C. and vacuum dried in a solid or molten state to remove the aromatic compounds after the reaction and purify it. Alternatively, the polyphenol derivative in a fluid state after distillation and heated can be directly vacuum dried to remove the aromatic compounds after the reaction and purify it.

[0106] <Reprecipitation>

[0107] When aromatic compounds remain in the polyphenol derivative obtained by distillation or vacuum drying, the polyphenol derivative obtained by the above distillation can be further dissolved in a solvent such as acetone, and ion exchange water or the like which is a poor solvent for the polyphenol derivative is added to perform reprecipitation, thereby removing the aromatic compounds after the reaction and purifying.

[0108] In the purification step, the above-mentioned filtration, distillation, vacuum drying and reprecipitation may be repeated, or any one of them or a combination of two or more of them may be performed.

[0109] It should be noted that the amount of aromatic compounds remaining in the polyphenol derivative is not particularly limited, but is usually less than 30%, preferably less than 10%, more preferably less than 5%, and further preferably less than 1%.

[0110] [Polyphenol derivatives]

[0111] The polyphenol derivative of the present invention may be produced by any method as long as the effects of the present invention are not impaired, but is preferably a polyphenol derivative produced by the above-mentioned method for producing a polyphenol derivative.

[0112] As mentioned above, lignin can contain H-type skeleton, G-type skeleton, and S-type skeleton. 31 The total ratio of the relative abundance ratio H(%) of the H-type skeleton to the relative abundance ratio S(%) of the S-type skeleton obtained by the integral value of P-NMR measurement [(2H+G) / S] can be set to 2.3 or more. 31 The presence ratio of the aliphatic hydroxyl group relative to the total presence ratio of the aliphatic hydroxyl group and the aromatic hydroxyl group, which is obtained by the integral value of the P-NMR measurement, can be set to less than 27%. If the above ratio [(2H+G) / S] is 2.3 or more, the reactivity with the existing plastic material tends to be good. Similarly, if the presence ratio of the aliphatic hydroxyl group is less than 27%, the reactivity with the existing plastic material tends to be good.

[0113] In addition, from the viewpoint that the reactivity of the polyphenol derivative can be further improved and a molded product with improved physical properties such as bending strength can be provided, the above ratio [(2H+G) / S] is preferably 2.4 or more, more preferably 2.5 or more, and more preferably 2.6 or more. There is no restriction on the upper limit of the above ratio [(2H+G) / S] as long as it does not impair the effect of the present invention, but from the viewpoint of productivity, it is preferably 10.0 or less, more preferably 7.0 or less, and more preferably 5.0 or less. In addition, from the same viewpoint, the above ratio of aliphatic hydroxyl groups is preferably less than 25%, more preferably less than 23%, and more preferably less than 20%, and the closer to 0%, the more preferred.

[0114] It should be noted that the relative existence rates of the S-type skeleton, H-type skeleton and G-type skeleton and the amount of aliphatic hydroxyl groups are based on the 31 The value obtained by integrating the P-NMR measurement is 31 For details of P-NMR measurement, see MAGNETIC RESONANCE IN CHEMISTRY, VOL. 33, 375-382 (1995). In the present invention, more specifically, the measurement can be carried out by the method described in the examples described later.

[0115] <Molecular weight and softening point>

[0116] In the polyphenol derivative of the present invention, R 3 and R 4 The molecular chain is changed, so the molecular weight is reduced. In this way, the lignin is reduced in molecular weight, and can be efficiently extracted as a polyphenol derivative, while the miscibility (kneading or stirring) with other resin materials is improved, and it is expected to provide a molded product with improved physical properties such as bending strength.

[0117] In addition, in the polyphenol derivative of the present invention, since an aromatic compound is inserted into the substitution site, even if the molecular weight is reduced, the softening point does not decrease much.

[0118] Therefore, the softening point of the polyphenol derivative of the present invention can be preferably 90°C or higher, more preferably 130°C or higher, and further preferably 150°C or higher. If the softening point is 90°C or higher, it is less likely to cause problems such as expansion during molding / post-curing of the resin composition material containing the polyphenol derivative. In addition, the softening point of the polyphenol derivative is preferably 210°C or lower, more preferably 200°C or lower, further preferably 190°C or lower, further preferably 180°C or lower, and further preferably 160°C or lower. If the softening point is 210°C or lower, the resin composition material containing the polyphenol derivative is easier to handle.

[0119] The weight average molecular weight of the polyphenol derivative of the present invention is less than 5000, and the abundance ratio of the polyphenol derivatives having a molecular weight LogM of 2.15 to 2.20 is less than 0.7% by mass.

[0120] When the weight average molecular weight of the polyphenol derivative is 5,000 or more, it is difficult to improve the physical properties of the molded article, such as the flexural strength.

[0121] The weight average molecular weight of the polyphenol derivative is preferably 3,000 or more and 4,000 or less, preferably 2,000 or more and less than 3,000, preferably 1,000 or more and less than 2,000, and preferably 600 or more and less than 1,000.

[0122] In addition, if the presence ratio of the molecular weight LogM 2.15 to 2.20 of the polyphenol derivative is 0.7% by mass or more, there is a possibility that problems such as swelling will occur during molding / post-curing of the resin composition material containing the polyphenol derivative. The presence ratio of the molecular weight LogM 2.15 to 2.20 of the polyphenol derivative is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, and the lower the presence ratio, the better.

[0123] In addition, regarding the polyphenol derivatives of the present invention, for example:

[0124] When the weight average molecular weight is 3,000 or more and 4,000 or less, the softening point is preferably 140° C. or more and 210° C. or less.

[0125] When the weight average molecular weight is 2,000 or more and less than 3,000, the softening point is preferably 120° C. or more and 190° C. or less.

[0126] When the weight average molecular weight is 1,000 or more and less than 2,000, the softening point is preferably 100° C. or more and 170° C. or less.

[0127] When the weight average molecular weight is 600 or more and less than 1,000, the softening point is preferably 90° C. or more and 170° C. or less.

[0128] The above-mentioned cases can be used differently depending on the properties of the existing plastic material to be reacted. By improving the miscibility, it is expected that the reactivity of the polyphenol derivative will be improved, and a molded product with improved physical properties such as flexural strength can be provided.

[0129] In addition, the said weight average molecular weight can be measured by the method described in the Example mentioned later.

[0130] In addition, it is preferred that, using the method for producing polyphenol derivatives of the present invention, 50% by mass or more of the lignin contained in the second-generation ethanol fermentation residue or the second-generation ethanol saccharification residue is extracted as a polyphenol derivative, more preferably 60% by mass or more is extracted as a polyphenol derivative, further preferably 70% by mass or more is extracted as a polyphenol derivative, further preferably 80% by mass or more is extracted as a polyphenol derivative, further preferably 90% by mass or more is extracted as a polyphenol derivative.

[0131] The method for calculating the polyphenol content in the second generation ethanol fermentation residue and the second generation ethanol saccharification residue will be specifically described in the Examples described below.

[0132] [Resin composition materials and molded articles containing polyphenol derivatives]

[0133] The present invention also provides: a material containing a polyphenol derivative, particularly a resin composition material containing a polyphenol derivative, and a molded product using the material, which contains a polyphenol derivative produced by the production method of the polyphenol derivative and any one or more polyphenol derivatives of the polyphenol derivatives. In addition, the resin composition material containing a polyphenol derivative may contain, in addition to the polyphenol derivative obtained by the production method, one or more resin components such as thermosetting resins and thermoplastic resins, aldehydes, etc. The components other than the polyphenol derivatives are described below.

[0134] (Thermosetting resin)

[0135] The resin composition material containing the polyphenol derivative may further contain a thermosetting resin.

[0136] As the thermosetting resin, other general thermosetting resins such as phenolic resin, epoxy resin, polyurethane resin, melamine resin, urea-formaldehyde resin, unsaturated polyester resin, silicone resin, alkyd resin can be enumerated. Among them, because they have phenolic hydroxyl groups in the same way as polyphenol derivatives, they can react with polyphenol derivatives and can also be used as the diluent of polyphenol derivatives, so preferred phenolic resins. Among the phenolic resins, more preferably linear phenolic resins and resol phenolic resins. These thermosetting resins can use one or more than two.

[0137] The content of the thermosetting resin in the plastic material containing the polyphenol derivative may be determined according to the purpose, but is preferably 100 to 300 parts by mass, more preferably 150 to 250 parts by mass, based on 100 parts by mass of the polyphenol derivative, from the viewpoint of obtaining good physical properties and moldability.

[0138] (aldehydes)

[0139] Furthermore, the above-mentioned resin composition material containing a polyphenol derivative may further contain aldehydes.

[0140] A self-curing molding material can be obtained by using a polyphenol derivative-containing resin composition material containing a polyphenol derivative and an aldehyde.

[0141] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, furfural, benzaldehyde, phenylacetaldehyde, and salicylaldehyde. Among them, formaldehyde is preferred.

[0142] The molar ratio of the phenol group to formaldehyde in the polyphenol derivative [formaldehyde / phenol group] is preferably 1.0 to 2.5, more preferably 1.2 to 2.0. When the molar ratio is within the above range, there is no possibility that the curing speed during the reaction will decrease.

[0143] From the viewpoint of promoting the curing reaction between the polyphenol derivative and the aldehyde, it is preferred to use a base. As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, tetramethylammonium hydroxide, alkylamine, etc. can be used.

[0144] The temperature and reaction time during the curing reaction of the polyphenol derivative and the aldehyde are not limited, but are usually about 60 to 130° C., and the reaction time is usually about 0.5 to 5 hours.

[0145] The resin composition material containing the polyphenol derivative may further contain one or two or more selected from thermosetting resins and aldehydes.

[0146] (Bulking Agent)

[0147] The resin composition material containing the polyphenol derivative may further contain a filler, which may be an inorganic filler or an organic filler.

[0148] Examples of the inorganic filler include spherical or crushed fused silica, crystalline silica and other silica powders, alumina powder, glass powder, glass fiber, glass flakes, mica, talc, calcium carbonate, alumina, hydrated alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, magnesium oxide and the like.

[0149] Examples of the organic filler include carbon fiber, aramid fiber, paper powder, wood powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell / nut powder, chitin powder, and starch.

[0150] Inorganic filler and organic filler can use 1 kind or use 2 or more kinds, and its content is determined according to purpose.When containing inorganic filler and / or organic filler, when the content of inorganic filler and / or organic filler is appropriate, good physical property and formability can be obtained, so it is preferred.From this viewpoint, about the content of inorganic filler and / or organic filler, relative to 100 mass parts of polyphenol derivatives, preferably 50~200 mass parts, more preferably 80~150 mass parts.

[0151] (Curing agent)

[0152] The resin composition material containing the polyphenol derivative may further contain a curing agent.

[0153] Examples of the curing agent include hexamethylenetetramine, hexaformaldehyde, and paraformaldehyde, and these can be used alone or in combination of two or more.

[0154] In order to further increase the curing speed and degree of curing, an inorganic base such as calcium hydroxide, sodium hydroxide, potassium hydroxide, calcium oxide, and magnesium oxide, a Lewis acid such as zinc chloride and zinc acetate, a catalyst such as triethylamine, etc. may be used in addition to the curing agent. These may be used alone or in combination of two or more.

[0155] (Other additives)

[0156] The resin composition material containing the polyphenol derivative of the present embodiment may be added with various additives within a range that does not impair the properties of a molded article obtained from the resin composition material. In addition, a compatibilizer, a surfactant, etc. may be further added according to the purpose.

[0157] As the compatibilizer, a resin into which polar groups are introduced by adding maleic anhydride, epoxy or the like to a thermoplastic resin, for example, maleic anhydride-modified polyethylene resin, maleic anhydride-modified polypropylene resin, and various commercially available compatibilizers can be used in combination.

[0158] Examples of the surfactant include straight-chain fatty acids such as stearic acid, palmitic acid, and oleic acid, and branched and cyclic fatty acids such as rosin, but are not particularly limited thereto.

[0159] Further, as additives that can be matched in addition to the above substances, there can be mentioned flexibilizers, heat stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, defoamers, thixotropy imparting agents, mold release agents, antioxidants, plasticizers, low stress agents, coupling agents, dyes, light scattering agents, a small amount of thermoplastic resins, etc. These can be used alone or in combination of two or more.

[0160] (Thermoplastic resin)

[0161] As the thermoplastic resin that can be blended in the resin composition material containing the polyphenol derivative, an amorphous thermoplastic resin having a glass transition temperature of 200° C. or less, or a crystalline thermoplastic resin having a melting point of 200° C. or less is preferred. Examples of the thermoplastic resin include polycarbonate resins, styrene resins, polystyrene elastomers, polyethylene resins, polypropylene resins, polyacrylic resins (polymethyl methacrylate resins, etc.), polyvinyl chloride resins, cellulose acetate resins, polyamide resins, low melting point polyester resins represented by polyesters of terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol (PET, PBT, etc.), polylactic acid and / or copolymers containing polylactic acid, acrylonitrile-butadiene-styrene resins (ABS resins), polyphenylene oxide resins (PPO), polyketone resins, polysulfone resins, polyphenylene sulfide resins (PPS), fluororesins, silicone resins, polyimide resins, polybenzimidazole resins, polyamide elastomers, and copolymers thereof with other monomers.

[0162] When a polyphenol derivative is used as an additive for a thermoplastic resin, for example, conventionally known means such as those listed in Japanese Patent Application Laid-Open No. 2014-15579, International Publication No. 2016 / 104634, etc. can be used. The content of the thermoplastic resin in the polyphenol derivative resin composition material is preferably 30% by mass or more and 99.9% by mass or less, more preferably 40% by mass or more and 99.9% by mass or less, and particularly preferably 50% by mass or more and 99.9% by mass or less, relative to the total amount of the resin composition material, from the viewpoint of obtaining significant fluidity and strength.

[0163] The resin composition material containing the polyphenol derivative may contain, in addition to the thermoplastic resin, a resin, an additive, and a filler that are compatible with the resin composition material.

[0164] (Mixing and forming)

[0165] The ingredients used in the resin composition material containing the polyphenol derivative can be prepared and kneaded by premixing using commonly used equipment such as a ribbon mixer or a drum tumbler, and then using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder, a roll kneader, a compound motion kneader, etc. The heating temperature during kneading is usually appropriately selected within the range of 100 to 300° C.

[0166] There is no particular limitation on the method for molding the resin composition material containing the polyphenol derivative. For example, compression molding, injection molding, transfer molding, mold forming, FRP molding, etc. can be mentioned. In addition, when the resin composition material is a thermoplastic resin composition material, extrusion molding, injection molding, etc. can be mentioned as the method for molding into a prescribed shape.

[0167] As an example of a molded product using a resin composition material containing a polyphenol derivative, there can be mentioned a molded product obtained by curing a resin composition material prepared by mixing a polyphenol derivative with a curing agent, and a molded product obtained by further mixing various fillers as needed, and then curing a general phenolic resin obtained industrially, or a molded product obtained by molding after curing, and a molded product obtained by molding a resin composition material mixed with a polyphenol derivative and a thermoplastic resin, etc. As such a molded product using a resin composition material containing a polyphenol derivative, there can be mentioned, for example, heat insulating materials for housing, electronic components, resins for flake sand, resins for coated sand, resins for impregnation, resins for lamination, resins for FRP molding, automobile parts, reinforcing materials for automobile tires, OA equipment, machinery, information and communication equipment, industrial materials, etc.

[0168] In addition to resin components, polyphenol derivatives may be used in materials containing polyphenol derivatives. Examples of materials containing polyphenol derivatives other than resin components containing polyphenol derivatives include carbon materials such as carbon black / carbon fiber, lubricants such as lubricant base materials, foods / cosmetics with antioxidant / antibacterial properties, cement additives, concrete additives, adhesives, rubber compositions, packaging materials such as gas barrier films, agricultural materials such as plant vitality agents / soil improvers, inks / toners, adhesives, surfactants, ultraviolet absorbers, battery electrode materials, growth promoters for aquatic organisms, and anti-discoloration agents for foods.

[0169] Example

[0170] Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited thereto.

[0171] <Calculation of lignin content in second-generation ethanol saccharification residue (raw material)>

[0172] The content of lignin contained in the biomass residue used in the examples was calculated by analyzing constituent sugars after pretreatment as shown below.

[0173] [Pre-processing]

[0174] As a pretreatment, the raw material was pulverized using a Wiley mill and dried at 105° C. to obtain a sample.

[0175] [Composition sugar analysis]

[0176] Take an appropriate amount of the above sample, add 72% by mass sulfuric acid, and place it at 30°C while stirring continuously for 1 hour. While mixing the reaction solution with pure water, transfer it completely to a pressure bottle, treat it in an autoclave at 120°C for 1 hour, and filter to obtain a filtrate and a residue. The monosaccharides in the filtrate are quantified by high performance liquid chromatography. It should be noted that C6 polysaccharides (mainly glucans) are defined as cellulose, and C5 polysaccharides (mainly xylans) are defined as hemicellulose.

[0177] [Lignin]

[0178] The residue obtained by filtration during the analysis of constituent sugars was dried at 105°C, and the weight was measured to calculate the decomposition residue ratio. Then, the ash content was corrected to calculate the lignin content.

[0179] <Properties of lignin derivatives and raw material lignin>

[0180] In addition, various measurements were performed on the lignin derivatives obtained in each example or the lignin in the raw material by the following methods.

[0181] [Molecular weight determination]

[0182] The weight average molecular weight (Mw) of the lignin derivative obtained in each example and the lignin in the raw material was determined by GPC (gel permeation chromatography) in terms of molecular weight converted to standard polystyrene. The measuring apparatus and conditions are as follows.

[0183] ·Separation column: 2 pieces of "TSKgel Super Multipore HZ-M" manufactured by Tosoh Corporation

[0184] ·Eluent: Tetrahydrofuran

[0185] Eluent flow rate: 1.0mL / min

[0186] Detector: Differential Refractive Index (RI)

[0187] ·Measurement temperature: 40℃

[0188] [Existence ratio of components with molecular weight LogM 2.15 to 2.20]

[0189] According to the spectrum of the molecular weight of lignin obtained by GPC (gel permeation chromatography) (the y-axis depicts dw / dLogM, the x-axis depicts LogM), find the position (LogM) of the expected peak at the peak top or shoulder peak, and set them as the average (A) of the Gaussian function. In addition, for the value of dispersion (S) and each Gaussian function, set an arbitrary number (X) after establishing the existence. Prepare a Gaussian function corresponding to the number (N) of expected peaks or shoulders, and assign three variables A, S, and X to each of them. Calculate the correlation coefficient R based on the synthetic function (linear sum) of N Gaussian functions and the y-axis of the GPC spectrum: dw / dLogM 2 , to make R 2 The three variables A, S, and X of each Gaussian function are operated in a way that the maximum value is achieved. Specifically, the solver of spreadsheet software such as Excel is used for this operation. Here, it is necessary to make R 2 A, S, and X of each function are appropriately manipulated so as to reach at least 0.9999. This manipulation is performed, and the ratio of the composite function of a plurality of Gaussian functions existing in the molecular weight LogM 2.15 to 2.20 to the composite of all Gaussian functions is defined as the abundance ratio of the molecular weight LogM 2.15 to 2.20 component.

[0190] [Softening point (℃)]

[0191] The lignin derivative or raw material (solid sample) obtained in each example was crushed with a mortar, sieved (40 mesh) to remove large particles, and the crushed sample was placed in an aluminum cup (circular upper part φ60, lower part φ53×depth 15mm), and 10 to 20 mg was placed. The aluminum cup containing the sample was placed on a heating plate (ASONEND-2A) and covered with a glass plate (thickness 0.5mm). After heating to 80°C, the temperature was visually observed through the glass every time it was increased by 10°C, and the temperature at which the dissolution was visually confirmed was used as the softening point.

[0192] [Relative existence rate of basic skeleton (%) and hydroxyl ratio (%)]

[0193] (1) A solvent prepared by mixing deuterated chloroform, pyridine and cyclohexanol (internal standard) was added to the lignin derivative or raw material (solid sample) obtained in each example, and then 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane was added as a derivatizing agent, and the mixture was heated at 50° C. for 1 hour. Then, the measurement was carried out under the following conditions: 31 P-NMR determination.

[0194] It should be noted that since the comparative raw material lignin 2 was not completely dissolved in the solvent, only the soluble portion was measured. The measuring apparatus and conditions are as follows.

[0195] Pulse width: 30°

[0196] Round trip time: 2 seconds

[0197] ·Measurement range: -60~200ppm

[0198] Cumulative times: 200 times

[0199] The signal from cyclohexanol as an internal standard was set at 145.2 ppm, 144.0-142.0 ppm was identified as the S-type skeleton, and 141.0-136.6 ppm was identified as the G-type skeleton. The relative abundance % of each basic skeleton was calculated based on the integral value. The relative abundance % of the H-type skeleton was calculated by subtracting the relative abundance % of the S-type skeleton and the G-type skeleton from the total aromatic hydroxyl amount.

[0200] In addition, 150.0-145.5 ppm was identified as aliphatic hydroxyl groups, and 144.7-136.6 ppm was identified as aromatic hydroxyl groups. Based on the integral curve, the amount of aliphatic hydroxyl groups (mol / g) and the amount of aromatic hydroxyl groups (mol / g) were calculated to determine the percentage of each hydroxyl group.

[0201] (2) Existence rate ratio and reaction point

[0202] Based on the relative abundance % of each basic skeleton mentioned above, it is calculated:

[0203] · The ratio of the sum of twice the relative abundance rate H (%) of the H-type skeleton and the relative abundance rate G (%) of the G-type skeleton to the relative abundance rate S (%) of the S-type skeleton [(2H+G) / S];

[0204] The total of the reaction points based on the relative abundance ratio H (%) of the H-type skeleton and the relative abundance ratio G (%) of the G-type skeleton [2H+G].

[0205] 〔Lignin derivatives〕

[0206] [Example 1]

[0207] (1) Reaction process

[0208] 100.1 parts by mass (100.1 g, 55.0 g as lignin) of the second generation ethanol saccharification residue (lignin content: 55% by mass), 20 parts by mass of phenol, and 200 parts by mass of ethanol were placed in a 1.0 L stirrable pressure container and heated / stirred at 2.6 MPa and 200°C for 4 hours.

[0209] (2) Refining process

[0210] (2-1) Filter

[0211] A pressure filter equipped with No. 2 filter paper is assembled, and the reaction solution obtained in the above reaction step is added thereto. The pressure is increased to 0.1 to 0.4 MPa with compressed air or nitrogen, and then filtered.

[0212] (2-2) Distillation

[0213] The filtrate after the filtration was heated (40 to 60° C.) under reduced pressure (5 to 10 kPa) using an evaporator to perform reduced pressure distillation to remove ethanol and phenol.

[0214] (2-3) Decompression and drying

[0215] In order to remove the phenol remaining in the distillation, the mixture was heated (120 to 150° C.) under reduced pressure (1.0 to 5.0 kPa) to perform vacuum drying to remove the phenol, thereby obtaining a lignin derivative 1 (52.9 g).

[0216] The calculated amount of the lignin derivative (30.0 g) relative to the amount of lignin charged (calculated value: 55.0 g) was used as the yield, and the yield was calculated according to the following formula. The result was 54%.

[0217] Yield (%) = [(amount of lignin derivative) / (amount of lignin fed)] × 100

[0218] [Example 2]

[0219] The same procedure as in Example 1 was carried out except that phenol was changed to 37 parts by mass and ethanol was changed to 183 parts by mass, thereby obtaining a lignin derivative 2 (lignin derivative amount: 52.9 g, yield: 96%).

[0220] [Example 3]

[0221] The same procedure as in Example 1 was carried out except that phenol was changed to 10 parts by mass and ethanol was changed to 210 parts by mass, thereby obtaining a lignin derivative 3 (amount of lignin derivative: 26.4 g, yield: 48%).

[0222] [Example 4]

[0223] A lignin derivative 4 (lignin derivative amount: 52.1 g, yield: 95%) was obtained in the same manner as in Example 1 except that phenol was changed to 51 parts by mass and ethanol was changed to 169 parts by mass.

[0224] [Example 5]

[0225] The same procedure as in Example 1 was carried out except that phenol was changed to 20 parts by mass, ethanol was changed to 100 parts by mass, and water was changed to 100 parts by mass, to obtain lignin derivative 5 (lignin derivative amount 47.6 g, yield 86%).

[0226] [Example 6]

[0227] The same procedure as in Example 3 was carried out except that ethanol was changed to 180 parts by mass and water was changed to 20 parts by mass, to obtain a lignin derivative 6 (lignin derivative amount 37.3 g, yield 68%).

[0228] [Example 7]

[0229] The same procedure as in Example 3 was carried out except that ethanol was changed to 160 parts by mass and water was changed to 40 parts by mass, to obtain lignin derivative 7 (lignin derivative amount 39.8 g, yield 72%).

[0230] [Example 8]

[0231] The same procedure as in Example 1 was carried out except that 0.2 parts by mass of sulfuric acid was added and the reaction time was changed to 2 hours, thereby obtaining a lignin derivative 8 (amount of lignin derivative: 37.8 g, yield: 69%).

[0232] [Example 9]

[0233] The same procedure as in Example 1 was followed except that phenol was set to 44 parts by mass, ethanol was set to 154 parts by mass, water was set to 22 parts by mass, the reaction temperature was set to 220° C., and the reaction time was set to 2 hours, to obtain lignin derivative 9 (lignin derivative amount 42.4 g, yield 77%).

[0234] [Example 10]

[0235] The same procedure as in Example 9 was carried out except that the reaction temperature was 200° C. and the reaction time was 4 hours, thereby obtaining a lignin derivative 10 (amount of lignin derivative: 37.8 g, yield: 69%).

[0236] [Example 11]

[0237] The same procedure as in Example 10 was carried out except that 0.2 parts by mass of sulfuric acid was added to obtain a lignin derivative 11 (amount of lignin derivative: 43.6 g, yield: 79%).

[0238] [Example 12]

[0239] The same procedure as in Example 10 was carried out except that anisole was used as phenol to obtain a lignin derivative 12 (amount of lignin derivative: 36.8 g, yield: 67%).

[0240] [Example 13]

[0241] The same procedure as in Example 11 was carried out except that anisole was used as phenol to obtain a lignin derivative 13 (amount of lignin derivative: 39.7 g, yield: 72%).

[0242] [Example 14]

[0243] The same procedure as in Example 11 was carried out except that toluene was used as phenol to obtain a lignin derivative 14 (amount of lignin derivative: 35.1 g, yield: 64%).

[0244] [Example 15]

[0245] A lignin derivative 14 (lignin derivative amount 46.3 g, yield 84%) was obtained in the same manner as in Example 10 except that phenol was changed to 66 parts by mass and ethanol was changed to 132 parts by mass.

[0246] Tables 1 and 2 show the results of measuring the properties of the lignin derivatives 1 to 15 obtained in Examples 1 to 15 by the above-mentioned methods.

[0247] In addition, in the molecular weight measurement, part of the lignin derivative 5 was insoluble in the eluent, and therefore the molecular weight measurement (Mw) of Example 5 could not be analyzed.

[0248] [Comparative Example 1]

[0249] As Comparative Example 1, the properties of lignin in the second generation ethanol saccharification residue as a raw material were analyzed. However, since only a small amount of lignin in the second generation ethanol saccharification residue is soluble in various organic solvents, it cannot be analyzed by the above method.

[0250] [Comparative Example 2]

[0251] Kraft lignin (Lignin, alkali (product model number 370959) manufactured by SIGMA-ALDRICH) was used as Comparative Example 2. The properties of the kraft lignin were analyzed, but since the kraft lignin contains a large amount of components that are insoluble in various organic solvents, the analysis based on the above method was limited to a portion of the analysis.

[0252] [Comparative Example 3]

[0253] Comparative lignin 1 (amount of lignin derivative: 25.9 g, yield: 47%) was obtained in the same manner as in Example 8 except that phenol was not added and ethanol was changed to 220 parts by mass.

[0254] [Comparative Example 4]

[0255] Comparative lignin 2 (lignin derivative amount 43.3 g, yield 79%) was obtained in the same manner as in Example 1 except that phenol was not added and ethanol was changed to 110 parts by mass and water was changed to 110 parts by mass.

[0256] [Table 1]

[0257] Table 1

[0258]

[0259] Aromatic compound ratio (mass %) * : [Amount of aromatic compounds / total amount of aromatic compounds and solvents] × 100

[0260] [Table 2]

[0261]

[0262] As mentioned above, the lower the softening point of the lignin derivative, the easier it is to mix with the resin. In addition, for the lignin derivative, the less the amount of aliphatic hydroxyl groups, and the greater the ratio [(2H+G) / S] which is an index of reactivity, the easier it is to react with the resin. In addition, by making the molecular weight of the lignin derivative not too small but having a certain degree of size, when it is made into a molded product, the physical properties such as bending strength tend to become good.

[0263] From the above viewpoints, if we examine Tables 1 and 2, it can be seen from the comparison between Examples 1 to 15 and Comparative Examples 3 and 4 that based on the production method of the present invention, the following lignin derivatives can be obtained at a certain yield, that is, since the molecular weight does not become too small and the softening point is below 210°C, the lignin derivatives show good compatibility with the resin and good reactivity. In particular, it can be seen that by adjusting the proportion of aromatic compounds used, the selection and proportion of the solvent used, it is possible to achieve both a better low softening point and a high yield. In addition, it can be seen that in Comparative Examples 3 and 4 where no aromatic compounds are used, the proportions of components with a molecular weight of 50 to 300 are 0.70% by mass and 0.26% by mass, respectively, and when used as a resin component material, there is a possibility of causing undesirable conditions such as swelling.

[0264] Therefore, it can be seen from Tables 1 and 2 that the lignin derivatives of Examples are modified in terms of molecular weight and composition, and are therefore useful as materials containing lignin derivatives, particularly resin composition materials.

[0265] Furthermore, the second generation ethanol saccharification residue of Comparative Example 1 and the kraft lignin of Comparative Example 2 as raw materials cannot be used directly as resin composition materials. In contrast, according to the production method of the present invention, a lignin derivative that can actually be used as a resin composition material can be obtained.

[0266] 〔Cured product〕

[0267] Next, using lignin derivatives 2, 6, 8 of Examples 2, 6, and 8, the second-generation ethanol saccharification residue as raw material (comparative raw material lignin 1) of Comparative Example 1, the sulfate lignin of Comparative Example 2 (comparative raw material lignin 2), the comparative lignin 1 of Comparative Example 3, and the comparative lignin 2 of Comparative Example 4, resin composition materials and molded bodies formed using the materials are manufactured in the following examples.

[0268] The resin composition materials and molded products were evaluated by the following methods.

[0269] (Ease of mixing)

[0270] In Examples 16 to 18 and Comparative Examples 5 to 8, the ease of kneading was evaluated based on the following indexes.

[0271] A: Easy to mix

[0272] B: Although difficult, it can be mixed

[0273] C: Unable to mix

[0274] (Stirring properties)

[0275] In Examples 19 to 21 and Comparative Examples 9 to 12, the ease of stirring during the reaction was evaluated based on the following indexes.

[0276] A: Easy to stir

[0277] B: Although difficult, it can be stirred

[0278] C: Unable to stir

[0279] (Bending Strength)

[0280] A 5 mm×50 mm×1 mm sample was cut out from the molded article obtained in each example, and the bending strength was measured using Instron 5566 manufactured by Instron Japan in a 3-point bending mode, a span of 30 mm, and a speed of 2 mm / min, and evaluated based on the indexes.

[0281] A: The sample is not easy to break

[0282] B: The sample has broken

[0283] C: The sample broke immediately

[0284] -: Poor forming

[0285] [Examples 16 to 18]

[0286] 35 parts by mass of a linear phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-53195), 50 parts by mass of wood powder, 15 parts by mass of the lignin derivatives 2, 6, and 8 of Examples 2, 6, and 8, 7 parts by mass of hexamethylenetetramine as a curing agent, and 1 part by mass of zinc stearate as an internal release agent were mixed and kneaded at 110 to 120° C. for 3 minutes using a two-roll kneader to obtain a resin composition material containing a lignin derivative.

[0287] The resin composition material containing the lignin derivative obtained above was pressed into a heated mold cavity, molded by transfer molding at 175°C for 3 minutes, and then cured in an oven at 180°C for 8 hours to obtain a molded body.

[0288] Table 3 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0289] [Comparative Example 5]

[0290] A resin composition material and a molded body were obtained in the same manner as in Example 16 except that the second generation ethanol saccharification residue (comparative raw material lignin 1) was used as a raw material instead of the lignin derivative.

[0291] Table 3 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0292] [Comparative Example 6]

[0293] A resin composition material and a molded body were obtained in the same manner as in Example 16 except that kraft lignin (comparative raw material lignin 2) was used instead of the lignin derivative.

[0294] Table 3 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0295] [Comparative Example 7]

[0296] A resin composition material and a molded body were obtained in the same manner as in Example 16 except that comparative lignin 1 was used instead of the lignin derivative.

[0297] [Comparative Example 8]

[0298] A resin composition material and a molded body were obtained in the same manner as in Example 16 except that comparative lignin 2 was used instead of the lignin derivative.

[0299] Table 3 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0300] [Table 3]

[0301] Table 3

[0302]

[0303] [Examples 19 to 21]

[0304] In a 0.5 L separable flask equipped with a reflux device and a stirring blade, 50 parts by mass (50.0 g) of each of the lignin derivatives 2, 6, and 8 of Examples 2, 6, and 8 and 30 parts by mass of a 40% by mass formaldehyde aqueous solution were added and stirred. The molar ratio of formaldehyde to the phenol in the lignin derivative was 1.5. 35 parts by mass of a 50% by mass sodium carbonate aqueous solution was slowly added dropwise, and heated at 100° C. for 2 hours to obtain a liquid composition.

[0305] Then, 54 parts by mass of wood powder was added and stirred until the mixture was uniform, thereby obtaining a resin composition material containing a lignin derivative.

[0306] The resin composition material containing the lignin derivative obtained above was decompressed to remove moisture, and was press-molded under the conditions of a surface pressure of 0.2 MPa, 180° C., and 10 minutes, and then cured in an oven at 200° C. for 4 hours to obtain a molded body.

[0307] Table 4 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0308] [Comparative Example 9]

[0309] A resin composition material and a molded body were obtained in the same manner as in Example 19 except that the second generation ethanol saccharification residue (comparative raw material lignin 1) as a raw material was used instead of the lignin derivative.

[0310] Table 4 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0311] [Comparative Example 10]

[0312] A molded body was obtained in the same manner as in Example 19 except that kraft lignin (comparative raw material lignin 2) was used instead of the lignin derivative.

[0313] Table 4 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0314] [Comparative Example 11]

[0315] A molded body was obtained in the same manner as in Example 19 except that Comparative Lignin 1 was used instead of the lignin derivative.

[0316] [Comparative Example 12]

[0317] A molded body was obtained in the same manner as in Example 19 except that Comparative Lignin 2 was used instead of the lignin derivative.

[0318] Table 4 shows the results of the above evaluations of the above resin composition materials and the molded products.

[0319] [Table 4]

[0320] Table 4

[0321]

[0322] The results of Comparative Examples 7, 8, 11, and 12 using Comparative Lignin 1 or 2 obtained without involving aromatic compounds in the reaction were: it was not possible to achieve excellent kneading properties, stirring properties, and bending strength. In contrast, as shown in Tables 3 and 4, the lignin derivatives obtained in the present invention have excellent kneading properties and stirring properties during the reaction, so it can be seen that the miscibility has been improved. In addition, it can be seen from the bending properties of the molded bodies obtained in the examples that molded bodies with good physical properties have been obtained. It should be noted that, according to Comparative Examples 5, 6, 9, and 10, it can be seen that the second-generation ethanol saccharification residue and sulfate lignin used as raw materials are difficult to use directly as resin composition materials.

[0323] Therefore, it can be seen from Tables 1 to 4 that the polyphenol derivatives obtained by the production method of the present invention have a low softening point and excellent kneading and stirring properties, so they can be easily mixed with resins, and have highly reactive reaction points and excellent bending strength, so they can easily react with resins. In addition, by adjusting the usage ratio of the aromatic compound, the selection and usage ratio of the solvent used, it is possible to achieve a more excellent low softening point, high yield and good economic efficiency.

[0324] That is, the polyphenol derivative obtained by the production method of the present invention is useful as a plastic material that satisfies the following four conditions: (i) being inexpensive, (ii) being able to be produced in large quantities, (iii) being easily mixed with a resin, and (iv) being easily reactive with a resin.

[0325] Industrial Applicability

[0326] The polyphenol derivative of the present invention is low-molecularized and has improved miscibility with other plastic materials, and has increased reaction points. Through the improvement of miscibility and the increase of reaction points, it can be expected that the physical properties of the molded product will be improved. Furthermore, since mixing becomes easy, it is not necessary to have a large-scale device with high cost when manufacturing a solidified part. In addition, since lignin, which was almost discarded in the past, can be effectively utilized, it is also effective for environmental protection.

Claims

1. A method for producing a polyphenol derivative, comprising: A step of reacting a composition containing polyphenol with an aromatic compound having ortho-para-directing groups in a solvent without a catalyst, The aromatic compound is a phenol compound represented by the following formula (1): In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 15 carbon atoms, and R 1 and R 2 Optional same or different, The mass ratio of the phenol compound to the lignin in the polyphenol-containing composition, i.e., phenol compound / lignin, is 0.1 to 2. The solvent comprises water and an organic solvent, The mass ratio of the organic solvent to water [organic solvent: water] is 95:5 to 50:

50.

2. The method for producing a polyphenol derivative according to claim 1, wherein The polyphenol-containing composition is lignite.

3. The method for producing a polyphenol derivative according to claim 1, wherein The polyphenol in the polyphenol-containing composition is lignin.

4. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is at least one of biomass and biomass residue.

5. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is any one or more of second-generation ethanol saccharification residues, second-generation ethanol fermentation residues, sulfite lignin, sulfate lignin, alkali lignin and tannin.

6. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is any one or more of second-generation ethanol saccharification residues and second-generation ethanol fermentation residues.

7. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is a second-generation ethanol saccharification residue obtained by saccharification of plant-based biomass.

8. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is a second-generation ethanol saccharification residue obtained by saccharifying plant biomass through any treatment selected from the group consisting of an organic solvent method, a pressurized hot water method, a steam explosion method, an ammonia treatment method, an ammonia explosion method, an acid treatment method, an alkali treatment method, an oxidative decomposition method, a pyrolysis method, and a microwave heating method.

9. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is a second-generation ethanol fermentation residue obtained by fermentation of plant-based biomass.

10. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The polyphenol-containing composition is a second-generation ethanol fermentation residue obtained by subjecting plant biomass to any treatment selected from an organic solvent method, a pressurized hot water method, a steam explosion method, an ammonia treatment method, an ammonia explosion method, an acid treatment method, an alkali treatment method, an oxidative decomposition method, a pyrolysis method, and a microwave heating method, followed by a fermentation treatment.

11. The method for producing a polyphenol derivative according to claim 7, wherein The plant-based biomass is herbaceous biomass.

12. The method for producing a polyphenol derivative according to claim 11, wherein The herbaceous biomass is any one selected from the group consisting of empty shells of oil palm, wheat straw, rachis / stems / leaves / residues of corn, bagasse, sugarcane tails and energy sugarcane.

13. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is any one selected from phenol, m-cresol, and 3,5-dimethylphenol.

14. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is phenol.

15. The method for producing a polyphenol derivative according to claim 1, wherein In the formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a hydroxyl group or a linear or branched alkyl group having 1 to 5 carbon atoms.

16. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is any one selected from phenol, resorcinol and phloroglucinol.

17. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is any one selected from 3-alkylphenol, 5-alkylresorcinol and 3,5-dialkylphenol.

18. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is any one selected from the group consisting of m-cresol, 3-ethylphenol, and 3-propylphenol.

19. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is any one selected from 5-methylresorcinol, 5-ethylresorcinol, and 5-propylresorcinol.

20. The method for producing a polyphenol derivative according to claim 1, wherein The phenol compound is any one selected from 3,5-dimethylphenol, 3-methyl-5-ethyl-phenol, and 3,5-diethylphenol.

21. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The solvent includes a polar solvent.

22. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The organic solvent is selected from alcohols, ketones, ethers and aromatics.

23. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The solvent comprises an organic solvent having 1 to 6 carbon atoms and water, The organic solvent having 1 to 6 carbon atoms is any one selected from alcohols, ketones, ethers and aromatics.

24. The method for producing a polyphenol derivative according to claim 22, wherein The alcohol is any one selected from methanol, ethanol and isopropyl alcohol.

25. The method for producing a polyphenol derivative according to claim 22, wherein The ketone is any one selected from acetone and methyl ethyl ketone.

26. The method for producing a polyphenol derivative according to claim 22, wherein The ether is tetrahydrofuran.

27. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The organic solvent is selected from ethanol and acetone.

28. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The solvent is a combination of ethanol and water.

29. The method for producing a polyphenol derivative according to claim 1, wherein The mass ratio [organic solvent: water] is 90:10 to 50:

50.

30. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The phenol compound is used in an amount of 4% by mass to 95% by mass based on the total amount of the phenol compound and the solvent.

31. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The phenol compound is used in an amount of 10% by mass to 70% by mass based on the total amount of the phenol compound and the solvent.

32. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The phenol compound is used in an amount of 10% by mass to 50% by mass based on the total amount of the phenol compound and the solvent.

33. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The phenol compound is used in an amount of 20% by mass to 40% by mass based on the total amount of the phenol compound and the solvent.

34. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The mass ratio of the phenol compound to the lignin in the polyphenol-containing composition, that is, phenol compound / lignin, is 0.1 to 1.

35. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The reaction is carried out at a reaction temperature greater than 140° C. and less than 350° C.

36. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The reaction is carried out at a reaction temperature greater than 140° C. and less than 250° C.

37. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein The reaction is performed under the condition that the reaction time is 1 hour to 8 hours.

38. The method for producing a polyphenol derivative according to any one of claims 1 to 3, wherein It also has a solid-liquid separation process.

39. The method for producing a polyphenol derivative according to claim 38, wherein In the solid-liquid separation step, the reaction liquid after the reaction step is filtered to perform solid-liquid separation, and a polyphenol derivative is obtained in the filtrate.

40. The method for producing a polyphenol derivative according to claim 39, wherein In the solid-liquid separation step, the reaction liquid after the reaction step is filtered at 20°C to 100°C.

41. The method for producing a polyphenol derivative according to claim 39, wherein In the solid-liquid separation step, the reaction liquid after the reaction step is filtered at 0.1 MPa to 0.99 MPa.

42. The method for producing a polyphenol derivative according to claim 38, wherein After the reaction step, the solution containing the polyphenol derivative is subjected to reduced pressure distillation to obtain the polyphenol derivative.

43. The method for producing a polyphenol derivative according to claim 42, wherein The reduced pressure distillation is carried out at 40°C to 200°C.

44. The method for producing a polyphenol derivative according to claim 42, wherein The reduced pressure distillation is carried out at 3 kPa to 20 kPa.

45. The method for producing a polyphenol derivative according to claim 42, wherein The reduced pressure distillation is performed after the solid-liquid separation step.

46. ​​A lignin derivative produced by the method for producing a polyphenol derivative according to any one of claims 1 to 45, wherein the lignin derivative has a weight average molecular weight of less than 5000 and a content of molecular weights LogM 2.15 to 2.20 of less than 0.7 mass %. The lignin derivative according to claim 46 , which has a weight average molecular weight of 3,000 to 4,000. The lignin derivative according to claim 46 , which has a softening point of 90° C. or higher. The lignin derivative according to claim 46, which has a weight average molecular weight of 3000 to 4000 and a softening point of 140°C to 210°C.

50. The lignin derivative according to claim 46, wherein the lignin derivative is used 31 The abundance ratio of the aliphatic hydroxyl group relative to the total abundance ratio of the aliphatic hydroxyl group and the aromatic hydroxyl group, which is determined by the integrated value of the P-NMR measurement, is less than 27%.

51. The lignin derivative according to claim 46, wherein the lignin derivative is used 31 The ratio of the sum of twice the relative abundance ratio H of the H-type skeleton and the relative abundance ratio G of the G-type skeleton to the relative abundance ratio S of the S-type skeleton obtained by the integral value of the P-NMR measurement [(2H+G) / S] is 2.3 or more, The units of the relative abundance ratio S, the relative abundance ratio H and the relative abundance ratio G are %.

52. A material containing a lignin derivative, comprising at least one lignin derivative selected from the group consisting of a lignin derivative produced by the method for producing a polyphenol derivative according to any one of claims 1 to 45 and a lignin derivative according to any one of claims 46 to 51.

53. A resin composition material containing a lignin derivative, comprising at least one lignin derivative selected from the group consisting of a lignin derivative produced by the method for producing a polyphenol derivative according to any one of claims 1 to 45 and a lignin derivative according to any one of claims 46 to 51. 54 . The resin composition material containing a lignin derivative according to claim 53 , further comprising at least one of a thermosetting resin and an aldehyde.

55. The resin composition material containing a lignin derivative according to claim 54, wherein The thermosetting resin is a phenolic resin.

56. The resin composition material containing a lignin derivative according to claim 55, wherein The phenolic resin is a linear phenolic resin or a resol phenolic resin.

57. The resin composition material containing a lignin derivative according to claim 54, wherein The content of the thermosetting resin is 100 to 300 parts by mass based on 100 parts by mass of the lignin derivative.

58. The resin composition material containing a lignin derivative according to claim 54, wherein The aldehydes are any of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, furfural, benzaldehyde, phenylacetaldehyde and salicylaldehyde.

59. The resin composition material containing a lignin derivative according to claim 54, wherein The aldehyde is formaldehyde.

60. The resin composition material containing a lignin derivative according to claim 59, wherein The molar ratio of the phenolic group contained in the lignin derivative to the formaldehyde [formaldehyde / phenolic group] is 1.0 to 2.

5.

61. The resin composition material containing a lignin derivative according to any one of claims 53 to 60, wherein The composition further contains at least one filler selected from inorganic fillers and organic fillers.

62. The resin composition material containing a lignin derivative according to claim 61, wherein The organic filler material is any one or more selected from carbon fiber, aramid fiber, paper powder, wood powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell, nut powder, chitin powder and starch.

63. The resin composition material containing a lignin derivative according to claim 61, wherein The content of the filler is 50 to 200 parts by mass based on 100 parts by mass of the lignin derivative.

64. The resin composition material containing a lignin derivative according to any one of claims 53 to 60, wherein The invention further contains at least one curing agent selected from the group consisting of hexamethylenetetramine, hexamethyleneformaldehyde and paraformaldehyde.

65. The resin composition material containing a lignin derivative according to claim 64, wherein The composition further contains at least one inorganic base selected from the group consisting of calcium hydroxide, sodium hydroxide, potassium hydroxide, calcium oxide and magnesium oxide.

66. A molded article, which is formed by using any one or more of the resin composition materials containing a lignin derivative according to any one of claims 53 to 65.

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