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WO2004031298A1 - Materiau composite en verre avec matrice en lignine - Google Patents

Materiau composite en verre avec matrice en lignine Download PDF

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Publication number
WO2004031298A1
WO2004031298A1 PCT/JP2003/011704 JP0311704W WO2004031298A1 WO 2004031298 A1 WO2004031298 A1 WO 2004031298A1 JP 0311704 W JP0311704 W JP 0311704W WO 2004031298 A1 WO2004031298 A1 WO 2004031298A1
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Prior art keywords
lignin
derivative
composite material
phenol compound
hydroxyl group
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PCT/JP2003/011704
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English (en)
Japanese (ja)
Inventor
Masamitsu Funaoka
Yukiko Nagamatsu
Juichi Ino
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Japan Science and Technology Agency
Nippon Sheet Glass Co Ltd
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Japan Science and Technology Agency
Nippon Sheet Glass Co Ltd
Japan Science and Technology Corp
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Publication of WO2004031298A1 publication Critical patent/WO2004031298A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin

Definitions

  • 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
  • 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.
  • 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.
  • cellulose resin 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.
  • 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.
  • 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.
  • 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.
  • the cellulose in the lignocellulosic composite has been reused by repeating fiberization and sheeting.
  • 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.
  • a lignophenol derivative phenolic compound of carbohydrates and lignin
  • 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).
  • 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.
  • Japanese Unexamined Patent Publication No. 2001-26189 Japanese Unexamined Patent Publication No. 2001-26189. Disclosure of the invention
  • 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.
  • This lignin matrix is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • 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.
  • One or more lignin polymers selected from the group consisting of
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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.
  • 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 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;
  • 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.
  • 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.
  • 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.
  • HM group crosslinkable group
  • 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. 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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)
  • the polymer skeleton can be cleaved at this element site.
  • 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 lignin-containing material preferably a lignocellulosic material, which has been affinityd by a predetermined phenolic compound
  • an acid preferably a lignocellulosic material, which has been affinityd by a predetermined phenolic compound
  • 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.
  • wood any type of wood such as conifers and hardwoods can be used.
  • various herbaceous plants and related agricultural and industrial wastes can be used.
  • a monovalent phenol compound, a divalent phenol compound, a trivalent phenol compound, or the like can be used as the phenol compound for solvating the lignocellulose-based substance or sorbing the lignocellulose-based material.
  • the monovalent phenol compound examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the amount introduced into the lignin matrix can be controlled.
  • 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.
  • Second unit the carbon atom para to the phenolic hydroxyl group of the phenol derivative is rigged
  • 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.
  • a phenol compound having no substituent at at least one ortho position (preferably, all ortho positions) is used.
  • 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.
  • 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.
  • 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
  • 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.
  • phenol compound examples include p-cresol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, resorcinol , Homocatechol, pyrogallol, and phloroglucinol.
  • the acid added to the lignocellulosic material is not particularly limited, but preferably has an action of swelling the cell opening.
  • 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
  • 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.
  • sulfuric 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.
  • a phenolic compound in liquid form for example, p-cresol or 2,4-dimethylphenol
  • a concentrated acid as described above, for example, 72% sulfuric acid
  • 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.
  • 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.
  • a solvent eg, ethanol or acetone
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • the introduction frequency can be easily adjusted depending on the number of carbon atoms and the branched form.
  • the substituent is a methyl group, the introduction position can be controlled while maintaining a high introduction frequency.
  • 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.
  • 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.
  • 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.
  • 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.
  • a prepolymer having a hydroxymethyl group introduced as a crosslinkable group (methylolated) is exemplified.
  • 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.
  • the crosslinkability can be adjusted.
  • the prepolymer 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). ).
  • the prepolymer 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).
  • 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.
  • formaldehyde, acetoaldehyde, propion Aldehydes, datalaldehydes and the like can be mentioned. Considering the introduction efficiency and the like, it is preferable to use formaldehyde.
  • polymerizable compounds such as various diisocyanates can be used.
  • 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,
  • 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 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.
  • 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.
  • 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.
  • 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.
  • the alkali treatment is performed by bringing the lignophenol derivative into contact with an alkali. Preferably, it is heated.
  • 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.
  • the primary derivative 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.
  • 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.
  • a sodium hydroxide solution can be used for a lignophenol derivative into which p-cresol has been introduced.
  • 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.
  • 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.
  • the heating temperature 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.
  • cleavage of C2-aryl ethers due to participation of adjacent groups in the C1 phenol nucleus involves the formation of an arylcoumarin structure.
  • 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.
  • 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.
  • 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.
  • this treatment condition is preferably used for a lignophenol derivative derivatized with p-cresol or 2,4-dimethylphenol.
  • 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.
  • 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.
  • the material other than the glass material combined with the 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.
  • the organic material various natural or synthetic resins can be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • S i, S e, T e , ⁇ element glass mainly containing such A s, H 2 0, HP_ ⁇ 3, H 3 PO 4 hydrogen bonds glass whose main component, S i 0 2, B 2 0 3, P 2 ⁇ 5, G E_ ⁇ 2, A s 2 ⁇ 5, S b 2 0 3, B i 2 0 3, P 2 0 3, V 2 ⁇ 3, S b 2 ⁇ 5, A s 2 ⁇ 3, SO 3, Z R_ ⁇ 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,
  • a 1 2 0 3 - or alumino Houkei silicate glass such as C a O-based glass, N a 2 ⁇ _ C a soda lime glass, such as O- S i ⁇ 2-based glass (K can comprise 2 ⁇ or A 1 2 ⁇ 3) Ru may be used.
  • the glass material has a property of swelling in the air.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a composite material 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.
  • 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)
  • the accessibility by alkali can be easily secured by using a glass material as the material to be composited.
  • 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.
  • various additives can be included depending on the use of the composite material.
  • 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.
  • cellulosic fibers or cellulose 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.
  • 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.
  • 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.
  • a glass material for example, a sheet-like body or a cylindrical body in which glass fibers are entangled
  • the composite material 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.
  • the lignophenol derivative inherently has caking properties, it can exert a binding force even when pressed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • a chemically stable material typically, an inorganic material
  • a prepolymer of a primary derivative using only a 2,4-substituted phenol compound for example, 2,4-dimethylphenol
  • 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.
  • the primary derivative pre-polymer using only a phenol compound having 1 or less substitutions for example, p-cresol
  • its network structure is The structure can firmly constrain the composite material and maintain the shape of the composite material.
  • 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 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.
  • 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.
  • 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.
  • the lignophenol derivative and the inside of the crosslinked product In the first device 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.
  • 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.
  • decompositing by a simple process is advantageous in that the cost of reuse can be reduced.
  • it is advantageous that it can be decomposed even under mild alkaline conditions.
  • 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.
  • 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.
  • 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.
  • lignophenol When decomposing, lignophenol is simultaneously or separately induced.
  • a dissolution treatment with a conductor-affinity solvent can also be performed.
  • 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.
  • 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.
  • Example 2 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.
  • Type of glass material (Hereinafter indicated by product symbol. All are manufactured by Nippon Sheet Glass Co., Ltd.)
  • EGlass flake (scale) powder average thickness about 5 m, particle size of 45 m to 300 m is 65% or more
  • 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
  • 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 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).
  • 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.
  • the molded article of the controller was very brittle and easily collapsed when strongly touched.
  • 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.
  • 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.
  • the results for the control molded product 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.
  • 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.
  • Example 3 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.
  • a stainless steel net was installed 1 to 2 mm above the upper surface of the molded product to suppress further floating.
  • 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).
  • 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%).
  • 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.
  • 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.
  • 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.
  • the primary derivative obtained using p-cresol was used.

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Abstract

Cette invention concerne un matériau composite comprenant un polymère de lignine et un matériau en verre. Le polymère de lignine est pris dans le groupe composé de dérivés de lignophénol possédant des unités de 1,1-bis(aryl)-propane qui s'obtient par liaison de l'atome de carbone d'un phénol dans une position ortho par rapport au groupe hydroxy phénolique à l'atome de carbone en position C1 de l'unité d'arylpropane de lignine ; des dérivés secondaires ou plus qui s'obtiennent en soumettant les dérivés susmentionnés à une ou deux réactions prises parmi le traitement de blocage hydroxy, un traitement alcalin et l'introduction de groupes réticulants ; et des polymères obtenus par réticulation de dérivés secondaires ou plus obtenus par introduction de groupes réticulants. L'invention concerne également une technique d'obtention d'un composant par mélange de lignine et d'un matériau en verre et une technique consistant à décomposer un matériau en verre composite en ses constituants et à récupérer ces derniers.
PCT/JP2003/011704 2002-10-02 2003-09-12 Materiau composite en verre avec matrice en lignine Ceased WO2004031298A1 (fr)

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JP2001261839A (ja) * 2000-03-16 2001-09-26 Masamitsu Funaoka リグニン系リサイクル材料
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US4764597A (en) * 1987-06-15 1988-08-16 Westvaco Corporation Method for methylolation of lignin materials
JPH02233701A (ja) * 1989-03-08 1990-09-17 Masamitsu Funaoka リグノセルロース系物質をポリフェノールと炭水化物とに分離する方法およびこの方法によって得られたポリフェノール系物質
JPH0343442A (ja) * 1989-07-12 1991-02-25 Hitachi Chem Co Ltd リグノセルロース−フェノールノボラック樹脂及びリグノセルロース−フェノールノボラック樹脂形成物の製造法
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