WO2004031298A1 - Glass composite material having lignin matrix - Google Patents

Abstract

A composite material comprising a lignin polymer and glass material wherein the lignin polymer is selected from the group consisting of lignophenol derivatives having 1,1-bis(aryl)- propane units which are formed by bonding the carbon atom of a phenol at a position ortho to the phenolic hydroxyl group to the C1-position carbon atom of arylpropane unit of lignin; secondary or higher derivatives obtained by subjecting the above derivatives to one or two reactions selected from among hydroxyl-blocking treatment, alkali treatment, and introduction of crosslinking groups; and polymers prepared by crosslinking the secondary or higher derivatives obtained through the introduction of crosslinking groups. The invention further provides both a technique of compounding a component resulting from lignin with glass material and a technique of separating the glass composite material into constituents and recovering them.

Description

 Description Glass composite material with lignin matrix

 The present invention relates to a lignophenol derivative derived from lignin, a secondary derivative thereof, and a composite material using a higher derivative as a matrix. More specifically, the present invention relates to a composite material in which a lignophenol derivative and / or a secondary derivative thereof are used as a matrix and a glass material is combined. In addition, the present invention relates to a compounding technique capable of decomposing the derivative by subjecting the derivative to a structural change by physicochemical treatment. Background art

 Many artificial structures include composite materials such as fiber reinforced plastics and reinforced concrete that retain filler as a reinforcing material in the matrix.However, artificial composite materials are pursued with priority on functions such as strength. . For this reason, at the present time, there is no consideration given to a method of rationally disassembling the composite matrix and the dispersing material, or use in the next stage at the time of composite formation. Therefore, once these artificial structures are constructed and become useless, they cannot be decomposed into their respective materials, and are either discarded as they are or are crushed and used for aggregates and roadbed materials. , There is almost no way to reuse.

On the other hand, typical composite materials in nature include plant cell walls. The plant cell wall expresses high physical strength and durability by forming a strong composite structure of cellulose and lignin. In other words, on the cell wall of the plant, there is a cellulose resin The fibrils are entangled in different orientations to form a skeleton, and the skeleton has a complex structure in which lignin, which is a hydrophobic network polymer, is filled. In addition, hemicellulose exists so as to cover the cellulose skeleton, enhancing affinity with lignin and contributing to toughening of the composite structure. The lignocellulosic composite structure in a plant maintains its composite state for a long period of time, and once returned to the soil, the composite state is easily released by microorganisms in the ground and flows into the natural carbon cycle. be able to.

 In other words, the lignocell-orbital complex is an important and enormous carbon resource that plays a role in regulating the global carbon supply balance. Therefore, when considering the use of this complex, it is important to utilize cellulose and lignin in the long term to maintain the carbon supply balance.

 To date, there are various uses of lignocellulosic composites, but they are often used in combination with other materials as molding materials such as fibers and chips in addition to woodwork. From a functional viewpoint of the molded body, these molding materials are combined with a thermosetting resin to form a molded body. However, the use of thermosetting resin makes it difficult to separate fibers and chips at the time of disposal, and as a result, it is difficult to reuse lignocellulosic resources.

 On the other hand, the cellulose in the lignocellulosic composite has been reused by repeating fiberization and sheeting. However, lignin separated at the same time is mainly consumed as fuel, and only part of it is reused for limited uses.

The present inventors have made studies based on the swelling of carbohydrates by concentrated acids. The lignocellulosic material is a phenolic compound of carbohydrates and lignin (hereinafter referred to as a lignophenol derivative) while suppressing the inactivation of lignin by combining the destruction of the resulting tissue structure with the solvation of lignin with a phenolic compound. (See, for example, Japanese Patent Application Laid-Open No. H2-233071). As a method of utilizing the lignophenol derivative obtained by this method, for example, it has been reported to apply it to a molding material such as a cellulosic fiber to produce a molded article (Japanese Patent Application Laid-Open No. Hei 9-279890). No. 4). Such a lignophenol derivative is a lignin-based polymer having 1,11-bis (aryl) propane as a high-frequency constituent unit, and has been found to potentially have high caking properties (Japanese Patent Laid-Open No. No. 9 _ 27 8 904).

 Further, such a lignophenol derivative can impart crosslinkability by being converted to methylol, and can form a linear or network-like crosslinked structure, and at the same time, is again reduced in molecular weight and dissolved in a solvent by alkali treatment. This has also been found by the present inventors (Japanese Unexamined Patent Publication No. 2001-26189). Disclosure of the invention

However, to date, an artificial composite material has been formed using the lignin-derived section of the lignocellulose complex as a matrix, and the composite structure has been released based on the structural transformation of the lignin-derived section. Decomposition has not been found at all. Also, there is no known information about the sequential use of the lignin-derived category through the process of decomposing a complex state by this structural transformation. Also, no attempt has been made to combine a glass material that does not exhibit any cohesive properties with a lignin-derived category. Therefore, an object of the present invention is to provide a technique for combining a lignin-derived section with a glass material and a technique for decomposing the composite material once obtained.

 The present inventors have found that when the lignophenol derivative and its further derivatives have specific units, the glass material can be well constrained to form a matrix of the composite material, and at the same time, the depolymerization and structural transformation based on the presence of this unit. As a result, they found that the glassy composite material was decomposed, and completed the present invention.

 That is, according to the present invention, the following means are provided.

 A composite material having a lignin-based matrix,

 This lignin matrix is

 The following (a) to (e):

 (a) a carbon atom ortho to the phenolic hydroxyl group of the phenolic compound,

A lignophenol derivative having a first 1,1-bis (aryl) propane unit bonded to the carbon atom at the C 1 position of aryl propanenit of lignin

 (b) a lignophenol derivative obtained by subjecting the lignophenol derivative to one kind of reaction selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit; Secondary derivative

 (c) The lignophenol derivative is obtained by performing at least two kinds of reactions selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit. Secondary derivatives,

 (d) a cross-linked derivative of a secondary derivative in which a secondary derivative obtained by a cross-linkable group introduction reaction among the secondary derivatives is cross-linked, and

(e) Among the higher derivatives, higher derivatives obtained through a crosslinkable group introduction reaction Crosslinked product of higher derivative with crosslinked conductor

One or more lignin polymers selected from the group consisting of

 Glass material,

And a composite material comprising:

Further, the (a) lignophenol derivative is a lignocellulose-based material to which one or more phenol compounds containing at least one phenol compound in which at least one ortho position to a phenolic hydroxyl group is not substituted are added to an acid. ₍ A preferred form in the present composite material is that the phenolic compound preferably has a substituent at the para-position and the remaining ortho-position is not substituted. Is more preferably a p-resol. In another preferred embodiment of the present composite material, the phenol compound preferably has a substituent at the para position and the remaining ortho position. The phenolic compound is, furthermore, the phenolic compound is 2,4-dimethylphenol Door is preferable.

 In still another preferred embodiment of the composite material of the present invention, the phenol compound includes a phenol compound having a substituent at the para-position and the remaining ortho position not substituted, and a para-position and a remaining ortho position. This is a form including a phenol compound having a substituent. More preferably, the phenolic compounds are p-cresol and 2,4-dimethylphenol.

In this composite material, the lignophenol derivative had the carbon atom para to the phenolic hydroxyl group of the phenol compound bonded to the carbon atom at the C1 position of aryl propaneunitite of lignin. It is preferable to have a second 1,1-vis (aryl) propane unit. In a preferred form of the composite material, the lignophenol derivative is a phenolic compound. A form obtained by contacting a lignocellulose-based material to which a phenol compound containing at least one phenol compound not substituted at the ortho position with respect to the hydroxyl group and a phenol compound not substituted at least at the para position with an acid It is. In these, the phenolic compound constituting the second unit preferably has substituents at two ortho positions, and more preferably, each phenolic compound is 2,6-dimethylphenol. is there.

 The composite material preferably contains a non-swellable inorganic material, and preferably contains an alkali-swellable organic material. Cellulose-based materials are preferable as the organic material that can be swollen by force. The present invention relates to a method for producing a composite material having a lignin-based matrix,

 The following (a) to (c):

 (a) The first 1,1-bis (aryl) propane unit in which the carbon atom ortho to the phenolic hydroxyl group of the phenolic compound is bonded to the carbon atom at position C1 of the aryl propane unit of lignin Lignophenol derivative having

 (b) a lignophenol derivative obtained by subjecting the lignophenol derivative to one kind of reaction selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit; Secondary derivatives, and

 (c) a higher-order lignophenol derivative obtained by subjecting the lignophenol derivative to two or more reactions selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit. Derivative

One or more lignin polymers selected from the group consisting of

Glass material, Provided by a step of pressing and Z or heating to form a matrix composition containing the same.

 In the present production method, it is a preferred embodiment that the lignin-based matrix contains at least a lignin-based polymer that has undergone a cross-linkable group-introducing reaction as a constituent material, and is crosslinked during the molding step. The lignophenol derivative in the lignin-based polymer that has undergone the crosslinkable functional group introduction reaction is characterized in that the phenol compound constituting the first unit has a substituent at the para position and the remaining ortho position is substituted. It is a more preferred embodiment that the phenol compound is not substituted and / or has a substituent at the para position and the remaining ortho position.

 The present invention also provides a method for using a composite material molded article having a lignin-based matrix,

 The lignin-based matrix comprises one or two or more lignin-based polymers selected from the group consisting of (a) to (e), and a glass material;

And

 Contacting the molded body with an alkaline solution to separate the lignin-based polymer and the glass material;

 Recovering the lignin-based polymer and the glass material after the ally treatment,

A method is also provided.

The composite material of the present invention is characterized in that the first unit provided by the lidanophenol derivative, the secondary derivative, and the higher derivative in the polymer material is a low-molecular-weight compound formed by cross-linking the derivative of these derivatives. Structural transformation. This loosens or collapses the lignin-based matrix, and at the same time separates the other complexed material from the lignin-based matrix. As a result, the composite material is decomposed. Here, decompositing means loosening or at least partial collapse of the composite state of the composite material. Decompositing also means separating matrix constituent materials from the composite material to such an extent that at least partial recovery of the matrix constituent materials is possible. Further, the production method of the present invention provides a composite material that is easily decomposed. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a diagram showing that a primary derivative having a first unit can be obtained by a phase separation treatment on natural lignin having arylpropane nit.

 The upper part of Fig. 2 shows a prepolymer obtained by adding a crosslinkable group (HM group) to a primary derivative obtained by introducing 2,4-dimethylphenol as a phenol compound, and the lower part shows a crosslinked form of the prepolymer. It shows the state where it was done.

 FIG. 3 is a diagram showing a decomposing mechanism of the following derivative.

 FIG. 4 is a diagram showing a scheme in which various lignophenol derivatives are combined with an inorganic material.

 FIG. 5 is a diagram showing an embodiment of a crosslinked structure obtained in a matrix of a composite material.

 FIG. 6 is a diagram showing a decompositing mechanism in a crosslinked product.

 FIG. 7 is a table showing the weight, dimensions, density, and the like of the composite obtained in Example 3. FIG. 8 is a table showing the weight, dimensions, density, and the like of a composite using four types of glass materials.

 FIG. 9 is a view showing a test result of a Prinell hardness of the composite shown in FIG. FIG. 10 is a diagram showing the water absorption of the composite shown in FIG.

FIG. 11 is a diagram showing a volume expansion coefficient of the composite shown in FIG. FIG. 12 is a graph showing the recovery of a lignophenol derivative (alkali-treated product) after the complex shown in FIG. 8 is decomposed. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described in detail.

 The composite material of the present invention has a lignin-based matrix, and comprises, in the lignin-based matrix, one or more of the above-described lignin-based polymers (a) to (e) and a glass material. And

 Such a composite material can be obtained by molding the composition for a composite material containing the lignin-based polymer of the above (a), (b) and (c) by applying pressure and Z or heating. In particular, when these lignin-based polymers have been subjected to a crosslinkable group introduction reaction, under a predetermined heating condition, the composite having the matrix containing the lignin-based polymer of the above (d) and (e) is obtained. Material can be obtained.

 Hereinafter, the (matrix) composition for a composite material will be described, and then the finally obtained composite material and its use will be described.

 First, the lignin-based polymers (a), (b), and (c), which are components of the composite material composition of the present invention and components of the lignin-based matrix of the composite material, will be described.

 In the lignin polymer (a), the carbon atom ortho to the phenolic hydroxyl group of the phenol compound is bonded to the carbon atom at the benzyl position (position C1 in the side chain) of the phenylpropane unit of lignin. This is a lignophenol derivative with the first 1,1-bis (aryl) propane unit. The lignin-based polymers (b) and (c) can be obtained by further derivatizing the lignophenol derivative of (a).

In addition, these lignin polymers are phenol compounds of phenol. Includes lignophenol derivatives having a second 1,1-bis (aryl) propane unit with the carbon atom para to the hydroxyl group bonded to the carbon atom C1 of the arylpropane unit of lignin in _t these various lignin polymer that can be both have a first unit described above. In addition, in the above (d) and (e), which are crosslinked products of these lignin-based polymers, the introduced phenol compound in the first unit is retained. That is, in these lignin-based polymers, a structural site for decomposing the first unit, more specifically, the introduced phenol compound in the first unit (hereinafter referred to as a switching element in this specification) Alternatively, the polymer skeleton can be cleaved at this element site.

 Therefore, by using the lignin-based polymer of the above (a) to (e), it is possible to achieve both the complexation and the decomposition by the lignin-based matrix.

 On the other hand, the second unit, unlike the first unit, suppresses cleavage of the polymer skeleton at the site. That is, the introduced phenol compound in the second unit can be used as a structural site that restricts decomposition (hereinafter, also referred to as a second element in the present specification).

In the following description, a lignophenol derivative having a (-)-th unit, which is a lignin-based polymer of (a), is referred to as a primary derivative. This primary derivative and other secondary derivatives formed from this primary derivative are referred to as primary derivatives. The concept encompassing the above (b)) and the higher derivative (the above (c)) is referred to as a lignophenol derivative. In particular, when the type of derivative is not specified, it is described as a lignophenol derivative. When a particular reference is made to each derivative, the primary derivative, the secondary derivative and the higher derivative shall be described respectively. Cross-linking group introduction reaction is applied to secondary derivatives and higher derivatives. What has been introduced with a crosslinkable group is referred to as a crosslinkable body. Furthermore, the term “crosslinked product of lignophenol derivative” includes both the crosslinked product of the secondary derivative ((d) above) and the crosslinked product of the higher derivative ((e)). When it does not matter, it is referred to as a cross-linked product. When distinguishing between a cross-linked product of a secondary derivative and a cross-linked product of a higher-order derivative, it is referred to as a secondary cross-linked product or a higher cross-linked product, respectively.

 (Lignophenol derivative)

 (Primary derivative)

 The primary derivative can usually be obtained by contacting a lignin-containing material, preferably a lignocellulosic material, which has been affinityd by a predetermined phenolic compound, with an acid. A more general description of the lignophenol derivative and a production process thereof have already been described in Japanese Patent Application Laid-Open Nos. 2-23701, 9-279894, and International Publication W-9. No. 9/142, No. 2, No. 201-644 94, No. 201-266 No. 1, No. 201, No. 201, No. 1, No. 1, No. 1, No. 1, No. 200 No. 1-343233 (the contents of these patent documents are entirely incorporated herein by reference).

 Hereinafter, this manufacturing process will be described.

In this production process, the lignocellulose-based material is solvated with a phenolic compound in advance, or the phenolic compound is adsorbed on the lignocellulose-based material, and then the lignocellulose-based material is brought into contact with an acid to form a lignocellulose composite. At the same time, the phenolic compound is selectively grafted to the C 1 position (benzyl position) of the arylpropane unit of natural lignin, thereby producing a lignophenol derivative. Is a method that can be separated into lignophenol derivatives and lignophenol derivatives. It means a polymer containing a 1,1-bis (aryl) propane unit in which a phenol compound is introduced at the C 1 position via a C—C bond. The lignophenol derivative itself is a mixture of a lignin-derived polymer obtained by reacting and separating from a lignocellulosic material, and the amount and molecular weight of the introduced phenol compound in the obtained polymer is determined by the amount of the starting ligno compound. It varies depending on the cellulosic material and reaction conditions.

 The term "lignocellulosic material" used in the present invention refers to wood-based materials, various materials that are mainly wood, such as wood flour and chips, as well as agricultural waste associated with wood resources such as waste materials, offcuts, and waste paper. And industrial waste. As the type of wood to be used, any type of wood such as conifers and hardwoods can be used. In addition, various herbaceous plants and related agricultural and industrial wastes can be used.

 As the phenol compound for solvating the lignocellulose-based substance or sorbing the lignocellulose-based material, a monovalent phenol compound, a divalent phenol compound, a trivalent phenol compound, or the like can be used.

 Specific examples of the monovalent phenol compound include a phenol that may have one or more substituents, a naphthol that may have one or more substituents, and a phenol that may have one or more substituents. Examples include good anthrol and anthroquinone ol which may have one or more substituents.

 Specific examples of the divalent phenol compound include catechol optionally having one or more substituents, resorcinol optionally having one or more substituents, and one or more substituents. And hydroquinone.

Specific examples of the trivalent phenol compound include pyrogallol which may have one or more substituents. In the present invention, one or more of a monovalent phenol compound, a divalent phenol compound and a trivalent phenol compound can be used, but a monovalent phenol is preferably used.

 The type of the substituent which the monovalent to trivalent phenol compound may have is not particularly limited, and may have any substituent. Preferably, the electron-withdrawing group (halogen atom And the like, for example, a lower alkyl group-containing substituent having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. Examples of the lower alkyl group-containing substituent include a lower alkyl group (such as a methyl group, an ethyl group, and a propyl group) and a lower alkoxy group (such as a methoxy group, an ethoxy group, and a propoxy group). Further, it may have an aromatic substituent such as an aryl group (such as a phenyl group). Further, it may be a hydroxyl group-containing substituent.

 These phenol compounds are introduced into the phenylpropane unit by bonding the carbon atom at the ortho or para position to the phenolic hydroxyl group to the carbon atom at the C1 position of the phenylpropane unit of lignin. Will be entered. Therefore, in order to secure at least one introduction site, it is preferable that a substituent is not present in at least one of the ortho position and the para position.

 From the above, in the present invention, in addition to the unsubstituted phenol compound, one or more phenol compounds of various substituted forms having at least one unsubstituted ortho or para position are appropriately selected and used. That's a thing.

 In this process, by selecting the type of the phenol compound to be used, the frequency of introducing a crosslinkable functional group into the obtained primary derivative can be adjusted, and as a result, the crosslinking reactivity of the prepolymer can be controlled.

That is, the site of introduction of the crosslinkable group is ortho to the phenolic hydroxyl group. And para. The site at which the phenol of the introduced phenol is introduced into the phenylpropane unit is also at the ortho or para position with respect to the phenolic hydroxyl group. Therefore, the site and amount of introduction of the crosslinkable functional group into the introduced phenolic compound are controlled by the manner in which the substituents are introduced at the ortho and para positions (up to 3 sites) relative to the phenolic hydroxyl group in the introduced phenolic compound. In addition, the amount introduced into the lignin matrix can be controlled. For example, the substitution mode of the introduced phenol compound, the binding site to lignin, and the introduction site of the bridging group are as shown in the following table.

Induction of lignin phenol

 To be introduced: I; Nol derivative 1st 2nd ω 2 ュ ¾ 1H φ * A to Repropane の

 Embodiment of the substituent of the polymer form

 Presence or absence of an introduction site at the binding position

~ Yes ('Rig Yes (Rig

Ortho position (2 position, 6 nin to nin to nin, "to ¹ " unsubstituted position) or para (2 or more)

 (4th) is Orto is Para

 l for ¾ J for J

 Ortho position (there is second place

 Yes (one: para) Network

2nd or 6 Yes No

 Or 6th position) y position substitution

 1 substitution 4th position (para position) Yes (one: ortho position) No Yes Network Ortho position (2nd network

4-position substitution Yes (one: ortho position) Yes No

 No. 6) Type

2.4 Substitution 6th position (ortho position) No Yes No Linear! ¹ J

2 replacement

 2, 6 Substitution 4-position (para-position) No No Yes Linear type 1st unit: Carbon nuclear power ortho to phenolic hydroxyl group of phenol derivative

 The 1.1 bis (arylamine) attached to the carbon atom at position C1 of the side chain of the phenylpropane unit of nin

 Le) Propane unit

 Second unit: the carbon atom para to the phenolic hydroxyl group of the phenol derivative is rigged

 1, 1—bis (aryl amide) attached to the carbon atom at position C1 of the side chain of the phenylpropane unit of nin

 Le) Proper unit

When the bridging group is introduced, the site and number of the cross-linking group can be controlled, and as a result, the cross-linking density of the cross-linked product obtained by cross-linking the cross-linking product can also be controlled.

 In order to obtain a primary derivative having the first unit, a phenol compound having no substituent at at least one ortho position (preferably, all ortho positions) is used. In addition, a phenol compound having at least one ortho-position (position 2 or 6) having no substituent and having a substituent at the para-position (position 4) (typically, a 2- or 4-position substitution) A monovalent phenol compound is preferred. Most preferably, it is a phenol compound having no substituent at all ortho positions and having a substituent at the para position (typically a 4-substituted monovalent phenol compound). Therefore, the 4-substituted phenol compound and the 2,4-substituted phenol compound can be used alone or in combination of two or more.

 In order to obtain a primary derivative having a second unit, a phenol compound having no substituent at the para position (typically, a monovalent phenol compound substituted at the 2-position (or 6-position)) is preferable, and more preferably At the same time, a phenol derivative (typically a 2,6-substituted monovalent phenol compound) having a substituent at the ortho position (preferably all ortho positions) is used. That is, it is preferable to use one or a combination of two or more of the 2-position (or 6-position) substituted phenol compound and the 2- or 6-position substituted phenol. Preferred specific examples of the phenol compound include p-cresol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, resorcinol , Homocatechol, pyrogallol, and phloroglucinol.

In particular, to build the first unit in a lidanophenol compound, p-Cresol and / or 2,4-dimethylphenol can be used. To build the second unit, 2,6-dimethylphenol can be used.

 The acid added to the lignocellulosic material is not particularly limited, but preferably has an action of swelling the cell opening. For example, 65% by weight or more of sulfuric acid (preferably, 72% by weight of sulfuric acid), 85% by weight or more of phosphoric acid, 38% by weight or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid Mouth acetic acid, formic acid and the like can be mentioned. Preferred acids are 65% or more (more preferably 72% or more) sulfuric acid, 85% or more (more preferably 95% or more) phosphoric acid, trifluoroacetic acid, or formic acid. In order to efficiently recover water-soluble polysaccharides, oligosaccharides and monosaccharides derived from cellulose and micelles, it is preferable to use sulfuric acid. It is preferable to use an acid having a low acid strength such as phosphoric acid.

 The following three methods can be used to convert lignin in a lignocellulosic material into a lignophenol derivative and separate it. In addition, it is not limited to these methods.

The first method is a method described in Japanese Patent Application Laid-Open No. H2-233701. In this method, a phenolic compound in liquid form (for example, p-cresol or 2,4-dimethylphenol) is infiltrated into a lignocellulosic material such as wood flour, and lignin is converted into a solvent by the phenolic compound. Then, a concentrated acid (as described above, for example, 72% sulfuric acid) is added to the lignocellulosic material and mixed to dissolve the cellulose component. According to this method, a phenol compound obtained by solvating lignin and a concentrated acid obtained by dissolving a cellulose component form a two-phase separation system. Lignin solvated with a phenolic compound has a phenolic compound phase Only at the contacting interface is the acid contacted and the reaction takes place. That is, the cation at the side chain C 1 position (benzyl position), which is a highly reactive site of the basic lignin structural unit generated by interfacial contact with an acid, is attacked by the phenol compound. As a result, the phenol compound is introduced into the C 1 position via a C—C bond, and the benzyl compound is cleaved to reduce the molecular weight. As a result, lignin is reduced in molecular weight, and at the same time, a lignophenol derivative in which a phenol compound is introduced at the C 1 position of the basic structural unit is formed in the phenol compound phase. From this phenolic compound phase, the lidanophenol derivative is extracted. The primary derivative is obtained as an aggregate of low molecular weight lignins in which the benzyl aryl ether bond in the lignin has been cleaved to reduce the molecular weight. It is known that some phenolic compounds are introduced into the benzyl position via the phenolic hydroxyl group.

 FIG. 1 shows that a primary derivative having the first unit in the present invention can be obtained by performing a phase separation treatment on natural lignin having arylpropane unit.

 The extraction of the primary derivative from the phenol compound phase can be performed, for example, by the following method. That is, the phenolic compound phase is added to a large excess of ethyl ether, and the resulting precipitate is collected and dissolved in acetone. Remove the acetone-insoluble part by centrifugation and concentrate the acetone-soluble part. The acetone-soluble part is dropped into a large excess of ethyl ether, and the sedimentation fraction is collected. The primary derivative is obtained by distilling off the solvent from this precipitation section. The crude primary derivative can be obtained by simply removing the acetone-soluble part by distillation under reduced pressure.

The second and third methods involve adding a solid or liquid phenolic compound (eg, p-cresol or 2,4-diene) to a lignocellulosic material. After infiltration with a solvent (eg, ethanol or acetone) in which methylphenol is dissolved, the solvent is distilled off (the sorption step of the phenol compound). Next, a concentrated 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 phenolic compound was converted into a cation at the highly reactive site (side chain C 1 position) of the lignin generated by contact with the concentrated acid. When attacked, phenolic compounds are introduced. In addition, the benzyl aryl ether bond is cleaved to lower the molecular weight of lignin. The properties of the obtained primary derivative are the same as those obtained by the first method. Then, in the same manner as in the first method, the lignophenol compound converted to a phenol compound is converted into a liquid phenol compound.

-Extract with the compound. The extraction of the primary derivative from the liquid phenolic compound phase can be performed in the same manner as in the first method (this is referred to as the second method). Alternatively, the entire reaction mixture after the concentrated acid treatment is poured into excess water, the insoluble fraction is collected by centrifugation, deoxidized, and dried. Acetone or alcohol is added to the dried product to extract a lignophenol derivative. Further, similarly to the first method, the soluble fraction is dropped into excess ethyl ether or the like to obtain a primary derivative as an insoluble fraction (this is referred to as a third method). The specific examples of the method for preparing the lignophenol derivative have been described above. However, the present invention is not limited thereto, and the derivative can be prepared by appropriately improving these methods.

Thus, in addition to having at least the first unit, the phenolic compound used was grafted at the C-position of the phenylpropane unit of lignin at the ortho or para position of the phenolic compound used. A primary derivative having a bis (aryl) propane unit can be obtained. In addition, in the obtained primary derivative, usually, arylpropane unit in which phenol is not graphed also remains. FIG. 1 schematically shows the generation of a primary derivative having a first unit from lignin (having an arylpropane unit).

 The frequency of introduction of the phenol compound varies depending on the presence, position, size, etc. of the substituent of the phenol compound to be introduced. Therefore, the frequency of introduction can be adjusted. In particular, the frequency of introduction can be easily adjusted by steric hindrance due to the size of the substituent. When controlling the position of introduction using a substituent, if a lower alkyl group is used as the substituent, the introduction frequency can be easily adjusted depending on the number of carbon atoms and the branched form. When the substituent is a methyl group, the introduction position can be controlled while maintaining a high introduction frequency.

 The general and general properties of the primary derivative obtained from the lignocellulosic material are described below. However, there is no intent to limit the lignophenol derivative in the present invention to those having the following properties.

 (1) The weight average molecular weight is about 2000 to 2000.

 (2) It has almost no conjugated system in the molecule and its color tone is extremely pale. Typically, it is a pale pinkish white powder.

 (3) Approximately 170 ° (derived from conifers, has a solid-liquid phase transition point at approximately 130 ° C derived from hardwoods.

(4) Easily soluble in methanol, ethanol, acetone, dioxane, pyridine, tetrahydrofuran, dimethylformamide, etc. By subjecting the primary derivative to an alkali treatment, a cross-linking introduction reaction, a hydroxyl group protection treatment, or the like, a further derivative (secondary derivative) of the primary derivative can be obtained. That is, an alkali-treated product and a crosslinkable product (prepolymer) are obtained, and a hydroxyl-protected product can be obtained. Further, a higher derivative can be obtained by further performing a different derivatization treatment on the secondary derivative subjected to any of the derivatization treatments. The lignophenol derivative inherently has caking properties, and when used as a constituent material of a lignin-based matrix, a glass material that does not have collective properties by itself is satisfactorily restrained to form a composite lignin. A system matrix can be constructed.

 Hereinafter, the secondary derivative and the derivatization step will be described.

 (Crosslinkable group introduction reaction)

 Prevolimer is obtained by reacting a primary derivative with a compound capable of forming a crosslinkable group under alkaline conditions to introduce a crosslinkable group at the ortho-position and / or para-position of the phenolic hydroxyl group in the lignophenol derivative. be able to.

 That is, the prepolymer is obtained by mixing a primary derivative with a compound capable of forming a crosslinkable group and reacting the primary derivative in a state where the phenolic hydroxyl group of the primary derivative can be dissociated. The state in which the phenolic hydroxyl group of the primary derivative can be dissociated is usually formed in an appropriate alkaline solution. The kind, concentration and solvent of the alkali used are not particularly limited as long as the phenolic hydroxyl group of the primary derivative can be dissociated. For example, a 0.1 N aqueous solution of sodium hydroxide can be used.

Under such conditions, the crosslinkable group is introduced at the ortho or para position of the phenolic hydroxyl group. Therefore, the introduction position of the crosslinkable group is roughly determined by the type and combination of the phenol compound used. That is, when di-substituted at the ortho and para positions, the crosslinkable group is not introduced into the introduced phenol nucleus, but is introduced into the phenolic aromatic nucleus on the lignin host side. Since the phenolic aromatic nucleus on the mother side is mainly present at the polymer terminal of the primary derivative, a prepolymer having a crosslinkable group introduced mainly at one terminal of the polymer is obtained. Figure 2 shows the primary derivative obtained using 2,4-dimethylphenol as the introduced phenolic compound. In (1), a prepolymer having a hydroxymethyl group introduced as a crosslinkable group (methylolated) is exemplified.

 When the substitution is 1 or less at the ortho and para positions, a crosslinkable group is introduced into the introduced phenol nucleus and the phenolic aromatic nucleus of the lignin base. Therefore, a crosslinkable group is introduced over the length of the polymer chain in addition to the terminal of the polymer chain, and a polyfunctional prepolymer is obtained. FIG. 3 shows a prepolymer obtained by introducing a hydroxylmethyl group into the primary derivative obtained by using p-cresol as the introduced phenolic compound.

 Therefore, by combining a 2-substituted phenol compound with a phenol compound having 1 or less substitution, the crosslinkability can be adjusted. In the present invention, when a 2-substituted phenol compound represented by 2,4-dimethylphenol and Z or 2,6-dimethylphenol is used, the prepolymer has a linear polymer-forming ability (FIG. 2, right side). ). In addition, when a phenol compound having one or less substitutions represented by p_cresol is used, the prepolymer has a network polymer forming ability (FIG. 2, left). By using a combination of a 2-substituted phenol compound and a phenol compound having 1 or less substitutions, the network properties can be adjusted.

The type of the crosslinkable group to be introduced into the primary derivative is not particularly limited. The lignin may be any as long as it can be introduced into the aromatic nucleus on the mother body side or the aromatic nucleus of the introduced phenol compound. Examples of the crosslinkable group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a 1-hydroxyvaleraldehyde group and the like. The crosslinking group-forming compound is a nucleophilic compound, which is a compound that forms or retains a crosslinking group after bonding. For example, formaldehyde, acetoaldehyde, propion Aldehydes, datalaldehydes and the like can be mentioned. Considering the introduction efficiency and the like, it is preferable to use formaldehyde. In addition, polymerizable compounds such as various diisocyanates can be used.

 From the viewpoint of efficiently introducing the crosslinkable group when mixing the primary derivative and the crosslinkable group-forming compound, the crosslinkable group-forming compound is preferably introduced into the lignophenol derivative by the aromatic nucleus and z of the aryl propane unit of lignin. It is preferable to add 1 mole or more of the phenol nucleus. More preferably,

It is 10 mole times or more, more preferably 20 mole times or more.

 Next, in a state where the lignophenol derivative and the compound capable of forming a crosslinkable group are present in the solution, the liquid is heated as necessary to introduce the crosslinkable group into the phenol nucleus. The heating condition is not particularly limited as long as the crosslinkable group is introduced, but is preferably from 40 to 100 ° C. If the temperature is lower than 40 ° C, the reaction rate of the crosslinkable group-forming compound is extremely low, which is not preferable. Is not preferred. More preferably, it is 50 to 80 t, and for example, about 60 ° C. is particularly preferable. The reaction is stopped by cooling the reaction solution or the like, acidifying (approximately pH 2) with an appropriate concentration of hydrochloric acid or the like, and removing acid and unreacted crosslinkable group-forming compound by washing, dialysis and the like. After analysis, collect the sample by freeze-drying. If necessary, dry under reduced pressure over phosphorus pentoxide.

 The prepolymer obtained in this way contains the first unit and the second unit, the 1,1-bis (aryl) propane unit, the ortho position to the phenolic hydroxyl group in the arylpropane unit of the lignin and the Z or para position. It has a crosslinkable group at the position.

The first preferred crosslinkable form is an ortho and / or para position relative to the phenolic hydroxyl group of the phenol nucleus introduced in the first and Z or second units. And a crosslinkable unit having a crosslinkable group. Further, the second preferred crosslinkable compound is an ortho-position and / or a para-position of the phenolic hydroxyl group of the phenol nucleus on the lignin host side in the first and Z or second units and / or the phenylpropane unit. And a crosslinkable unit having only a crosslinkable group. Further, the third crosslinkable body is provided with the first crosslinkable unit and the second crosslinkable unit.

 The weight average molecular weight of the present prepolymer is not particularly limited, but is usually about 2000 to 2000, preferably about 2000 to 10000. The amount of the crosslinkable group to be introduced is usually about 0.01 to 1.5 mol ZC in many cases.

 (Hydroxyl protection treatment)

 In the hydroxyl group protection treatment, an acetyl group (an acetyl group, a propionyl group, a butylyl group, a valeryl group, a benzoyl group, a toluoyl group, preferably an acetyl group) is introduced into the phenolic or alcoholic hydroxyl group of the lignophenol derivative. It is preferable to perform the above. Specifically, it is performed by contacting with acetic anhydride or the like. The hydroxylation is protected by the acylation treatment. Therefore, the development of characteristics due to hydroxyl groups is suppressed. For example, hydrogen bonding may be reduced, which may reduce associative properties.

 (Al power treatment)

The alkali treatment is performed by bringing the lignophenol derivative into contact with an alkali. Preferably, it is heated. In the alkali treatment, as shown in FIG. 3, the C 2 -position carbon is attacked by the phenoxide ion of the introduced phenol compound in the first unit. That is, once this reaction occurs, the C 2 aryl ether bond is cleaved. The present invention The phenol compound introduced into the unit is used as a switching element for decomposing. That is, in the obtained secondary derivative, the first unit needs to be retained. Therefore, the alkali treatment as a derivatization step is performed to such an extent that the C 2 aryl ether bond is not cleaved in all the first units, and ultimately an incomplete alcoholic reaction capable of maintaining the first unit. Processing will be required.

 For example, in the mild alkali treatment, as shown in FIG. 3, when the primary derivative has the first unit, the phenolic hydroxyl group of the introduced phenol compound is cleaved, and the resulting phenoxide ion becomes C (2) The C 2 position constituting the aryl bond can be attacked by an intramolecular nucleophilic reaction to cleave the ether bond to reduce the molecular weight.

 Cleavage of the C 2 aryl ether bond results in the formation of a phenolic hydroxyl group in the lignin nucleus (see the dotted circle on the right in Figure 3). In addition, by the intramolecular nucleophilic reaction, a structure in which the introduced phenol nucleus forms a coumaran skeleton with the phenylpropane unit into which the phenol nucleus is introduced (aryl coumaran unit) is expressed.

 As a result, the phenolic hydroxyl group on the phenolic compound side (Fig. 3, left side, inside the dotted circle) was moved to the lignin nucleus side (Fig. 3, right side, inside the dotted line circle).

 For this reason, in the lignophenol compound having the first unit, (1) the lower molecular weight due to the cleavage of the C 2 aryl ether bond, (2) the expression of the aryl cumarane structure, (3) A phenolic hydroxyl group is expressed on the lignin nucleus side that has been linked by a C 2 aryl ether bond.

In the alkali treatment, specifically, a crosslinked product of a lignophenol derivative is dissolved in an alkaline solution, reacted for a certain period of time, and if necessary, heated. It is done by doing. The alkaline solution that can be used for this treatment is not particularly limited as long as it can dissociate the phenolic hydroxyl group of the introduced phenol compound in the lignophenol derivative, and in particular the type and concentration of the alkali and the type of the solvent are not limited. . This is because if the phenolic hydroxyl group is dissociated under an alkali, a coumaran structure is formed due to an adjacent group participation effect. For example, for a lignophenol derivative into which p-cresol has been introduced, a sodium hydroxide solution can be used. For example, the alkali concentration range of the alkali solution can be 0.5 to 2 N, and the treatment time can be about 1 to 5 hours. Moreover, the lignophenol derivative in the alkaline solution easily develops a coumaran structure when heated. Conditions such as temperature and pressure during heating can be set without any particular limitation. For example, by heating the alkaline solution to 100 ° C. or higher (for example, about 140 ° C.), the molecular weight of the crosslinked product of the lignophenol derivative can be reduced. Further, the crosslinked product of the lignophenol derivative may be reduced in molecular weight by heating the alkaline solution to a temperature equal to or higher than the boiling point thereof under pressure.

In addition, at the same alkaline solution and the same concentration, when the heating temperature is in the range of 120 ° C to 140 ° C, the higher the heating temperature, the lower the molecular weight due to the cleavage of the C2-aryl ether bond. I know it will be done. It is also found that within this temperature range, the higher the heating temperature, the more the phenolic hydroxyl group derived from the aromatic nucleus derived from the lignin matrix and the less the phenolic hydroxyl group derived from the introduced phenol compound. Therefore, the degree of molecular weight reduction and the degree of conversion from the C1-position-introduced phenolic compound side of the phenolic hydroxyl group to the phenolic nucleus of the ridinin parent can be adjusted by the reaction temperature. In other words, the lowering of the molecular weight is promoted, or more phenolic hydroxyl groups become A reaction temperature of about 80 to 140 ° C. is preferable to obtain an arylcoumarane compound converted to

 As described above, cleavage of C2-aryl ethers due to participation of adjacent groups in the C1 phenol nucleus involves the formation of an arylcoumarin structure.However, the reduction of the molecular weight of a crosslinked product of a lignophenol derivative is not always achieved by arylclaman. It does not need to be performed under well-formed conditions (around 140 ° C), but may be performed at higher temperatures (for example, around 170 ° C) depending on the material or purpose. In this case, the once formed Craman ring is cleaved and the phenolic hydroxyl group is regenerated on the introduced phenolic compound side, resulting in the induction of a material with different phenolic activity and a higher phenolic activity than that at 140 ° C. From the above, the heating temperature in the alkali treatment is not particularly limited, but is preferably from 80 ° C. to 200 ° C. If the temperature is much lower than 80 ° C., the reaction does not proceed sufficiently, and if the temperature greatly exceeds 200 ° C., undesired side reactions tend to be generated.

 As a preferred example of the treatment for the formation of the Cramman structure and the accompanying reduction in molecular weight, a 0.5 N aqueous solution of sodium hydroxide is used as an alkaline solution, and the heating time is 140 ° C. in a autoclave for 60 ° C. The condition of minutes can be mentioned. In particular, this treatment condition is preferably used for a lignophenol derivative derivatized with p-cresol or 2,4-dimethylphenol.

 (Higher derivatives)

 Various secondary derivatives can be obtained by these secondary derivatization treatments. Furthermore, by performing the above-described treatments (preferably, different kinds of treatments) on these secondary derivatives, higher secondary derivatives can be obtained. It can be derivatized.

In this case, combining the structural features generated by the processing performed Higher order derivatives to be retained can be obtained. For example, an alkali treatment and a cross-linking introduction reaction, an alkali treatment and a hydroxyl group protection treatment, and a cross-linking group introduction reaction and a hydroxyl protection treatment can be combined.

 (Composite material composition)

 A composite material can be obtained by molding a composite material composition containing such a lignin-based polymer (various derivatives other than a crosslinked body) and a glass material to be composited with a lignin-based matrix.

 There is no particular limitation on the material other than the glass material combined with the lignin-based matrix, and various organic materials and inorganic materials can be used. As the organic material, various natural or synthetic resins can be used. For example, a cellulosic material can be used. The glass material may be any material having an inorganic vitreous property. Therefore, it includes not only entirely vitreous materials but also partially or almost entirely vitreous materials. In order to take advantage of the glass material as the material to be composited, it is preferable to use a glass material that is almost entirely or entirely vitreous.

 Further, crystallized glass having crystallinity is also included in the glass material of the present invention. The amount of crystals in the crystallized glass is not particularly limited, and can be included in the glass material of the present invention.

Since the lignin-based matrix has a good binding force, even a material having little or no self-assembly such as a glass material can be well maintained in the matrix. Accordingly, the glass material can be employed in any of various forms such as an irregular shape, a spherical particle shape, a needle shape, a flake shape, a chip shape and the like, in addition to a fiber material or the like having a confounding property. In order to enhance the retention by the matrix, it is preferable that the surface has a shape such as an uneven stripe, a bulge, or a fold. Fig. 4 illustrates a scheme for combining various lignophenol derivatives with a glass material.

As the glass material, those having various compositions can be used. S i, S e, T e , 〇, element glass mainly containing such A s, H ₂ 0, HP_〇 _3, H ₃ PO ₄ hydrogen bonds glass whose main component, S i 0 _2, B ₂ 0 _3, P ₂ 〇 _5, G E_〇 _2, A s ₂ 〇 _{5, S b 2 0 3,} B i 2 0 3, P 2 0 3, V 2 〇 _3, S b ₂ 〇 _5, A s ₂ 〇 _3, SO _3, Z R_〇 oxide _{glasses 2} and the main component, full Tsu fluoride glass containing B e F ₂ as the main component, chloride glasses mainly comprising Z n C 1 _2, G e sulfide glass containing _{S 2, a s 2 S 3} , K 2 C0 3, Mg C0 3 carbonate glass whose main component, N aN0 _3, KN0 _3, nitrate glass mainly containing a g NO ₃ , and _{N a 2 S 2 0 3 ·} H 2 0, T 1 2 S 0 4, can be used in combination of one or more kinds of sulfuric glasses composed mainly of such Miyoupan _(among others, It is preferable to use oxide glass, such as silicate glass and phosphorus. Glasses, can be preferably used borate glass. Main component further Gay silicate glass is gay silicate glass shall be the main component S i 0 _2, the N a ₂ 〇- S i 〇 ₂ system main component Kei acid Al force Riga Las Seo one da-lime glass composed mainly of N a ₂ 0- C a O- S I_〇 _2, the K ₂ O-C A_〇 one S i 〇 ₂ system to Chikarari lime _{glass, K 2 0_ P b O -} S i 0 2 system is referred to as seed component lead (alkaline) _{glass, B a O- S i 0 2} - B 2 0 3 system as main components Bariumugarasu, N a ₂ 〇 one B ₂ 0 ₃ - S i 0 ₂ system Hougei silicate glass mainly composed _{of, C a O- S 1 0 2} - Aruminohou mainly composed of eight 1 ₂ 0 ₃ -〇 & 〇 system can be used Gay acid glass good Mashiku is, C A_〇 one S i 〇 _{2 -. a 1 2 0 3} - or alumino Houkei silicate glass such as C a O-based glass, N a ₂ 〇_ C a soda lime glass, such as O- S i 〇 _2-based glass (K can comprise ₂ 〇 or A 1 ₂ 〇 ₃₎ Ru may be used. It is preferable that the glass material has a property of swelling in the air. Here, the term “swelling property” means that when immersed in the solution, the swelling due to a decrease in the weight or hydration of the inside of the molecule by the force is observed. In consideration of the decompositing of the composite material by the alkali treatment, the tissue is softened or swelled by the alkali during the alkali treatment, thereby allowing the alkali to penetrate and introduce the lignin matrix into the lignin matrix. The collapse of the polymer skeleton is likely to occur due to the decomposed element, and the decomposition of the composite material can be promoted by swelling or softening of the glass material.

Glass materials are generally alkali-swellable, especially glass material with or main component containing S io ₂ is force re swelling tends to be higher. Therefore, it is possible to use a glass material having Al swelling property within a range that does not impair the physical properties of the composite material.

 In addition, the glass material is hydrated when exposed to water, and the elution of the alkali component is promoted. Therefore, in the case of the alkali treatment, the decompositing of the composite material can be further promoted by the elution of the alkali from the glass.In addition, since the chemical change of the glass material due to the alkali treatment is relatively small, This is preferable because reusability is easily ensured. The swelling properties of glass materials differ depending on their composition, and also differ in alkali strength and thermal conditions. Preferably, the alkali swelling property is exhibited in a certain temperature range. That is, it is preferable that the resin be swollen by the heat in a temperature range for the heat treatment to be carried out. Alternatively, it is also possible to set the temperature of the alkali treatment based on the temperature dependence of the alkali swelling of the glass material used.

In addition, by using a glass material as the material to be composited, it is possible to form a composite material using a material to be composited that does not have alkali swelling properties. Even in this case, the accessibility to the first element by the alkali can be enhanced, and good decombination can be realized. In addition, de-combination can be realized under mild conditions. The ability to achieve decompositing under milder conditions can minimize the level of structural transformation of the lignin-based polymer and the material to be composited, which constitute the lignin-based matrix, and the decomposed material after separation can be separated. The degree of freedom in deriving lignin-based polymers (which have been reduced in molecular weight) can be increased, and the sequential use of the composite material can be ensured.

 In addition, from the viewpoint of ensuring high water resistance in the lignin-based matrix, the material to be composited can be prepared so as to be mainly composed of an alkali non-swellable material and to contain a glass material. From such a viewpoint, it is possible to preferably use an inorganic material having an alkali non-swelling property.

By combining a first glass material having an alkali swelling property such as a glass material containing Si ₂ and a _second glass material having a lower swelling force than the first glass material, a composite material is obtained. The strength and the decomposability can be adjusted.

 When the lignin-based polymer produced in the lignin-based matrix is a crosslinked body and is a network-type polymer material (the composition for a composite material is a lignin-based polymer) In the case where it is contained as a polymer), the accessibility by alkali can be easily secured by using a glass material as the material to be composited.

In addition, it is preferable that the glass material can easily ensure uniform dispersibility from the viewpoint of ensuring alkali permeability. Therefore, it is preferable that at least the form before compounding has a form such as a powder form or a fibrous form. If it is fibrous, it may be monofilament or composite fibrous. You may. Further, it may be a network-like or sheet-like body containing a fibrous body as a component.

 The content of the glass material varies depending on the crosslinked structure of the lignin matrix to be obtained and the type and composition of the other materials to be compounded, but the appropriate content is determined by the telkari treatment of the composite material. It can be easily confirmed by a decomposite test. For example, when a prepolymer obtained by converting a primary derivative using p_cresol as an introduced phenol compound into a methylol is used as a lignin polymer, 100 parts by weight of the lignin polymer, glass material 9 When molded using a composite material composition containing 100 parts by weight, both can be easily separated by alkali treatment.

 Further, in the present composition, in addition to the above-described materials, various additives can be included depending on the use of the composite material. In particular, by using various fillers such as organic fillers having plasticity at room temperature or flexibility at room temperature, the composite material can be imparted with internal stress relaxation and toughness. The shape may be spherical or irregular, but may be fibrous. Typically, cellulosic fibers or cellulose powder (including fine fiber powder) can be used. Therefore, the cellulosic fiber or the cellulosic fine fiber powder has an swelling property, which not only imparts relaxation of internal stress and toughness to the composite material, but also promotes decomposition. In addition, any organic filler having alkali swelling property can be preferably used for the same purpose without being limited to cellulosic materials.

The ratio between the lignin-based polymer and the glass material in the present composition can be appropriately set in consideration of the function and the molding method to be imparted to the composite material.In addition, the present composition is formed by molding the present composition. The resulting composite material It is preferable that the lignin-based polymer is contained so that the lignin-based polymer is present in the composite material in an amount sufficient to decompose the composite material by reprocessing. The appropriate amount for decompositing in a composite material depends on the type of lignin-based polymer and the type of material to be composited in the final composite material. It can be easily confirmed by a decomposing test by reprocessing.

 The method of preparing the composition for the composite material and the composition form can be appropriately selected in consideration of the form of the material to be composited and the like, and can take various forms. It can also be obtained by mixing a powdery lignophenol derivative with a glass material. It can also be obtained by infiltrating a glass material with a lidanophenol derivative dissolved in a suitable solvent and then distilling off the solvent. The lignophenol derivative liquid is infiltrated into a glass material (for example, a sheet-like body or a cylindrical body in which glass fibers are entangled) that has been given a shape by some means, and the solvent is distilled off. Can also be obtained.

 (Composite material)

 The composite material (composite) can be obtained by imparting a shape and forming a lignin-based matrix by heating and Z or pressurizing the composite material composition. '

 The molding method is not particularly limited, and various molding methods such as compression molding, injection molding, extrusion molding, professional molding, foam molding, casting molding and spinning can be employed as required.

 Since the lignophenol derivative inherently has caking properties, it can exert a binding force even when pressed. Preferably, pressure is applied in a heated state. Heating and pressurization may be performed simultaneously, or one of the steps may be performed first and the other may be performed sequentially.

Heating, etc., when prevolimer is contained as a lignin polymer Thus, a crosslinked structure as shown in FIG. 5 can be obtained in the matrix of the composite material simultaneously with molding.

 The conditions for thermal crosslinking when the prepolymer is contained are not particularly limited as long as the crosslinking reaction can proceed. You may heat at a fixed temperature for a fixed time. In addition, for example, it is possible to heat to about 150 ° C to 180 ° C under the program condition of 1 ° (: up to 2 ° CZ) and then cool it down. After holding for 1 hour after reaching the set temperature, cooling conditions can be mentioned, etc. Fig. 6 shows various crosslinked structures.

 As described above, the crosslinked structure formed by crosslinking depends on the substitution site and substitution number of the introduced phenol nucleus. The left side of FIG. 5 shows that a network-type polymer material can be obtained by, for example, converting a lignophenol derivative using p-cresol as a 1-substituted phenol into methylol to form a prevolimer and thermally crosslinking. This is because, in this prepolymer, a crosslinkable group is introduced throughout the molecular chain. On the other hand, the right side of Fig. 5 shows that a lignophenol derivative using 2,4-dimethylphenol as a disubstituted phenol is converted into a methylol to form a prepolymer, which is thermally crosslinked to form a linear crosslinked structure. It is shown. This is because in such a prepolymer, a crosslinkable group is mainly introduced at one terminal of the polymer.

 Further, in the center of FIG. 5, by using a mono-substituted phenol and a di-substituted phenol as the introduced phenol compounds (typically, p-cresol and 2,4-dimethylphenol), a phenol compound based on both is obtained. It is shown that a crosslinkable group is introduced into a primary derivative having a unit to form a prepolymer, and as a result, a polymer material in which a network type and a linear type are mixed can be obtained.

The composite material obtained in this manner is made of a lignin-based polymer. It has the characteristics of Rix and the characteristics of the composite material. Even when the lignin-based matrix does not have a crosslinked structure formed during molding and is mainly composed of lignin-based polymers that are primary, secondary, and higher derivatives. Based on its inherent caking properties To form a matrix. In addition, when immersed in a solvent having a high affinity for the lignophenol derivative, such as the solvent in which the primary derivative described above is dissolved, for example, THF, the matrix easily dissolves in a solvent such as THF, and the composite material is dissolved in the solvent. Collapse.

 Further, when the lignin-based matrix has a network-like or liner-like crosslinked structure newly generated during molding, the matrix is constituted by the inherent caking property and the crosslinked structure. Irrespective of the form of the crosslinked structure (network type and linear type), the crosslinked product is uniformly distributed in the matrix, and can provide roughly similar strength characteristics and dimensional stability (water resistance or water absorption). it can. Therefore, especially when a chemically stable material (typically, an inorganic material) having little or no interaction between the materials is used, the mechanical strength and dimensional stability of the composite material are reduced by lignin. It has the advantage that it is not greatly affected by the matrix, and that the properties of inorganic materials can be easily obtained.

On the other hand, when immersed in a solvent having a high affinity for the lignophenol derivative such as the solvent in which the primary derivative is dissolved, for example, THF, the higher the linearity of the cross-linked structure formed during molding, the easier it becomes. Dissolved in THF and the composite collapsed. When a prepolymer of a primary derivative using only a 2,4-substituted phenol compound (for example, 2,4-dimethylphenol) is crosslinked, it can be easily treated by immersion in a solvent having affinity for a Lidanoff phenol derivative. It is possible to disrupt the composite form. In addition, when the primary derivative pre-polymer using only a phenol compound having 1 or less substitutions (for example, p-cresol) is crosslinked, its network structure is The structure can firmly constrain the composite material and maintain the shape of the composite material.

 In the present invention, the fact that the lignophenol derivative has the first unit and that the crosslinked product holds the first element (the phenol compound introduced at the ortho position) in the first unit. Based on this, by subjecting the composite material to alkali treatment, it is possible to reduce the molecular weight of the lignophenol derivative constituting the matrix. That is, by subjecting the composite material of the present invention to a force treatment, the reaction shown in FIGS. 3 and Z or FIG. 6 is caused in the lignin-based matrix, and the lignin-based polymer is depolymerized to decompose the composite material. Can be realized. Therefore, according to the present invention, the present composite material (especially, a molded article) is brought into contact with an alkali solution to separate the lignin-based polymer from the glass material, and the lignin-based polymer and the glass material after the alkali treatment are separated from each other. Can be recovered. The lignin-based polymer and glass material thus recovered have sufficient reusability.

 The alkali treatment is performed on the composite material as it is, preferably on a small or powdered product by grinding or the like. The alkali treatment conditions are not particularly limited as long as the composite material can be decomposed. Various conditions disclosed in the section of the above-described processing can be employed. For example, by heating an alkaline solution such as NaOH of about 0.1 N to 0.5 N to 100 ° C. or more (for example, about 140 ° C.), the lignophenol derivative and its cross-linked body can be heated. Low molecular weight can be achieved. It can be heated above the boiling point under pressure. As relaxed conditions, a temperature of about 80 ° C. or more and about 150 or less can be adopted. In addition, it can be performed at a temperature of about 150 ° C. or more and about 170 ° C. or less.

According to this treatment, the lignophenol derivative and the inside of the crosslinked product In the first device, these can be selectively reduced in molecular weight to break down the lignin matrix. Due to the reduction in molecular weight, lignin-based polymers such as lignophenol derivatives of lignin-based matrices can be easily separated and recovered. Glass materials are also easily separated and collected. Therefore, all of these materials are easily available for sequential use.

 In particular, the lignin-based polymer is reduced in molecular weight by alkali treatment, and a new partial structure or phenolic hydroxyl group is developed, so that the degree of freedom for further derivatization is increased.

 Furthermore, decompositing by a simple process, such as reprocessing, is advantageous in that the cost of reuse can be reduced. In particular, it is advantageous that it can be decomposed even under mild alkaline conditions.

 In particular, in the present invention, decompositing is easily achieved in the phenol compound (switching element) inside the polymer of the lignin-based matrix. Therefore, as described above, since the type and frequency of introduction of the phenolic compound to be introduced can be easily controlled, the introduction amount of the switching element can be controlled, and as a result, the decompositing performance according to the composite material to be obtained is obtained. Or a decomposed form.

 In addition, as described above, a lignin-based matrix having a crosslinked structure exhibits similar physicochemical properties regardless of the crosslinked structure. The performance differs greatly. This means that the dissolving solvent performance and the decompositing performance can be adjusted by the difference in the crosslinked structure.

 Further, if necessary, the access porosity of the lignin-based polymer in the lignin-based matrix to the lignin-based polymer can be easily adjusted by using a glass material, and the decompositing performance can also be adjusted.

When decomposing, lignophenol is simultaneously or separately induced. A dissolution treatment with a conductor-affinity solvent can also be performed. Here, as the affinity solvent, one or more solvents selected from methanol, ethanol, acetone, dioxane, pyridine, tetrahydrofuran, and dimethylformamide can be used simultaneously or sequentially. . This dissolving treatment can be performed prior to the decomposing step by the alkali treatment, or can be performed at a later stage.

【Example】

 Hereinafter, the present invention will be described with reference to specific examples. The present invention is not limited to the following examples.

 (Example 1)

Preparation of primary derivative

 Approximately 100 g of a defatted sample of hinoki (Chamaecyparis obtusa) wood flour (lignocellulosic material) was placed in a 500 ml beaker, and an acetone solution of p-cresol (3 units per 9 units of lignin C) was added. The mixture was stirred with a glass rod, the beaker was covered with aluminum foil and parafilm, and allowed to stand for 24 hours. Thereafter, the wood flour was vigorously stirred in the draft, and the acetone was completely distilled off to obtain wood sorbents of various phenolic compounds.

 To this distillate, 72 wt% sulfuric acid (500 ml) was added, and the mixture was added with 30%. After stirring vigorously for 1 hour, the mixture was poured into a large excess of water, and the insoluble fraction was recovered by centrifugation (350 rpm, 10 minutes, 25 ° C), deoxidation Then, the resultant was freeze-dried to obtain a primary derivative (ligno p-cresol).

 (Example 2)

Introduction of crosslinkable group into primary derivative

5 g of each of the primary derivatives obtained in Example 1 was added to 0. INNaOH aqueous solution 5 The mixture was dissolved in 00 ml, and about 45 ml of a 37% aqueous solution of formaldehyde was added, and the mixture was reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. After completion of the reaction, 1 N hydrochloric acid was added to acidify the solution to pH 2, the resulting precipitate was collected by centrifugation (conditions, etc.), deoxygenated, and lyophilized to introduce a hydroxymethyl group ( Methylol) was obtained. The obtained prepolymer was stored at -80 ° C.

 (Example 3)

Preparation of composite materials

 After dissolving each 10 Omg of the prepolymer obtained in Example 2 in tetrahydrofuran (THF), this solution was added to each of the following seven types of glass material powders of 90 Omg, mixed well, and continuously mixed. Each prepolymer was sorbed on the glass material powder by stirring to distill off the tetrahydrofuran.

 Type of glass material (Hereinafter indicated by product symbol. All are manufactured by Nippon Sheet Glass Co., Ltd.)

 (1) REV1

 E Glass fiber powder, average fiber length about 30 m, short fiber

 (2) REF160

 EGlass flake (scale) powder, average thickness about 5 m, particle size of 45 m to 300 m is 65% or more

 (3) REFG302

 E Glass flake (granular) powder

 (4) RCF015

 C glass flakes (amorphous) powder, average thickness about 5 / m, 45 m Pass particle size is more than 88%, average particle size about 15 zm

(5) REF015 EGlass flakes (amorphous) Powder, average thickness about 5 mm, 45 Mm Pass particle size is more than 88%, average particle size is about 15 m

 (6) RFP-ZF

 Glass fiber (waste) powder, short fiber mixed amorphous shape

 (7) PTSG30A

Porous flake powder, average thickness of about 1 m, average particle diameter of 13 im, specific surface area of 24 O m ² / g

 The composition of E glass and C glass is shown in the following table.

 [Table 2]

各種収着試料の各全量を、 S H I MA Z Uフロ一テスター C F T— 5 0 0 Dにて Initial Temp. ； 7 0。 (：、 Final Temp.; 1 8 0 °C , Rate； 1. 5 /分、 1 0 0 k gで圧縮成形して前記各プレボリマ一を架橋させ、 架橋体を含有する円柱状複合材料（成形体） （直径 1 0 mm)を作製した。 なお、 上記と同様のガラス材料 1 0 0 O m gから同様の成形条件にて成 形体を作製し、 コントロール成形体とした。 また、 特に、 四種類のガラ ス材料につき上記と同様にして別途成形体及びコントロール成形体を作 成した。

The total amount of each sorption sample was measured using SHI MA ZU flow tester CFT-500D, Initial Temp. (: Final Temp .; 180 ° C, Rate; 1.5 / min., Compression molding at 100 kg at 100 kg to crosslink each of the prepolymers, and to form a columnar composite material containing a crosslinked body (molded body). (Diameter: 100 mm) A molded body was produced from 100 mg of the same glass material as described above under the same molding conditions to obtain a control molded body. A molded body and a control molded body were separately formed for the glass material in the same manner as described above.

(Example 4) Evaluation of composite materials

 1. Appearance, dimensions, etc.

 Since the glass material used had almost no self-aggregation properties, the molded article of the controller was very brittle and easily collapsed when strongly touched. On the other hand, each of the molded bodies had a light beige color. The smaller the glass material particles, the higher the smoothness of the formed body.

 Figures 7 and 8 show the measurement results for weight, dimensions, and density. The dimensions were stable for the various compacts. The density of the compact prepared from porous glass (PTSG30A) was the lowest, about 0.9. In addition, only the amorphous powders REV1, RCF015, REF015, and RFP-ZF were able to keep their shapes as control compacts, but all were very brittle and collapsed easily.

 2. SEM observation

 Observation of the surface of various compacts using SEM (Hitachi Scanning Electron Microscope S-3000N) revealed that prepolymers were agglomerated by thermal crosslinking, and the matrix of the crosslinked body was discontinuously distributed between the glass material surface and the particles. I was told. In other words, it is considered that the crosslinked body forms a crosslinked structure and, in addition to the potential caking properties, strongly binds the material particles by agglomeration. This also means that the lignin-based polymer used is uniformly distributed between the glass material particles and functions well as a binder.

 3. Brinell Hardness

の深さまで陥入するのに必要 な荷重 N)を測定し， 以下の式（ 1 ) を用いて硬さ H_B(MPa)を測定した。 H_B=P/10 ( 1 ) The four types of molded products shown in FIG. 8 were subjected to SHIMADZU AG-1 10 kN according to JIS2117. A 10 mm diameter hard sphere is pressed into the center of the upper surface of each molded body at a speed of 0.5 mm / min.

The load N) required for indentation to the depth of was measured, and the hardness H _B (MPa) was measured using the following equation (1). H _B = P / 10 (1)

H _B : Brinell hardness (MPa)

 P: Load (N)

 As shown in Fig. 9, the results for the control molded product (the Brinell hardness was measured only for the control molded products of REV1 and RCF015) were 0.05 to 0.3 MPa, whereas the molded products of the test examples were tested. Each of the bodies had a pressure of about 6 to 12 MPa, and it was found that all crosslinked bodies strongly aggregated similar glass material particles and contributed to the improvement of physical strength. The molded body using the porous flake PTSG tended to have a slightly lower hardness than the other molded bodies. In addition, in the molded body using REF160, which is a scaly particle, cracks tended to hardly occur even when an iron ball was inserted. It was found that the form of the composite material affected the physical form of the compact.

4. Water absorption test

 Of the molded products obtained in Example 3, four types of molded products shown in FIG. 8 were placed on a stainless steel net, and immersed in a container filled with water to a depth of 3 cm from the bottom surface of the molded product. When the molded product floated, a stainless steel net was installed 1 to 2 mm above the upper surface of the molded product to suppress further floating. After immersion in water at 25 ° C for 60 minutes, the molded body was taken out and rolled on filter paper to quickly remove the surface moisture. It was dried at 60 ° C for 3 days. At that time, the weight and dimensions before, after and after drying were measured, and the water absorption Aw% and the volume expansion rate Vol% were determined using the following equations (2) and (3).

 Aw% = (Wt '-Wt) / Wt X 100 (2)

 Vol%-(Vol '-VoD / Vol X 100 (3)

 Aw% Water absorption (% of sam le weight)

 Wt Sample weight (g)

Wt 'Sample weight after water absorption test (g) Vol¾ ： Expansion rate of sample volume)

Vol: Sample volume (cm ³ )

Vol ': Sample volume after water absorption test or after re-drying (cm ³ )

 As a result, as shown in FIG. 10, the molded body subjected to the test showed a water absorption of about 20% to 50% after absorbing water for 1 hour. This is probably due to the slight hydrophilicity of glass, but PTSG30A, which has a porous structure in particular, showed a high water absorption (50%).

 Further, as shown in FIG. 11, the molded article in the water absorbing state did not show a large increase in volume. This was thought to be due to the fact that the glass material did not expand due to water absorption. In the case of the molded body using flake-shaped REF160, immersion in water showed a volume expansion of about 8%, and after drying, a volume increase of about 6% was observed. Visual observation showed fine delamination-like cracks, suggesting that the result was that water penetrated the cracks and was retained as it was.

 (Example 5)

Decompositing from composite materials

After pulverizing the four types of compacts shown in FIG. 8 among the compacts obtained in Example 3, 20 mg each was put into a 3 ml stainless steel autoclave containing two stainless steel poles, and 2 m 1 of 5 N NaOH was added, and the mixture was stirred for 30 minutes, and then heated at 140 ° C. and 170 ° C. for 1 hour each for alkali treatment. After the treatment, the mixture was cooled with cold water, and then the mixture was quantitatively taken out and separated into an insoluble fraction and a soluble fraction with a glass fiber filter paper having a constant weight measured. The insoluble fraction was washed with NaH and deionized water, dried with a filter dryer at 60 ° C for 3 days, and weighed. After measuring the total volume of the soluble fraction, the absorbance at 293 nm was measured. The content of the recovered lignophenol derivative (alkaline-treated product) was determined in a 0.5 N NaOH aqueous solution. It was calculated using a calibration curve prepared based on the absorbance at 293 nm of the ligno-p-cresol treated product at 140 ° C. and 170 treated product. When calculating the body weight, the primary derivative obtained using p-cresol was used.

For the secondary derivative of (Lignor P-cresol) after heat treatment with 0.5 N NaH at 170 ° C, a calibration curve was created based on the absorbance at 293 nm. Then, this calibration curve was used. The results are shown in FIG. As shown in Fig. 12, no material separation was achieved by the treatment at 140 ° C in any of the compacts, but the molding using PTSG as the glass material was achieved by the treatment at 170 ° C. Apart from the body, it was possible to almost completely separate the lidanophenol derivative and glass material. In the case of a molded body using PTSG, which is a porous glass, it was impossible to determine the recovery rate by UV treatment at 170 ° C, and the recovery rate was not measurable. Separation was a little more advanced than treatment. This is thought to be because the lignophenol derivative attached to the inside of the pores of the PTSG had poor contact with Alkyrie and reduced its separability.

Claims

The scope of the claims 1. a composite material having a lignin-based matrix,  The lignin-based matrix,  The following (a) to (e):  (a) a carbon atom ortho to the phenolic hydroxyl group of the phenolic compound, A lignophenol derivative having the first 1,1-bis (aryl) propane unit bonded to the carbon atom at position C1 of aryl propane unit of lignin  (b) a lignophenol derivative obtained by subjecting the lignophenol derivative to one kind of reaction selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit Secondary derivative  (c) the lignophenol derivative is obtained by performing at least two kinds of reactions selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit Higher derivatives,  (d) a cross-linked secondary derivative of the secondary derivative, wherein a secondary derivative obtained by a cross-linkable group introduction reaction is cross-linked, and  (e) Among the higher derivatives, a crosslinked product of a higher derivative in which a higher derivative obtained through a crosslinkable group introduction reaction is crosslinked. One or more lignin-based polymers selected from the group consisting of  Glass material, And a composite material. 2. The (a) lignophenol derivative includes a phenol compound in which at least one ortho position to a phenolic hydroxyl group is not substituted. The composite material according to claim 1, which is obtained by contacting a lignocell-based material to which one or more phenol compounds are added with an acid. 3. The composite material according to claim 1, wherein the phenol compound has a substituent at the para position and the remaining ortho position is not substituted. 4. The composite material according to claim 3, wherein the phenol compound is p-cresol.  5. The composite material according to claim 1, wherein the phenol compound has a substituent at a para position and a remaining ortho position.  6. The composite material according to claim 5, wherein the phenol compound is 2,4-dimethylphenol.  7. The phenol compound according to claim 1, wherein the phenol compound is a phenol compound having a substituent at the para position and the remaining ortho position is not substituted, and a phenol compound having a substituent at the para position and the remaining ortho position. A composite material according to item 1. 8. The composite material according to claim 7, wherein the phenol compound is p-cresol and 2,4-dimethylphenol.  9. The lidanophenol derivative is characterized in that the carbon atom at the para-position to the phenolic hydroxyl group of the phenolic compound is bonded to the carbon atom at the C1 position of aryl propane nit of lignin. The composite material according to claim 1, wherein the composite material has a single screw unit.  10. The lignophenol derivative was added with a phenol compound containing at least one phenol compound not substituted at the ortho position and at least one phenol compound not substituted at the para position with respect to the phenolic hydroxyl group. 10. The composite material according to claim 9, which is obtained by contacting a lignocellulosic material with an acid. 11. The composite material according to claim 9, wherein the phenol compound constituting the second unit has substituents at two ortho positions. 12. The composite material according to claim 11, wherein the phenol compound is 2,6-dimethylphenol.  13. The composite material according to claim 1, wherein the hydroxyl group protection treatment is a treatment for introducing an acyl group to a phenol and / or an alcoholic hydroxyl group in the lignophenol derivative.  1 4. The cross-linkable group introduction reaction is a nucleophilic compound with respect to the carbon atom at the ortho-position and the Z- or para-position of the phenolic hydroxyl group of the lignophenol derivative. The composite material according to claim 1, which is a reaction for introducing a compound that forms or retains a crosslinkable group after bonding to a carbon atom.  15. The composite material according to any one of claims 1 to 14, wherein the composite material contains an alkali non-swellable inorganic material.  1 6. The composite material according to any one of claims 1 to 14, wherein the composite material contains an alkali-swellable organic material.  17. The composite material according to claim 16, wherein the alkali-swellable organic material includes a cellulosic material.  1 8. A method for producing a composite material having a lignin-based matrix, comprising the following steps (a) to (c):  (a) The first 1,1-bis (aryl) in which the carbon atom ortho to the phenolic hydroxyl group of the phenolic compound is bonded to the carbon atom C-1 of the aryl propane unit of lignin ) Lignophenol derivatives having propane units  (b) The lignophenol derivative is obtained by performing one kind of reaction selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and has the first unit. Secondary derivatives, and (c) protecting the lignophenol derivative with a hydroxyl group, Higher-order derivative obtained by performing at least two kinds of reactions selected from re-treatment and cross-linking group introduction reaction, and having the first unit One or more lignin polymers selected from the group consisting of  Glass material, And pressurizing and Z or heating to form a matrix composition containing:  19. The method according to claim 17, wherein as a constituent material of the lignin-based matrix, at least a lignin-based polymer that has undergone a cross-linking group-introducing reaction is contained, and the lignin-based matrix is crosslinked during the molding step.  20. The lignophenol derivative in the lignin-based polymer that has undergone the crosslinkable group introduction reaction is such that the phenol compound constituting the first unit has a substituent at the para position and the remaining ortho position is a para-position. 10. The method according to claim 19, wherein the phenolic compound has an unsubstituted phenol compound and / or a substituent at the para position and the remaining ortho position.  21. A method of using a composite material molded article having a lignin-based matrix,  The lignin-based matrix,  The following (a) to (e):  (a) a carbon atom ortho to the phenolic hydroxyl group of the phenolic compound, A lignophenol derivative having the first 1,1-bis (aryl) propaneunit bonded to the carbon atom at position C1 of arylpropanunite of lignin (b) The lignophenol derivative is obtained by performing one type of reaction selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction. And a secondary derivative having the first unit  (c) The lignophenol derivative is obtained by performing at least two kinds of reactions selected from a hydroxyl group protection treatment, an alcohol treatment, and a crosslinkable group introduction reaction, and having the first unit. Secondary derivatives,  (d) a cross-linked derivative of a secondary derivative in which a secondary derivative obtained by a cross-linkable group introduction reaction among the secondary derivatives is cross-linked, and  (e) Among the above higher derivatives, crosslinked products of higher derivatives in which the higher derivatives obtained through a crosslinkable group introduction reaction are crosslinked. One or more lignin polymers selected from the group consisting of  Glass material, And  Contacting the molded body with an alkaline solution to separate the lignin-based polymer and the glass material;  Recovering the lignin-based polymer and the glass material after the heat treatment, A method comprising: