JP2001342353A - Lignocellulose composition comprising lignophenol derivative and cellulose component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a means to convert a wood resource having fixed material characteristics into a novel moldable resource, such as a plastic. SOLUTION: A lignocellulose composition comprising a lignophenol derivative and a cellulose component is obtained by adding an acid to a phenol derivative- supplemented lignocellulose substance and mixing these.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lignocellulosic composition comprising a lignophenol derivative and a cellulose component. For more details. The present invention relates to a lignocellulosic composition comprising a lignophenol derivative obtained by sorbing a phenol derivative to a lignocellulosic substance such as wood and then treating it with an acid, and a cellulose component.

[0002]

2. Description of the Related Art In modern society, the use of fossil resources has become indispensable. However, reproduction of fossil resources is impossible, and there is a fear of exhaustion in the near future. Biomass resources are attracting attention as one of the alternatives to fossil resources. Among the biomass resources, woody biomass is a huge resource on the earth, can be produced in a short period of time, is a resource that can be continuously supplied by appropriate maintenance, and after being used as a resource, It is attracting attention because it is decomposed in nature and reborn as a new biomass resource.

[0003] Woody biomass resources, ie, lignocellulosic resources, are composed of hydrophilic carbohydrates such as cellulose and hemicellulose and hydrophobic lignin (polyphenol), which are interpenetrating polymer networks (IPN) in the cell wall. It has a structure and exists in a complex state with complex intertwining. Lignocellulosic resources include:
The structure of such a composite material gives usefulness as various materials.

[0004] Considering the use form of lignocellulosic resources, as a first use form, it is processed as a composite material of a predetermined shape as a building material or a furniture material, or is used as a composite material, or is made of wood chips or fibers. There is a direct use form used as a molding material and the like, and a second use form is an indirect use form of extracting and pulping cellulose, which is a component of the composite. here,
When considering the effective use of forest resources in consideration of the depletion of fossil resources in the future, it is important to reuse forest resources in both forms of use.

[0005] However, at present, in a direct utilization form in which wood as a composite is directly used as a molded product,
Due to its shape and size, it is difficult to reuse wood, and it is often discarded after use. Further, when used as a molding material, it is difficult to reuse it because it contains a thermosetting resin as a binder. As described above, in the direct use mode, at present, it is difficult to reuse cellulose and the like and lignin constituting the complex.

[0006] In the indirect use form of extracting and pulping cellulose, which is a component of the composite, the fiber is formed into a sheet and the sheet is repeatedly formed to recycle the material. Lignin, a constituent component, is hardly used.
As described above, at present, lignin is not reused in any of the direct and indirect usage modes. Lignin is the second most abundant organic substance on earth after cellulose. Nevertheless, no attempt has been made to focus on lignin in wood as a composite to produce a reusable form of a wood product or to reuse such a wood product.

In order to use lignin effectively in woody (lignocellulosic) biomass,
First, it is necessary to separate the wood into its constituents.
The present inventors have found that, based on previous studies, the combination of swelling of carbohydrates by concentrated acid and the destruction of lignin by the combination of lignin solvation with phenol derivatives suppresses lignin inactivation and reduces A method for separating lignophenol derivatives and carbohydrates as constituents has been developed (JP-A-2-233701).
issue). As a method of utilizing the lignophenol derivative obtained by this method, for example, it has been reported that a molded article is produced by applying to a molding material such as a cellulose fiber (Japanese Patent Application Laid-Open No. 9-278904). However, the above patent publication does not describe the use of a cellulose component, which is a component other than lignin, of the lignocellulosic material.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide means for converting wood resources having fixed material properties into new functional resources which can be molded and processed like plastic. Another object of the present invention is to release a high degree of association (crystal structure) of cellulose by applying a phase separation system of a lignocellulosic substance, and at the same time, convert a lignin segment into a lignophenol-like phenolic linear polymer. To form a homogeneous system with the cellulose compartment. As a result, recrystallization of cellulose is inhibited, and at the same time, it flows as a whole at the melting temperature of lignophenol, and a material that can be freely molded is obtained.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by adding an acid to a lignocellulosic substance to which a phenol derivative has been added and mixing it, lignophenol is obtained. The present inventors have found that a uniform composition comprising a derivative and a cellulose component can be obtained, and that the obtained composition has plasticity, thereby completing the present invention.

According to the present invention, there is provided a lignocellulosic composition comprising a lignophenol derivative and a cellulose component, which is obtained by adding an acid to a lignocellulosic substance to which a phenol derivative has been added and mixing. Preferably, the lignophenol derivative component and the cellulose component form a homogeneous system. Preferably, an acid having an action of swelling cellulose and having a low action of hydrolyzing cellulose is used as the acid.

[0011] Preferably, the acid is phosphoric acid, formic acid or trifluoroacetic acid. Preferably, the phenol derivative to be added to the lignocellulose-based material is a phenol derivative having one or more substituents at the ortho and / or para positions.

Preferably, the phenol derivative to be added to the lignocellulose-based substance is a phenol derivative having at least one substituent selected from a lower alkyl group, a lower alkoxy group and a hydroxyl group in the ortho position and / or the para position. It is. Preferably, the composition of the present invention comprises p-cresol, 2,6-xylenol, 2,4-xylenol,
Methoxyphenol (Guaiacol), 2,6-dimethoxyphenol, catechol, resorcinol, homocatechol, pyrogallol and phloroglucinol; 95% phosphoric acid is added to a lignocellulosic substance to which a phenol derivative is added. It is a lignocellulosic composition obtained by mixing and comprising a lignophenol derivative and a cellulose component. Preferably, the lignophenol derivative is acylated or methylolated. Preferably, the lignocellulosic composition of the present invention is a plasticized material.

According to another aspect of the present invention, there is provided a molded article comprising the above-mentioned lignocellulose composition of the present invention. According to still another aspect of the present invention, the method includes a step of treating a lignocellulosic substance with a phenol derivative to add an acid to a mixture obtained by solvating the lignin component with the phenol derivative and mixing the mixture. A method for producing the lignocellulosic composition of the invention is provided.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method and an embodiment of the present invention will be described. The lignocellulosic composition of the present invention can be obtained by adding an acid to a lignocellulosic substance to which a phenol derivative has been added and mixing them. As the phenol derivative to be added to the lignocellulose-based substance, a monovalent phenol derivative, a divalent phenol derivative, a trivalent phenol derivative, or the like can be used. Specific examples of the monovalent phenol derivative include phenol which may have one or more substituents, naphthol which may have one or more substituents,
Examples include anthrol which may have the above substituents, anthroquinone ol which may have one or more substituents, and the like.

Specific examples of the divalent phenol derivative include catechol, which may have one or more substituents,
Examples thereof include resorcinol optionally having the above substituent, and hydroquinone optionally having one or more substituents. Specific examples of the trivalent phenol derivative include 1
Examples include pyrogallol which may have the above substituents.

The type of the substituent that the monovalent to trivalent phenol derivative may have is not particularly limited, and may have any substituent. Preferably, the electron-withdrawing group ( A group other than a halogen atom), for example, a lower alkyl group (e.g., methyl group, ethyl group, propyl group), a lower alkoxy group (e.g., methoxy group, ethoxy group, propoxy group), an aryl group (e.g., phenyl group), And a hydroxyl group. Further, at least one of the two ortho positions of the phenolic hydroxyl group on the phenol derivative is preferably unsubstituted. Preferred examples of the phenol derivative include p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol (Guaiacol), 2,6-dimethoxyphenol, catechol, resorcinol, homocatechol, pyrogallol and phlorogol. Lucinol and the like.

The overall function (hydrophilicity, hydrophobicity, physiological function, etc.) of the obtained lignocellulose composition of the present invention can be controlled by selecting the type of phenol derivative to be used. . The phenol derivative used in the present invention is preferably a phenol derivative having a substituent at the 4-position (para-position) and / or a phenol derivative having a substituent at the 2-position (ortho-position) and the 4-position (para-position). . A phenol derivative having a substituent at the 4-position (para-position) is a phenol derivative having no substituent at two ortho positions. A phenol derivative having a substituent at the 2-position (ortho-position) and 4-position (para-position) refers to a phenol derivative having no substituent at the 6-position (one ortho-position).

The lignophenol derivative is reacted with a compound capable of forming a crosslinkable functional group under alkaline conditions to prepare a crosslinkable lignophenol derivative having a crosslinkable functional group at the ortho position of the phenolic hydroxyl group in the lignophenol derivative. A polymer material can be prepared and used by crosslinking the crosslinkable lignophenol. In this case, the introduction frequency of the crosslinkable functional group can be adjusted by selecting the type of the phenol derivative to be used. That is, when a phenol derivative having a substituent at the 4-position (para-position) is used, the phenol derivative binds to the benzyl-position carbon atom of the phenylpropane unit of lignin at the 2-position or 6-position carbon atom. become. In this case, one of the remaining carbon atoms at the 2- or 6-position remains free and serves as a site for introducing a crosslinkable functional group.

On the other hand, when a phenol derivative having a substituent at the 2-position (ortho-position) and 4-position (para-position) is used, the phenol derivative has a carbon atom at the 6-position and the benzyl position of the phenylpropane unit of lignin. To the carbon atom of In this case, since the ortho and para positions in a free state do not exist, the introduced phenol derivative does not have a crosslinkable functional group introduction site. Therefore, the crosslinkable functional group is introduced only on the lignin host side.
As described above, a phenol derivative having a crosslinkable functional group-introducing site having a different reactivity, or a lignophenol derivative having no number of sites or introducing lignin by combining one or two or more different phenol derivatives is used. Can control the number of sites for introducing a crosslinkable functional group, and as a result, the crosslink density of the crosslinkable lignin derivative can be controlled.

That is, in a lignophenol derivative separated by treating a lignocellulosic substance with an acid in the presence of a phenol derivative or in a polymer material containing the same, a phenol derivative having a substituent at the 4-position (para-position) Is used as a reactive switching element, and the function or structure of the lignophenol derivative is controlled by using a phenol derivative having a substituent at the 2-position (ortho-position) and the 4-position (para-position) as a blocking switching element. It is also possible.

Further, when a phenol derivative having a substituent at the 2-position (ortho-position) and 6-position (ortho-position) is used as the introduced phenol derivative, the phenol derivative has a carbon atom at the 4-position and phenyl lignin. It will be attached to the benzylic carbon atom of the propane unit. In this case, since the ortho and para positions in a free state do not exist, the introduced phenol derivative does not have a crosslinkable functional group introduction site. Further, a phenol derivative having a substituent at the 2-position (ortho-position) and 6-position (ortho-position) does not exhibit a switching function, and thus functions as a stable control element. In the present invention, a phenol derivative having a substituent at the 4-position (para-position), a phenol derivative having a substituent at the 2-position (ortho-position) and 4-position (ortho-position), or a phenol derivative having a substituent at the 2-position (ortho-position) and 6-position ( A phenol derivative having a substituent at the ortho position) can be appropriately selected and used according to the purpose.

The "lignocellulosic material" used in the present invention includes woody materials, mainly various materials such as wood, for example, wood flour, chips, waste materials, and offcuts. As the wood to be used, any kind of wood, such as conifers and hardwoods, can be used. further,
Various herbaceous plants and samples related thereto, such as agricultural wastes, can also be used. As the acid added to the lignocellulose-based material, an acid having an action of swelling cellulose and having a low action of hydrolyzing cellulose is preferable.
Specific examples of the acid include 85% by weight or more of phosphoric acid, 38% by weight or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, and formic acid. Preferred acids are 85% by weight or more (preferably 95% by weight or more) phosphoric acid, trifluoroacetic acid, or formic acid.

Next, the method for producing the lignocellulose composition according to the present invention will be described in more detail. The lignocellulosic composition of the present invention contains a lignophenol derivative and a cellulose component. As used herein, the term "lignophenol derivative" refers to a polymer containing a diphenylpropane unit in which a phenol derivative is introduced via a CC bond at the α-position of the side chain of the phenylpropane unit of lignin. The amount and molecular weight of the introduced phenol derivative in this polymer vary depending on the lignocellulosic material as the raw material and the reaction conditions.

In order to obtain the lignocellulose composition of the present invention from the lignocellulose material, it is necessary to treat the lignin in the lignocellulose material with a phenol derivative to form a lignophenol derivative. Methods for converting lignin in a lignocellulosic material into a lignophenol derivative include the following two methods. The first method involves infiltrating a phenol derivative in liquid form (such as described above, for example, p-cresol) into a lignocellulosic material such as wood flour, solvating the lignin with the phenol derivative, The lignocellulosic material is added and mixed with a concentrated acid (as described above, for example, 95% phosphoric acid) to dissolve the cellulose component.
According to this method, a phenol derivative solvated with lignin and a concentrated acid in which a cellulose component is dissolved form a two-phase separation system. The lignin solvated by the phenol derivative is contacted with the acid only at the interface where the phenol derivative phase comes into contact with the concentrated acid phase, and the side chain α-position which is a high reaction site of the lignin basic structural unit generated by the contact with the acid. The cation at the (benzyl position) is attacked by the phenol derivative. As a result, the phenol derivative is C-
It is introduced at the C bond, and the molecular weight is reduced by the cleavage of the benzyl aryl ether bond. As a result, lignin is reduced in molecular weight, and at the same time, a lignophenol derivative in which a phenol derivative is introduced at the benzyl position of the basic structural unit is formed in the phenol derivative phase.

In the second method, a solvent (eg, ethanol or acetone) in which a solid or liquid phenol derivative is dissolved is penetrated into a lignocellulosic material, and then the solvent is distilled off (collection of the phenol derivative). Wearing process). Next, a concentrated acid (as described above, for example, 95% phosphoric acid) is added to the lignocellulosic material to dissolve the cellulose component. As a result, as in the first method, the lignin solvated with the phenol derivative becomes
High reaction site of lignin generated by contact with concentrated acid (side chain α
Is attacked by the phenol derivative,
A phenol derivative is introduced. Further, the benzyl aryl ether bond is cleaved to lower the molecular weight of lignin.

In order to prepare the lignocellulosic composition of the present invention from the above reaction mixture, all the reaction solutions after the concentrated acid treatment are poured into excess water, the insoluble fraction is collected by centrifugation, and It may be dried. The lignophenol derivative and the cellulose component are uniformly present in the dried product. The lignocellulosic composition of the present invention usually has fluidity. However, extracting the lignophenol fraction in the composition results in loss of fluidity. Therefore,
In the lignocellulosic composition of the present invention, it is considered that the lignophenol category exhibits an important plasticizing effect.

By acylating (eg, acetylating) the lignophenol derivative in the lignocellulose composition of the present invention, the fluidity of the composition can be increased. That is, in the lignocellulose-based composition of the present invention, the lignophenol derivatives tend to be bonded to each other or to the cellulose section by hydrogen bonding, and the materials are associated with each other. In this case, the flowability of the composition is not very high. However, acylation (for example, acetylation, etc.) of the lignophenol derivative can eliminate the association between the materials, whereby the flowability of the entire lignocellulose composition is improved, and processing into a molded article or the like is performed. In this case, the processing energy can be reduced. Furthermore, the lignophenol derivative in the lignocellulose composition of the present invention may be used after being converted to methylol. When a material that has been converted into methylol is used, a molded article having a relatively low density, a high water absorption, and excellent stability can be produced.

The lignocellulosic composition of the present invention can be processed into an arbitrary form, and is preferably used after being formed into a molded article, or as a resin material as a repair agent for wood products. For example, the lignocellulosic composition of the present invention can be molded into a desired shape by using a mold or passing through a die to produce a molded article. Examples of the molding method include injection molding, compression molding, fiber or film extrusion, profile extrusion, gas flow spinning, adhesive spinning, and substrate coating.

In producing a molded article using the lignocellulosic composition of the present invention, various provisional molding steps or molding methods before molding are selected and added depending on the type of material used, and further, other Additional steps can be added. Alternatively, the lignocellulosic composition of the present invention can be used in any form, such as a melt, particles, or a solution in a volatile solvent.

The use of the lignocellulosic composition of the present invention is not particularly limited. Examples of molded articles include packaging films, coated products (such as paper, cardboard and nonwoven fabric), fibers, nonwoven fabrics, extrusion nets, and the like. Personal hygiene articles, bottles and drinking containers, agricultural and horticultural films and containers, sustained release devices and the like. Alternatively, the lignocellulosic composition of the present invention can be used as a resin material, for example, as a repair agent for wood products.

The extraction and separation of the lignophenol derivative from the lignocellulose composition of the present invention can be carried out only by simple solvent immersion. Specifically, the lignocellulose-based composition of the present invention is immersed in a lignophenol derivative-affinity solvent (for example, acetone or the like), or is stirred in addition to immersion. The lignophenol derivative can be easily collected by collecting the solvent-soluble fraction. As described above, the lignocellulose composition of the present invention can easily separate and reuse its constituent components, and can effectively achieve resource circulation.

In the case of a product molded from the lignocellulosic composition of the present invention, the lignophenol derivative can be easily recovered after use of the product, similarly to the recovery of the lignophenol derivative from the lignocellulosic composition of the present invention. Can be. The recovery of the lignophenol derivative can be specifically performed as follows. That is, in a state where the original form of the molded body is maintained or processed into small pieces, the molded body is immersed in a lignophenol derivative-affinity solvent or stirred in addition to immersion. As a result, the lignophenol derivative is eluted in the solvent. By making the compact into small pieces and stirring in a solvent, rapid separation and extraction can be performed. When it is desired to maintain the original form of the molded article, the lignophenol derivative-affinity solvent is immersed in a non-aqueous solvent (for example, acetone) and extracted without stirring. The lignophenol derivative thus recovered can be used again in various fields including production of a molded article. Further, the cellulosic material separated at the same time can be reused again for various processed products including production of a molded article. Japanese Patent Application No. 2000 which is the basis of the priority claim claimed in the present application.
No.-96221 is incorporated herein by reference in its entirety.

[0033]

EXAMPLES Example 1: Preparation and evaluation of lignocellulosic composition (1) Preliminary experiment (1-1) Preparation of defatted sample Hinoki (Chamaecyparis obtusa) and beech (Fabus cren)
ata) wood powder was pulverized in a vibration mill (HEIKO Seisakusho TI-50) and passed through an 80 mesh sieve (IIDA Seisakusho) to obtain 80 mesh pass wood flour. After extracting the wood flour with ethanol: benzene = 1: 2 for 48 hours, the solvent was completely distilled off in a fume hood to obtain a test sample. (1-2) Measurement of moisture content of defatted sample 1 g of the defatted sample was precisely weighed in a weighing bottle of known constant weight, the absolute dry wood flour weight was measured with a blow dryer (105 ° C), and the air-dried wood before drying was measured. The water content was determined from the difference from the powder weight and used for the correction calculation.

(1-3) Measurement of lignin content of defatted sample (Klason method) 1 g of defatted sample was precisely weighed in a 100 ml beaker,
15 mL of 72% sulfuric acid was added little by little with a glass rod, and the mixture was reacted at 20 ° C. for 4 hours with sufficient stirring in a 20 ° C. water bath so that the reaction proceeded uniformly. After the reaction, the mixture was quantitatively transferred to a 1000 mL Erlenmeyer flask previously marked with 575 ml, and diluted with deionized water to a sulfuric acid concentration of 3%. The diluted treatment was heated and boiled for 2 hours with occasional addition of deionized water without a Liebig condenser to keep the sulfuric acid concentration at 3%. After the treatment, the content is filtered using a constant weight known 1G4 glass filter,
The insoluble material was washed with hot water, dried at 105 ° C., and the constant weight was measured (acid-insoluble lignin). If the filtrate is hardwood,
After diluting 10-fold with 3% sulfuric acid, JASCO UV-
The absorbance at 205 nm was measured at 520 to determine the amount of acid-soluble lignin.

<Method of calculating acid-soluble lignin> B = A / (110 × D) Lignin (%) = (B × V × 100) / (1000 ×
W) D: dilution ratio, W: sample weight, V: total filtrate volume, A: absorbance

(2) Phosphoric acid phase separation treatment (2-1) Sorption of phenol derivative Take 23 g of defatted wood powder in a 500 ml beaker, and add various phenol derivatives (p-cresol, 2,6-xylenol, 2,4 -Xylenol, 2-methoxyphenol (Guaiacol), 2,6-dimethoxyphenol, catechol, resorcinol, homocatechol, pyrogallol and phloroglucinol) in acetone (lignin C)
The mixture was stirred with a glass rod, the beaker was covered with aluminum foil and parafilm, and allowed to stand for 24 hours. afterwards,
Wood flour was vigorously stirred in the fume hood, and acetone was distilled off.

(2-2) Phosphoric acid treatment (phase separation treatment) 200 ml of 95% phosphoric acid was added to the phenol derivative sorptive wood flour.
(50 ° C.) was added in three portions, kneaded with a glass rod and a Teflon (registered trademark) spatula, and vigorously stirred at 50 ° C. for 1 hour. Thereafter, the reaction product was poured into about 3500 ml of deionized water to adjust the phosphoric acid concentration to 10% or less, the reaction was stopped, and the mixture was vigorously stirred for 1 hour with a stirrer to disperse the reaction product. Next, centrifugation (8800
rpm, 8 minutes, 4 ° C), the insoluble fraction was recovered, deacidified, freeze-dried and dried under reduced pressure to obtain a phase-separated wood powder.
The sample thus obtained is a composition (hereinafter also referred to as a lignocellulosic composition) containing a lignophenol derivative and a cellulose component uniformly.

(2-3) Fractionation of Phosphoric Acid Phase Separation-treated Wood Flour Hereinafter, the characteristics of the lignophenol derivative in the composition containing the lignophenol derivative and the cellulose component obtained in 2-2 uniformly are examined. For the purpose of, the lignophenol derivative was separated from the cellulose component. First,
(2-2) Phosphate-treated wood flour 8 obtained by phosphoric acid treatment
10 g was placed in a 300 ml Erlenmeyer flask, and acetone 2 was added.
Then, the mixture was sealed, and vigorously stirred with a stirrer for 24 hours. Then, centrifugation (3500 rpm, 5
And 5 ° C) and filtration (Whatman GF / A). The same operation was performed on the insoluble fraction to perform a second acetone extraction. After the solvent was distilled off, the residue was dried under reduced pressure over diphosphorus pentoxide.
The soluble fraction was concentrated to 20 ml with a rotary evaporator, and then vigorously stirred in a large excess of diethyl ether (diethyl ether 400 in a 500 ml Erlenmeyer flask).
ml), and the flocculent sediment was centrifuged (3500
rpm, 5 minutes, 5 ° C), and
After washing twice and distilling off the solvent, the residue was dried under reduced pressure over phosphorus pentoxide.

(2-4) Acetylation treatment Lignin sample (acetone soluble-ether insoluble fraction) 10
0 mg was placed in a 5 ml vial, 1 ml of pyridine was added, and the lignin sample was completely dissolved.
1 was added and left at room temperature for 48 hours. Thereafter, the reaction product was added dropwise to 40 ml of cold water, and the insoluble fraction was centrifuged (35
(00 rpm, 10 minutes, 5 ° C.), washed with cold water, freeze-dried and dried under reduced pressure.

(3) Physical Property Test and Structural Analysis of Material (3-1) Thermomechanical Analysis (TMA) In thermomechanical analysis, the phase transition point and the softening rate of the converted material were measured. The sample was placed in an aluminum van, a load was applied vertically downward, heat was applied to a predetermined temperature at a constant heating rate, and the displacement of the sample at that time was plotted. Measurement is Thermo
The measurement was performed using Plus TMA (8310) (manufactured by Rigaku Denki Co., Ltd.) under the following conditions. Sample weight: 5 mg Aluminum van: 5 mm diameter x 2.5 mm TMA load: 5.00 g Heating rate: 2 ° C / min Finish temperature: 250 ° C

(3-2) Measurement of Molecular Weight of Lignophenol Derivative by Gel Filtration Chromatography (GPC) In order to remove stabilizers and impurities, about 2 ml of rectified and degassed tetrahydrofuran (THF) and about 4 ml of lignophenol derivative 1 mg was added to the test tube, stirred with a touch mixer, and completely dissolved. Thereafter, one drop of a diluted p-cresol / THF solution was added as an internal standard substance, and the mixture was again stirred with a touch mixer to completely homogenize. The measurement is
The test was performed using SHIMADZU LC10 under the following conditions. Column: Shodex FK804, 803, 802, 801 Solvent: THF Flow rate: 1 ml / min Pressure: 28 to 30 kg / cm ² Detector: UV (280) Range: 0.32 Sample amount: 150 μl The calibration curve is polystyrene 390000 as a reference substance. , 2
33000, 100000, 25000, 9000, 4
000, 2200, 760, 474, 390, 266,
Prepared using bisphenol A and p-cresol.

(4) Results (4-1) Yield of lignocellulose mixture after treatment with various phenol derivatives / 95% phosphoric acid After sorption of phenol derivative and 95% phosphoric acid treatment (phase separation treatment) The yield of the lignocellulose mixture is shown in Table 1 below.

[0043]

[Table 1]

(4-2) Various phenol derivatives / 95%
Yield of acetone-soluble diethyl ether-insoluble fraction after treatment with phosphoric acid Various yields of acetone-soluble diethyl ether-insoluble fraction after treatment with various phenol derivatives / 95% phosphoric acid are shown in the following table. 2 and Table 3.

[0045]

[Table 2]

[0046]

[Table 3]

(4-3) Various phenol derivatives / 95%
Properties of acetone-soluble diethyl ether insoluble fraction after treatment with phosphoric acid Table 4 shows the average molecular weight of acetone-soluble diethyl ether insoluble fraction after treatment with various phenol derivatives / 95% phosphoric acid. Shown in GP used to calculate molecular weight
The measurement results of C are shown in FIG. 1 (hinoki) and FIG. 2 (beech).

[0048]

[Table 4]

(4-4) Yield of acetone-soluble diethyl ether-insoluble fraction after acetyl treatment The yield of acetone-soluble diethyl ether-insoluble fraction after acetyl treatment is shown in Table 5 below.

[0050]

[Table 5]

(4-5) Results of thermomechanical analysis (TMA) Various phenol derivatives / 95% phosphoric acid-treated lignocellulose, acetone-soluble diethyl ether-insoluble fraction, and acetone-soluble diethyl ether-insoluble fraction after acetylation 3 to 5 show TMA curve measurement results. TMA pattern of lignocellulose mixture after sorption of phenol derivative and 95% phosphoric acid treatment (phase separation treatment)
A phase transition point was observed in a temperature range of 50 to 200 ° C. These phase transition points are consistent with the phase transition points of the lignophenol fraction extracted from the phase-separated sample, and the lignophenol derivative is the plasticizer of the whole converter (lignocellulose mixture treated with the phenol derivative and phosphoric acid). It is shown that it has made an important contribution to the development.

Example 2 Preparation and Evaluation of Molded Article Consisting of Lignocellulosic Composition (1) Phosphoric acid treatme
nt) To 1 g of the defatted sample, an acetone solution of various phenol derivatives (p-cresol, guaiacol, catechol, or phloroglucinol) in an amount of 3 mol per ₉ units of lignin C was added, and after immersion, acetone was completely distilled off with stirring. Then, a uniform sorption sample was prepared. Add 10 ml of 95% phosphoric acid to the sorption sample,
After stirring vigorously at 0 ° C for 1 hour, the mixture is poured into a large excess of water, and the insoluble fraction is centrifuged (8800 rpm, 8 minutes, 5 ° C)
, And then lyophilized to obtain a lignocellulosic composite sample.

(2) Acetylation 7 g of a lignocellulose-based composite sample was dispersed in 70 ml of pyridine, 70 ml of acetic anhydride was added, and the mixture was reacted for 96 hours with stirring. After the reaction, the mixture was dropped into 3 L of 5 ° C. cold water, and the insoluble fraction was collected by centrifugation (8800 rpm, 8 minutes, 5 ° C.), washed with 5 ° C. cold water, and freeze-dried.

(3) Hydroxymethylation treatment (Hydroxymethy
lation) Add 140 ml of 0.5N NaOH to 7 g of the lignocellulose composite sample.
After stirring and dispersing for about 30 minutes, transfer to a 1 L three-necked flask.
And diluted 5 times with stirring. Install a reflux pipe and
37% formaldehyde solution (lignopheno
80mol / C ₉Times) and add 3 at 60 ° C in a hot water bath.
Allowed to react for hours. After the reaction, the mixture was acidified to pH 2 with 1N HCl.
And the resulting precipitate is centrifuged (8800 r.p.m., 10 min, 5
C), freeze-dried after deacidification. The obtained methylo
The cured product was stored at -80 ° C.

(4) Molding Method (Molding) A lignocellulose-based composite sample (original) and its acetylated product and methylolated product (500 mg) were each molded into a molding machine.
(10mm diameter), pre-forming, SHIMADZU flow tester CFT-5
It was placed in a 00D heated compression cylinder (10 mm diameter) and molded under the following molding conditions.

[0056]

[Table 6]

(5) Various tests (Test) Water absorption test Various lignocellulose-based composite molded bodies were placed on a stainless steel net and submerged in a container filled with water to a depth of 3 cm from the bottom of the molded body. When the molded body floated, a stainless steel net was placed 1-2 mm above the upper surface of the molded body to suppress further floating. After immersion in water at room temperature for 60 minutes, the molded body was taken out and rolled on a filter paper to quickly remove the moisture on the surface. Dry at 60 ° C. for 3 days. At that time, before water absorption,
After water absorption, measure the weight and dimensions after drying, and calculate
Using (1) and (2), the water absorption Aw% and the volume expansion coefficient Vol% were determined.

Aw% = (Wt′−Wt) / Wt × 100 (1) Vol% = (Vol′−Vol) / Vol × 100 (2) Aw%: water absorption (% to sample weight) Wt: sample weight (g) Wt ': Sample weight after water absorption test (g) Vol%: Volume expansion (% to sample volume) Vol: Sample volume (cm ³ ) Vol': After water absorption test (wet column in the table below) or Sample volume after re-drying (dry column in the table below) (cm ³ )

Hardness test (Brinell Hardness) The hardness test was carried out using SHIMADZU AG-1 10 kN according to JIS2117. 10mm diameter at the center of the upper surface of various lignocellulosic composite moldings
The hard sphere is pressed in at a speed of 0.5 mm / min, and the hard sphere is 1 / πmm = 0.32 m
The load P (N) required to indent to a depth of m was measured, and the hardness H _B (MPa) was measured using the following equation (3). H _B = P / 10 (3) H _B : Brinell hardness (MPa) P: Load (N)

(6) Results The results are shown in the following table.

[0061]

[Table 7]

[0062]

According to the present invention, it is possible to provide a novel composition capable of repeatedly and effectively utilizing both lignin and cellulose, which are components of the lignocellulose complex structure of forest resources, and to effectively use forest resources. It can be used. Further, according to the present invention, the lignin component can be recovered as a lignophenol derivative from the composition, and the lignin component of forest resources can be effectively used.

[Brief description of the drawings]

FIG. 1 shows the results of GPC measurement (hinoki) used for calculating the molecular weight. In FIG. 1, (1) is a ligno-
2,6-xylenol, (2) ligno-2,4-xylenol, (3) ligno-catechol, (4) ligno-homocatechol, (5) ligno-pyrogallol and (6) ligno-flow Shows loglucinol.

FIG. 2 shows GPC measurement results (beech) used for calculating a molecular weight. In FIG. 1, (1) is a ligno-
2,6-xylenol, (2) ligno-2,4-xylenol, (3) ligno-catechol, (4) ligno-homocatechol, (5) ligno-pyrogallol and (6) ligno-flow Shows loglucinol.

FIG. 3 shows measurement results of TMA curves of various phenol derivatives / 95% phosphoric acid-treated lignocellulose.
In FIG. 3, (1) is ligno-2,6-xylenol, (2) is ligno-2,4-xylenol, (3) is ligno-catechol, (4) is ligno-homocatechol, and (5) is ligno. -Pyrogallol and (6) indicate ligno-phloroglucinol.

FIG. 4 shows a measurement result of a TMA curve of an acetone-soluble diethyl ether-insoluble fraction. In FIG.
(1) Ligno-2,6-xylenol, (2) Ligno-2,4-xylenol, (3) Ligno-catechol, (4) Ligno-homocatechol, (5) Ligno-pyrogallol and ( 6) shows ligno-phloroglucinol.

FIG. 5 shows a measurement result of a TMA curve of an acetone-soluble diethyl ether-insoluble fraction after acetylation. FIG.
Wherein (1) is ligno-2,6-xylenol,
(2) Ligno-2,4-xylenol, (3) Ligno-catechol, (4) Ligno-homocatechol,
(5) shows ligno-pyrogallol and (6) shows ligno-phloroglucinol.

Continued on the front page F term (reference) 4C090 AA05 BA24 CA47 DA31 4F071 AA09 AA73 AH01 AH04 AH05 AH19 BC01 BC04 BC07 4J002 AB00X AH00W GB00 GG01 GG02 GK00

Claims (11)

[Claims] 1. A lignocellulosic composition comprising a lignophenol derivative and a cellulose component, which is obtained by adding an acid to a lignocellulosic substance to which a phenol derivative has been added and mixing. 2. The lignocellulosic composition according to claim 1, wherein the lignophenol derivative component and the cellulose component form a homogeneous system. 3. The lignocellulosic composition according to claim 1, wherein an acid having an action of swelling cellulose and having a low action of hydrolyzing cellulose is used as the acid. 4. The lignocellulosic composition according to claim 1, wherein the acid is phosphoric acid, formic acid or trifluoroacetic acid. 5. The phenol derivative added to the lignocellulosic substance is a phenol derivative having one or more substituents at the ortho and / or para positions.
5. The lignocellulosic composition according to any one of items 1 to 4. 6. The phenol derivative added to the lignocellulose-based material is a phenol derivative having at least one substituent selected from a lower alkyl group, a lower alkoxy group and a hydroxyl group at an ortho position and / or a para position. The lignocellulosic composition according to any one of claims 1 to 5. 7. Consisting of p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol (Guaiacol), 2,6-dimethoxyphenol, catechol, resorcinol, homocatechol, pyrogallol and phloroglucinol. 95% in lignocellulosic material added phenol derivative selected from group
A lignocellulosic composition comprising a lignophenol derivative and a cellulose component, obtained by adding and mixing phosphoric acid. 8. The lignocellulosic composition according to claim 1, wherein the lignophenol derivative is acylated or methylolated. 9. The lignocellulosic composition according to claim 1, which is a plasticized material. 10. A molded article comprising the lignocellulosic composition according to any one of claims 1 to 9. 11. The method according to claim 1, further comprising a step of adding an acid to a mixture obtained by treating the lignocellulosic substance with a phenol derivative to solvate the lignin component with the phenol derivative and mixing the mixture. The method for producing a lignocellulose composition according to any one of claims 1 to 7.