JP2016196416A - Method for producing lignin derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a lignin derivative with a controlled structure in producing the lignin derivative having two or more organic compounds introduced to lignin.SOLUTION: A method for producing a lignin derivative has a first step for the reaction between lignin and an organic compound, and a second step for the reaction between a reaction product of the first step and an organic compound different from the organic compound of the first step, where one of the first step and second step is conducted under an acidic condition and the other of them is conducted under an alkaline condition.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a lignin derivative. More specifically, the present invention relates to a method for producing a lignin derivative that can be used for a cement admixture or the like.

Lignin is one of the three major components of plant biomass such as wood (three major components: cellulose, hemicellulose, lignin), and is the most abundant on the earth as a natural aromatic polymer. . Regarding the structure of lignin, among the phenylpropanoids synthesized by the carbon compound assimilated by photosynthesis (primary metabolism) undergoing further metabolism (secondary metabolism), p-coumaryl alcohol, coniphenyl alcohol, Lignin monomer, the three basic skeletons of pill alcohol, is one-electron-oxidized by oxidase such as laccase and peroxidase to form phenoxy radical, which forms a complex three-dimensional network structure by radical coupling in an amorphous form. ing.

As described above, the molecular structure of lignin is complex, the chemical properties of lignin vary greatly depending on the isolation method used for isolation from plants, and lignin is basically a hydrophobic substance. Therefore, the use of lignin as an industrial material has been limited so far because it is poorly water-soluble.

However, on the other hand, various studies have been made to industrially use lignin that can be obtained at low cost. For example, sulfonated lignin with low electrolyte content suitable for use as a dye additive and a printing gel additive. (A) a step of ionizing the phenol component of lignin in an alkaline liquid medium, (b) a step of methylolizing the ionized phenol component of lignin, and (c) the medium Lowering the pH of the solution to an acidic range to precipitate methylolated lignin; (d) washing the precipitated lignin with water to remove inorganic salts and reaction residues; and (e) washing with water to purify the methylolated product. Sulfonated lignin in a liquid medium with a sodium salt of a compound containing sulfur and oxygen. Process for the preparation of the sodium salt of a sulfonated lignin is disclosed that (see Patent Document 1.).

JP-A-61-97484

As described above, industrial utilization of lignin derivatives has been studied, and methods for preparing lignin derivatives have been studied. However, in the conventional method, when two or more kinds of organic compounds are introduced into lignin, these compounds and lignin can be bound at various reaction sites, and thus lignin derivatives having various structures are generated. For this reason, the manufacturing method which can manufacture the lignin derivative by which the structure was controlled was calculated | required.

The present invention has been made in view of the above situation, and provides a method for producing a lignin derivative having a controlled structure when producing a lignin derivative in which two or more organic compounds are introduced into lignin. With the goal.

The present inventor has made various studies on a method for producing a lignin derivative in which two or more organic compounds are introduced into lignin. Depending on the type of the organic compound, the reactivity with lignin may be a case where the reaction solution is acidic. It was found that it was different from the alkaline case. Furthermore, when two kinds of organic compounds are introduced to lignin using the difference in reactivity of such organic compounds, one of these organic compounds is acidic under alkaline conditions and the other is acidic. The inventors have found that a lignin derivative controlled to have a certain structure can be produced by carrying out the reaction under the conditions, and have conceived that the above-mentioned problems can be solved brilliantly, thereby achieving the present invention.

That is, the present invention is a method for producing a lignin derivative, wherein the production method comprises a first step of reacting lignin and an organic compound, and a reaction product different from the organic compound of the first step and the organic product of the first step. The first step and the second step are a method for producing a lignin derivative, one of which is carried out under acidic conditions and the other is carried out under alkaline conditions.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The method for producing a lignin derivative according to the present invention is characterized in that a lignin derivative having a controlled structure can be produced by reacting lignin with two kinds of organic compounds.
One of the two types of organic compounds to be introduced has sufficient reactivity with lignin only under either acidic or alkaline conditions, and the other organic compound is sufficient under either acidic or alkaline conditions When these organic compounds react with lignin under conditions where both of the two organic compounds are reactive, these organic compounds are randomly bonded to lignin. Will be. On the other hand, in the first step, an organic compound having sufficient reactivity (hereinafter also referred to as the first organic compound) is allowed to react only under either acidic or alkaline conditions, and then in the second step. The other organic compound (hereinafter also referred to as the second organic compound) is added to the reaction system, and the liquidity opposite to that in the first step (that is, alkaline if the first step is acidic, the first step is When the reaction is carried out under acidic conditions, the first organic compound binds to lignin in the first step, and the reaction involving the unreacted first organic compound proceeds in the second step. Suppressed and the reaction between the second organic compound and the product of the first step proceeds. Here, the reactivity of the structural part derived from the first organic compound and the second organic compound in the product of the first step is higher than the reactivity of the structural part derived from lignin and the second organic compound. For example, the second organic compound is mainly bonded to the structural site derived from the first organic compound in the reaction product of the first step. Through such a two-step process, the structure introduced into lignin by two types of organic compounds can be controlled, and a lignin derivative with a controlled structure can be obtained.
In addition, the two kinds of organic compounds to be introduced into lignin have sufficient reactivity only under either acidic or alkaline conditions, and liquid properties having sufficient reactivity are opposite to each other. If it is liquid, the order in which the two kinds of organic compounds in the lignin derivative are combined can be controlled by controlling which of the conditions is acidic or alkaline. Thereby, a lignin derivative having a controlled structure is obtained.

The first step is a step of reacting lignin with the first organic compound, and the second step is a reaction between the reaction product of the first step and a second organic compound different from the first organic compound. It is a process to make.
One of the first step and the second step is performed under acidic conditions and the other is performed under alkaline conditions. Whether the first step or the second step is performed under acidic conditions or alkaline conditions, as described later, the solubility of lignin under acidic or alkaline conditions, the reactivity of organic compounds, and the first step And it can select suitably according to the combination etc. of the organic compound used in a 2nd process.
The method for producing a lignin derivative of the present invention may include other steps as long as it includes the first step and the second step.

The lignin molecule is a large molecule having a complicated three-dimensional network structure, and there are a plurality of reaction sites capable of reacting with an organic compound in one lignin molecule. For this reason, although a plurality of organic compounds can react with one lignin molecule, it is sufficient that at least one organic compound can be bound in the first step.

By performing the first step, a reaction product (hereinafter also referred to as a modified lignin) of the first step to which the organic compound is bonded, in which the reaction site has a structure represented by the following formula (1) is obtained. .

(In the formula, R ¹ represents a hydrogen atom or an alkoxy group, an .X ¹ be a plurality of bonded to the benzene ring, the .Y ¹ represent different divalent linking group and a direct bond or Y ¹ , .Y ² that represents a divalent linking group derived from the organic compounds, represents a group derived from an organic ^{compound-X. 1 - (Y 1} -X 1) n -Y 2 is not more attached to the benzene ring Z represents a hydrogen atom or a monovalent functional group, n represents the number of -Y ¹ -X ^1- repeats, and is a number from 0 to 200.)

In the first step, when a plurality of organic compounds are bonded to one lignin molecule, the organic compounds may be bonded to the benzene rings derived from lignin one by one directly or via a divalent linking group, A plurality of organic compounds may be bonded to at least one benzene ring derived from lignin directly or via a divalent linking group. When n is 1 or more, the organic compound is bonded to a group derived from an organic compound bonded to the benzene ring directly or via a divalent linking group, further directly or via a divalent linking group. . n is preferably 0 to 100, and more preferably 0 to 50.

In the above formula (1), the position at which the lignin-derived benzene ring at the reaction site of the modified lignin and -X ^1- (Y ¹ -X ¹ ) _n -Y ² are bonded is not particularly limited. At least one of the reaction sites is preferably bonded to the benzene ring and —X ¹ — (Y ¹ —X ¹ ) _n —Y ² at the ortho position of the hydroxyl group.

When X ¹ is a divalent linking group, the divalent linking group is not particularly limited as long as it is different from Y ^1, and examples thereof include a hydrocarbon group.
The divalent linking group in the lignin derivative of the present invention is preferably a divalent hydrocarbon group.
As a bivalent hydrocarbon group, a C1-C18 bivalent hydrocarbon group is preferable. A divalent hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a divalent hydrocarbon group having 1 carbon atom, that is, a methylene group is more preferable.

R ¹ is preferably a hydrogen atom or an alkoxy group having 1 to 18 carbon atoms. More preferably, they are either a hydrogen atom or an alkoxy group having 1 to 2 carbon atoms.
The monovalent functional group of Z is preferably an anionic functional group such as a hydroxyl group, a sulfonic acid group, or a carboxylic acid group; or a cationic functional group such as an amino group. More preferably, it is any one of a hydroxyl group, a sulfonic acid group, and a carboxylic acid group.

The organic compound used in the first step (hereinafter also referred to as the first organic compound) is not particularly limited as long as it can react with lignin under acidic or alkaline conditions. For example, an amine compound, Examples thereof include carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, (poly) alkylene glycol compounds, and phenols.

The amine compound is not particularly limited as long as it is a compound having an amino group, and examples thereof include monoalkylamines having 1 to 8 carbon atoms such as ethylamine; dialkylamines having 2 to 16 carbon atoms such as dimethylamine and diethylamine; 2 A monoalkanolamine having 1 to 8 carbon atoms such as aminoethanol and 2-propanolamine; a dialkanolamine having 2 to 16 carbon atoms such as diethanolamine and diisopropanolamine; and 2 to 2 carbon atoms such as 2- (methyl) aminoethanol 16 alkyl alkanolamines; alkylene diamines having 2 to 16 carbon atoms such as ethylenediamine and N-methylethylenediamine; dialkylenetriamines having 2 to 16 carbon atoms such as bis (2-aminoethyl) amine; 8 carbamide compounds; cysteamine, etc. Glycine, amino acids of glutamic acid; an amino alkanethiol having 1 to 8 carbon atoms ammonia; aromatic amines or their salts such as aniline and the like. Moreover, as an aromatic ring of aromatic amines, a C6-C14 aromatic ring comprised only by carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring; thiophene, imidazole, pyrazole, pyridine, indole, carbazole, etc. And a heterocyclic ring having 4 to 13 carbon atoms. Among these, a C6-C10 aromatic ring comprised only by a carbon atom, a C4-C9 sulfur atom, or a nitrogen atom containing heterocyclic ring is preferable. More preferably, it is a C6 aromatic ring composed of only carbon atoms, or a C4 sulfur atom or nitrogen atom-containing heterocycle. These may be used alone or in combination of two or more. In addition, the said carbon number shall mean the number of carbon which the whole compound has.

The amine compound is preferably a monoalkanolamine having 1 to 3 carbon atoms, a dialkanolamine having 2 to 6 carbon atoms, ammonia, urea, an amino acid, or an aromatic amine. More preferred are monoalkanolamines having 1 to 3 carbon atoms, dialkanolamines having 2 to 6 carbon atoms, ammonia and urea. Since these compounds are relatively inexpensive, they can be suitably used for industrial production of lignin derivatives. Moreover, from a viewpoint of the introduction | transduction efficiency with respect to lignin, More preferably, they are 2-aminoethanol and diethanolamine, More preferably, it is 2-aminoethanol.

The carboxylic acid group-containing compound is not particularly limited as long as it is a compound having a carboxylic acid group, and examples thereof include benzoic acid, phthalic acid, phenylacetic acid, naphthoic acid, and naphthaleneacetic acid. In addition, a compound in which two molecules of these carboxylic acid group-containing compounds are bonded to form an acid anhydride can also be used as a raw material for producing the lignin derivative of the present invention. In addition, amino acids, such as the above-mentioned glycine and glutamic acid, shall be contained in an amine compound. As will be described later, compounds having a phenolic hydroxyl group such as salicylic acid, hydroxyphenylacetic acid, hydroxynaphthoic acid, and hydroxynaphthaleneacetic acid are included in the phenols.
As said carboxylic acid group containing compound, what has aromatic rings, such as benzoic acid, is preferable. Specific examples and preferred forms of the aromatic ring are as described above.

The sulfonic acid group-containing compound is not particularly limited as long as it is a compound having a sulfonic acid group, and examples thereof include benzenesulfonic acid. In addition, as will be described later, compounds having a phenolic hydroxyl group such as hydroxybenzenesulfonic acid are included in phenols.
As the sulfonic acid group-containing compound, those having an aromatic ring such as benzenesulfonic acid are preferable. Specific examples and preferred forms of the aromatic ring are as described above.

The phosphoric acid group-containing compound is not particularly limited as long as it is a compound having a phosphoric acid group, and examples thereof include phenylphosphoric acid. As will be described later, compounds having a phenolic hydroxyl group such as hydroxyphenyl phosphoric acid are included in phenols.
As said phosphate group containing compound, what has aromatic rings, such as phenylphosphoric acid, is preferable. Specific examples and preferred forms of the aromatic ring are as described above.

The (poly) alkylene glycol compound is not particularly limited as long as it is a compound having a (poly) alkylene glycol chain.
The (poly) alkylene glycol compound has the following formula (2);
R ⁴ —X ² — [(R ² O) _q —R ³ ] _p (2)
(In the formula, X ² represents an oxygen atom, a sulfur atom, a divalent linking group or a trivalent linking group. R ³ and R ⁴ are the same or different and are a hydrogen atom or a monovalent organic group. R ² is the same or different and represents an alkylene group, p is a number of 1 or 2. q represents the average number of added moles of an oxyalkylene group, and is a number of 1 to 300. ).

In the above formula (2), the alkylene group represented by R ² is preferably an alkylene group having 2 to 18 carbon atoms. More preferably, it is a C2-C8 alkylene group, More preferably, it is a C2-C3 alkylene group. In the case of an alkylene group having 2 or 3 carbon atoms, the (poly) alkylene glycol chain is a (poly) ethylene glycol chain or a (poly) propylene glycol chain.
In the above formula (2), R ² represents the same or different and represents an alkylene group, and this is the same for all the R ² O alkylene groups present in q in the (poly) alkylene glycol compound. Means that it may be different.

In the above formula (2), when X ² is a divalent linking group, examples of the divalent linking group include structures of the following formulas (3-1) to (3-4).

(In Formulas (3-1) and (3-2), R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group. Q is a trivalent group having 1 to 5 carbon atoms. In formula (3-4), R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a hydrocarbon group, R ⁹ represents a hydrocarbon group, R ⁷ and R ⁸ And R ⁹ has 1 to 8 carbon atoms in total.)
In the case where X ² is a trivalent linking group, examples of the trivalent linking group include a nitrogen atom.

In the above formula (2), X ² represents an oxygen atom, a sulfur atom, a divalent linking group or a trivalent linking group, and the divalent linking group and the trivalent linking group are preferably those described above. Among these, as X ² , an oxygen atom or a sulfur atom is preferable. More preferably, it is an oxygen atom.

In the above formula (2), when R ³ and R ⁴ are monovalent organic groups, examples of the monovalent organic group include hydrocarbon groups having 1 to 30 carbon atoms. Among these, R ³ is preferably a hydrocarbon group having 1 to 4 carbon atoms. R ⁴ is preferably an aromatic hydrocarbon group.

In the above formula (2), when X ² is an oxygen atom, a sulfur atom or a divalent linking group, p is 1, and when X ² is a trivalent linking group, p is 2. .
In the above formula (2), q is preferably 1 to 300. More preferably, it is 2-200, More preferably, it is 5-100.

The above (poly) alkylene glycol compound is preferably a compound having a (poly) alkylene glycol chain and an aromatic ring. Specific examples and preferred forms of the aromatic ring are as described above. The (poly) alkylene glycol compound having an aromatic ring (hereinafter also referred to as an aromatic (poly) alkylene glycol compound) may be a compound having a structure comprising only a (poly) alkylene glycol chain and an aromatic ring, and (poly) A substituent other than the alkylene glycol chain may be bonded to the aromatic ring.
Examples of the substituent other than the (poly) alkylene glycol chain include an alkoxy group, an amino group, a sulfonic acid group, and a carboxylic acid group. These substituents may be bonded to one aromatic ring. Two or more may be combined. In addition, for example, an aromatic (poly) alkylene glycol compound having a hydroxy group as a substituent other than the (poly) alkylene glycol chain has a phenolic hydroxyl group, but has such a phenolic hydroxyl group as described later. A compound shall be contained in phenols.
An aromatic (poly) alkylene glycol compound having a benzene ring as the aromatic ring is represented by the following formula (4):

(Wherein R ¹⁰ represents a substituent other than a hydrogen atom or —X ² — (R ² O) _q —R ³ (hereinafter also referred to as a (poly) alkylene glycol chain-containing group). X ² , R ² , R ³ and q are the same as those in the above formula (2).
When R ¹⁰ is a substituent other than the (poly) alkylene glycol chain-containing group, the bonding position of the substituent is not particularly limited, but is preferably the meta position of the (poly) alkylene glycol chain-containing group.

In the above formula (4), the (poly) alkylene glycol chain-containing group in which X ² is an oxygen atom or a sulfur atom is produced by reacting (poly) alkylene glycol with a hydroxyl group of phenol or a thiol group of thiophenol. be able to.
In the formula (4), the (poly) alkylene glycol chain-containing group in which X ² is a divalent nitrogen atom-containing group represented by the formula (3-1) is obtained by adding (poly) alkylene glycol to a dialkylaminophenyl alkanol. It can be manufactured by adding it.
In the above formula (4), the (poly) alkylene glycol chain-containing group in which X ² is a divalent nitrogen atom-containing group represented by the formula (3-2) represents (poly) alkylene glycol on N-alkylaniline. It can be manufactured by adding it.
In the formula (4), the (poly) alkylene glycol chain-containing group having a structure in which X ² is the formula (3-3) is reacted with a (poly) alkylene glycol having an epoxy group at the terminal with respect to the hydroxyl group of phenol. It can be manufactured.
In the above formula (4), the (poly) alkylene glycol chain-containing group having a structure in which X ² is the formula (3-4) can be produced by reacting benzyl alcohol and ethylene oxide.
A compound having a structure other than a benzene ring as an aromatic ring can also be produced by the same method.

When the (poly) alkylene glycol compound is an aromatic (poly) alkylene glycol compound, the lignin and the aromatic (poly) alkylene glycol compound are the ortho-position or para-position of the (poly) alkylene glycol chain-containing group of the aromatic ring. It is preferable to combine with.

The phenols are not particularly limited as long as they are compounds having an aromatic ring and are compounds in which a hydrogen atom of the aromatic ring is substituted with a hydroxyl group. Specific examples and preferred forms of the aromatic ring are as described above. In addition, even if it is a compound corresponding to any of the amine compound, carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound, and (poly) alkylene glycol compound, the compound having a phenolic hydroxyl group is It shall be included in phenols.
Examples of the phenols include phenol, cresol, salicylic acid, hydroxyphenylacetic acid, hydroxynaphthoic acid, hydroxynaphthaleneacetic acid, hydroxybenzenesulfonic acid, hydroxyphenylphosphoric acid, (poly) alkylene glycol-containing phenolic compounds, and the like.
The (poly) alkylene glycol-containing phenolic compound is not particularly limited as long as it has a phenolic hydroxyl group and a (poly) alkylene glycol chain-containing group. For example, the aromatic (poly) represented by the above formula (4) Examples thereof include compounds in which R ¹⁰ of the alkylene glycol compound is a hydroxy group.

The first organic compound is a compound having reactivity with lignin under either acidic or alkaline conditions and extremely low reactivity with lignin and modified lignin under the other conditions. preferable. By using such a compound as the first organic compound, side reactions involving the first organic compound in the second step are suppressed by changing the liquid conditions of the reaction solution in the second step. be able to. Here, the compound having extremely low reactivity with lignin and modified lignin refers to a compound having a yield of less than 1 mol% when these are reacted.
Regarding the reactivity with the lignin and modified lignin, the compound having a phenolic hydroxyl group has reactivity under both acidic and alkaline conditions, and therefore the first organic compound does not have a phenolic hydroxyl group. It is preferable that it is a compound, ie, a non-phenolic compound.

In the above non-phenolic compound, an organic compound having reactivity to lignin under acidic conditions and extremely low reactivity under alkaline conditions includes (non-phenolic) carboxylic acid group-containing compounds, Examples include sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, and (poly) alkylene glycol compounds.
In the above non-phenolic compounds, organic compounds having reactivity with lignin under alkaline conditions and extremely low reactivity under acidic conditions include (non-phenolic) amine compounds and the like. .

When a compound having a polar group such as an amine compound, a carboxylic acid group-containing compound, a sulfonic acid group-containing compound, and a phosphoric acid group-containing compound is used as the first organic compound, the water solubility of the resulting modified lignin is improved. be able to. In the first step, even when lignin having extremely low water solubility under either acidic or alkaline conditions is used, the compound having a polar group is reacted under acidic or alkaline conditions where the lignin becomes water soluble. In the second step, solubility can be imparted to the modified lignin under acidic or alkaline conditions opposite to those in the first step, and the second step can be reacted with the second organic compound. Here, lignin having extremely low water solubility under acidic or alkaline conditions means lignin having an insoluble content of 9 g or more when 10 g of lignin is dissolved in 100 g of acidic aqueous solution of pH 1 or alkaline aqueous solution of pH 12 at 25 ° C. Point to. When such a compound having a polar group is reacted with lignin, 10 g of the obtained modified lignin is dissolved in 100 g of an acidic aqueous solution of pH 1 or an alkaline aqueous solution of pH 12 at 25 ° C. Less than 5 g.
The first organic compound is preferably an amine compound or a carboxylic acid group-containing compound.

In the first step, the method of reacting lignin with the first organic compound is not particularly limited, and examples thereof include the method (1) or (2).
(1) When the first organic compound has a reactive group capable of reacting with lignin, the lignin and the first organic compound are reacted as they are. Thereby, lignin and an organic compound will couple | bond together through a reactive group.
(2) The lignin and the first organic compound are reacted via a compound having a reactive group capable of reacting with lignin (hereinafter also referred to as a reactive group-containing compound). In this case, the first organic compound may or may not have a reactive group capable of reacting with lignin. Alternatively, the lignin, the first organic compound, and the reactive group-containing compound may be reacted at the same time, and the reaction product obtained after the first organic compound or lignin and the reactive group-containing compound are reacted in advance. The product may be reacted with lignin or the first organic compound.

When the first step is performed under alkaline conditions, the pH of the reaction between lignin and the first organic compound is not particularly limited as long as it is in the alkaline region, but is preferably pH 8-14. More preferably, it is pH 9-13, More preferably, it is pH 10-13. When the first organic compound is an acidic or neutral compound, the pH can be adjusted using a basic substance.
When the first organic compound is a basic compound, the pH of the reaction solution can be set to a basic region by adding the first organic compound, but the basicity other than the organic compound used for the reaction can be set. A substance may be used to adjust the pH. The basic substance other than the first organic compound is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium. The pH of the reaction solution can be measured with a pH meter (pH meter D-51: manufactured by Horiba, Ltd.).

When performing the first step under acidic conditions, the pH of the reaction between lignin and the first organic compound is not particularly limited as long as it is in the acidic region, but is preferably pH 0.1 to 3. More preferably, the pH is 0.5-2. When the first organic compound is a basic or neutral compound, the pH can be adjusted using an acid such as sulfuric acid.
When the first organic compound is an acidic compound, the pH of the reaction solution can be set to an acidic region by adding the first organic compound, but an acid other than the first organic compound used for the reaction May be used to adjust the pH. The pH of the reaction solution can be measured with a pH meter (pH meter D-51: manufactured by Horiba, Ltd.).
When the second organic compound in the second step has low reactivity under acidic conditions, the second organic compound is added at the start of the first step by performing the first step in this manner under acid conditions. Even in this case, in the first step, the reactivity between the second organic compound and lignin is low, and thus the reaction between lignin and the first organic compound proceeds.

In the first step, the amount of the organic compound to be introduced into the lignin is not particularly limited as long as at least one organic compound can be introduced into one molecule of lignin, but the weight of the organic compound used in the first step is It is preferable that it is 10-5000g with respect to 1000g of lignin. More preferably, it is 20-3000g, More preferably, it is 30-1000g.

In the first step, when a reactive group-containing compound is used, the reactive group-containing compound is not particularly limited as long as the lignin and the organic compound can be combined, but as the reactive group, an aldehyde group, a hydroxyl group, Examples include compounds having an epoxy group or the like.
As the reactive group-containing compound, an aldehyde compound is preferable.
The aldehyde compound is represented by the following formula (5);
R ¹¹ —CHO (5)
(Wherein R ¹¹ represents a hydrogen atom or a monovalent hydrocarbon group). When a compound having such a structure is used as the reactive group-containing compound, the lignin or organic compound may be represented by the following formula (6);

(Wherein, R ¹¹ is the same as R ¹¹ is of formula (5).) Through an intermediate group is introduced, represented by the lignin and organic compounds through a divalent hydrocarbon group Modified lignin having a bound structure can be produced. In this case, it becomes a modified lignin having a structure in which lignin and an organic compound are bonded via a divalent hydrocarbon group having one more carbon atom than R ¹¹ . That is, in this case, a divalent hydrocarbon group having one more carbon atom than R ¹¹ is a divalent linking group in the above formula (1). In formula (6), R ¹¹ is preferably a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably hydrogen. Is an atom. When it is a hydrogen atom, a modified lignin having a structure in which lignin and an organic compound are bonded via a methylene group can be produced.
When R ^{11 of} formula (6) is a hydrogen atom, the aldehyde compound of formula (5) is formaldehyde. When R ^{11 of} formula (5) is a hydrocarbon group having 1 to 3 carbon atoms, the aldehyde compound of formula (5) is acetaldehyde, propionaldehyde, or butanal, respectively.

In the first step, when the lignin, the organic compound, and the reactive group-containing compound are reacted at the same time, the amount of the reactive group-containing compound to be used is 10 to 500 mol% with respect to 100 mol% of the organic compound. Is preferred. More preferably, it is 30-300 mol%, More preferably, it is 80-150 mol%.

In the first step, when the lignin or lignin previously introduced with a reactive group is reacted with the organic compound or the organic compound previously introduced with a reactive group, the reaction temperature is preferably 20 to 120 ° C. More preferably, it is 50-90 degreeC. In this case, the reaction time is preferably 0.5 to 40 hours. More preferably, it is 1 to 20 hours.
In the said 1st process, when making a lignin, an organic compound, and a reactive group containing compound react simultaneously, it is preferable that reaction temperature is 20-120 degreeC. More preferably, it is 50-90 degreeC.
In this case, the reaction time is preferably 0.5 to 40 hours. More preferably, it is 1 to 20 hours.

For the reaction of lignin or a lignin previously introduced with a reactive group and an organic compound or an organic compound previously introduced with a reactive group, or a reaction between lignin, an organic compound and a reactive group-containing compound in the first step. The solvent to be used is not particularly limited as long as the reaction proceeds. In addition to water, organic solvents such as methanol, ethanol, propanol, ethylene glycol, dioxane, ethyl acetate, and dimethyl sulfoxide can also be used.
The amount of the solvent used is not particularly limited, but is preferably 20 to 10,000% by mass with respect to 100% by mass of lignin. More preferably, it is 100-3000 mass%, More preferably, it is 200-2000 mass%.

In the first step, in the method (2), when the organic compound or lignin and the reactive group-containing compound are reacted in advance, it is preferable to react the organic compound and the reactive group-containing compound in advance. .

The reaction between the organic compound and the reactive group-containing compound may be performed under either acidic or alkaline conditions, and is preferably determined depending on the reactivity with the organic compound and the reactive group-containing compound. When the reaction is carried out under the same conditions as in the first step, the reaction solution containing the reaction product can be used as it is in the first step, so the step of adjusting the acidic or alkaline conditions in the first step is omitted. be able to. For example, when the first organic compound is an amine compound and the reactive group-containing compound is an aldehyde compound, the reaction is preferably performed under alkaline conditions. The pH in the reaction between the organic compound and the reactive group-containing compound is as described for the pH in the first step.

In the reaction between the organic compound and the reactive group-containing compound, the amount of the reactive group-containing compound used is preferably 10 to 300 mol% with respect to 100 mol% of the organic compound. More preferably, it is 50-200 mol%, More preferably, it is 80-120 mol%.

The reaction temperature of the reaction between the organic compound and the reactive group-containing compound is preferably 10 to 60 ° C. More preferably, it is 20-50 degreeC.
The reaction time is preferably 0.5 to 10 hours. More preferably, it is 1 to 4 hours.
The solvent used in the reaction between the organic compound and the reactive group-containing compound is not particularly limited, and specific examples and preferred examples are as described above.

The lignin used in the first step is not particularly limited, and may be a woody lignin derived from a conifer or a broadleaf tree, or may be a herbaceous lignin. The cooking method is not particularly limited, and any of alkaline lignin obtained by alkali cooking, kraft lignin obtained by kraft cooking, acetic acid lignin obtained by acetic acid cooking, and lignin sulfonic acid obtained by sulfite cooking may be used. . It is preferable to select the type of lignin used depending on the liquidity (acidic or alkaline) of the reaction solution in the first step. For example, when the first step is performed under alkaline conditions, it is preferable to use water-soluble lignin under alkaline conditions. In this case, when water-soluble under alkaline conditions and water-solubility under acidic conditions is extremely low, as described above, by introducing an organic compound having a polar group in the first step, Underwater solubility can be improved. Examples of such lignin include alkali lignin, kraft lignin, and acetic acid lignin.

When the lignin is water-soluble under acidic and alkaline conditions, the first step can be performed under either acidic or alkaline conditions, and in consideration of the reactivity of the first organic compound, Since alkaline conditions can be determined, it is preferable. Examples of water-soluble lignin under such acidic and alkaline conditions include lignin sulfonic acid.

Although the weight average molecular weight of the said lignin is not specifically limited, For example, it is preferable to use lignin with a weight average molecular weight 1000-80000. More preferred is a lignin having a weight average molecular weight of 1500 to 70000, and still more preferred is a lignin having a weight average molecular weight of 2000 to 60000.
The weight average molecular weight can be measured by the GPC analysis method under the conditions described in Examples described later.

The second step of the production method of the present invention is a step of reacting the reaction product in the first step with an organic compound (second organic compound) different from the organic compound in the first step. When the first step is performed under alkaline conditions, the second step is performed under acidic conditions, and when the first step is performed under acidic conditions, the second step is performed under alkaline conditions.

The second organic compound is not particularly limited as long as it is a compound that can react with the reaction product of the first step under acidic or alkaline conditions and is different from the first organic compound. , Carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, (poly) alkylene glycol compounds and phenols. Specific examples and preferred examples of the amine compound, carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound and (poly) alkylene glycol compound are as described above.

Specific examples of the phenols are as described above.
Preferable phenols are phenol, cresol, salicylic acid, and hydroxyphenylacetic acid.

In the first step, an acidic condition using any one of a (non-phenolic) carboxylic acid group-containing compound, a sulfonic acid group-containing compound, a phosphoric acid group-containing compound, and a (poly) alkylene glycol compound as the first organic compound In the case where the reaction is performed under the conditions, it is preferable to use an amine compound or a phenol as the second organic compound.
The amine compound has reactivity with lignin and modified lignin under alkaline conditions, and has extremely low reactivity under acidic conditions. Therefore, at the start of the first step performed under acidic conditions, An organic compound, lignin, and an amine compound as the second organic compound can be added to the reaction system all at once.

In the first step, when the reaction is performed under alkaline conditions using an amine compound as the first organic compound, a (non-phenolic) carboxylic acid group-containing compound, a sulfonic acid group-containing compound, It is preferable to use any one of a phosphoric acid group-containing compound, a (poly) alkylene glycol compound, and phenols.
The above (non-phenolic) carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound and (poly) alkylene glycol compound are reactive to lignin under acidic conditions, and alkaline conditions The first organic compound, lignin, and these compounds as the second organic compound should be added to the reaction system at the beginning of the first step performed under alkaline conditions because the reactivity at the bottom is extremely low Can do.

Since the phenols are reactive to lignin and modified lignin under acidic and alkaline conditions, the conditions for the second step can be determined according to the acidic or alkaline conditions of the reaction solution of the first step. it can.

In the reaction product of the first step, the reaction site for bonding the second organic compound is not particularly limited, and is a carbon atom of a lignin-derived benzene ring to which the first organic compound is bonded in the first step. Alternatively, it may be a carbon atom of a benzene ring derived from lignin to which the first organic compound is not bonded, or an atom derived from the first organic compound in the above formula (1). Preferably, it is an atom derived from the first organic compound. In addition, a plurality of reaction sites exist in one molecule of the reaction product in the first step, and a plurality of second organic compounds can react with one molecule of the reaction product in the first step. In the second step, As long as at least one second organic compound can be reacted, the number of the second organic compound reacted with the reaction product of the first step is not particularly limited.

The lignin derivative of the present invention has a structure represented by the following formula (7) or (8) by performing the second step.

(Wherein R ¹² represents a hydrogen atom, an alkoxy group, or a group derived from the first organic compound bonded to the benzene ring directly or via a divalent linking group, and a plurality of R ¹² may be bonded to the benzene ring. .X ³ is .W ¹ representing a divalent linking group that is different from the direct bond or ^{Y 1} and ^{W 1} are .W ² that represents a divalent linking group derived from the second organic compound, the second Represents a group derived from an organic compound, m represents the number of repeating —X ³ —W ¹ —, and is a number of 0 to 200. R ¹ , X ¹ , Y ¹ , Z, and n are represented by the above formula ( The same as R ¹ , X ¹ , Y ¹ , Z and n in ¹ ).
The group derived from the alkoxy group, divalent linking group and first organic compound in R ¹² of the above formula (7) is derived from the alkoxy group, divalent linking group and first organic compound in the above formula (1). Same as the group.
When X ³ is a divalent linking group different from Y ¹ and W ¹ , specific examples and preferred examples of the divalent linking group are the same as the divalent linking group in X ¹ described above.
m is preferably 0 to 100, and more preferably 0 to 50.

If the group derived from the first organic compound introduced in the first step is more reactive with the second organic compound than the lignin-derived benzene ring, in the second step, the above formula (8 A lignin derivative having a reaction site represented by In the lignin derivative having the reaction site represented by the above formula (8), the first organic compound and the second organic compound are introduced at a specific position with respect to the lignin. It becomes a derivative.

As a combination of reaction conditions, lignin, and an organic compound in the first step and the second step of the present invention, for example, the following combinations (a) and (b) are preferable.
(A) First step: As lignin, at least one selected from the group consisting of lignin sulfonic acid, alkali lignin, kraft lignin and acetic acid lignin is used, and an amine compound is used as the first organic compound under alkaline conditions. Perform the reaction.
Second step: The second organic compound is selected from the group consisting of (non-phenolic) carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, (poly) alkylene glycol compounds, and phenols. The reaction is carried out under acidic conditions using at least one compound.

(B) First step: Lignin sulfonic acid is used as lignin, and (non-phenolic) carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound and (poly) are used as the first organic compound. The reaction is carried out under acidic conditions using at least one compound selected from the group consisting of alkylene glycol compounds.
Second step: An amine compound or phenol is used as the second organic compound, and the reaction is carried out under alkaline conditions.

In the case of (a) above, the amine compound as the first organic compound has low reactivity under acidic conditions. Therefore, by making the reaction solution acidic, a side reaction involving the amine compound in the second step is performed. Can be suppressed. That is, the lignin derivative in which the first organic compound and the second organic compound in the second step can be prevented from being randomly bonded to the reaction product of the first step, and the structure is controlled. Can be obtained.
Further, as the second organic compound, since it has low reactivity under alkaline conditions, (non-phenolic) carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound, and (poly) alkylene glycol Compounds are preferred. In this case, since the side reaction involving the second organic compound is unlikely to occur in the first step, the first organic compound, lignin and the second organic compound are collectively contained in the reaction system at the start of the first step. Can be added.
Further, in the case of (a) above, by introducing a polar group into lignin with an amine compound, water solubility under acidic conditions can be imparted to lignin, so that lignin with extremely low water solubility under acidic conditions is used. Can even be used.

In the case of (b) above, the (non-phenolic) carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound and (poly) alkylene glycol compound as the first organic compound are subjected to alkaline conditions. Therefore, the side reaction involving these compounds in the second step can be suppressed by making the reaction solution alkaline in the second step. That is, the lignin derivative in which the first organic compound and the second organic compound in the second step can be prevented from being randomly bonded to the reaction product of the first step, and the structure is controlled. Can be obtained.
In addition, the second organic compound is preferably an amine compound having low reactivity under acidic conditions. In this case, since the side reaction involving the second organic compound is unlikely to occur in the first step, the first organic compound, lignin and the second organic compound are collectively contained in the reaction system at the start of the first step. Can be added.

The pH of the reaction solution when the second step is performed under acidic or alkaline conditions is the same as the pH of the reaction solution in the first step.

In the second step, the method of reacting the reaction product of the first step with the second organic compound is not particularly limited, and examples thereof include the method (3) or (4).
(3) When the second organic compound has a reactive group capable of reacting with the reaction product of the first step, the reaction product of the first step, the second organic compound, and React. Thereby, the reaction product of the first step and the second organic compound are bonded via the reactive group.
(4) The reaction product of the first step and the second organic compound are reacted via the reactive group-containing compound. In this case, the second organic compound may or may not have a reactive group. Further, the reaction product of the first step, the second organic compound, and the reactive group-containing compound may be simultaneously reacted, and the second organic compound or the reaction product of the first step and the reactive group-containing compound After reacting in advance, the obtained reaction product may be reacted with the reaction product of the first step or the second organic compound. Preferably, the reaction product of the first step, the second organic compound, and the reactive group-containing compound are reacted at the same time.
The reactive group-containing compound is as described in the first step.
Other reaction conditions in the second step are the same as those in the first step.

The lignin derivative obtained by the production method of the present invention preferably has a weight average molecular weight of 1000 to 100,000. When the lignin derivative has such a weight average molecular weight, it becomes more suitable as a cement admixture described later. The weight average molecular weight of the lignin derivative is more preferably 1500 to 90000, and still more preferably 2000 to 80000.
The weight average molecular weight of the lignin derivative can be measured by using GPC under the conditions described in Examples described later.

The lignin derivative obtained by the production method of the present invention has a structure derived from lignin and a structure derived from an organic compound, and can be added to the cement composition to increase the fluidity of the cement composition. It can be suitably used as a cement admixture. Such a cement admixture containing the lignin derivative of the present invention is also one aspect of the present invention, and a cement composition comprising the cement admixture and cement is also one aspect of the present invention. It is.
When a lignin cement admixture is used, the problem is that the amount of entrained air in the cement composition is large. On the other hand, when at least one organic compound used in the production method of the present invention has a polar group such as an amine compound, the lignin derivative of the present invention has a polar group. Hydrophilicity is improved and the amount of entrained air can be reduced.

As the above-mentioned cement composition, those containing cement, water, fine aggregate, coarse aggregate and the like are suitable. As the cement, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate resistance, Various mixed cements (blast furnace cement, silica cement, fly ash cement); white Portland cement; alumina cement; super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement) ); Grout cement; oil well cement; low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high content of belite); ultra high strength cement; cement-based solidified material; Cement produced from one or more of incineration ash and sewage sludge incineration ash G) other such, these blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and a film obtained by adding a fine powder and gypsum limestone powder.
As the above aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia, etc. Refractory aggregate and the like.

Examples of the unit water amount per 1 m ³ of the cement composition, the cement use amount, and the water / cement ratio (mass ratio) include, for example, a unit water amount of 100 to 185 kg / m ³ , a use cement amount of 200 to 800 kg / m ³ , and a water / cement ratio. Cement ratio (mass ratio) is preferably 0.1 to 0.7. More preferably, the unit water amount is 120 to 175 kg / m ³ , the cement amount used is 250 to 800 kg / m ³ , and the water / cement ratio (mass ratio) is 0.2 to 0.65.

When the cement admixture of the present invention is used in a cement composition, the lignin derivative, which is an essential component of the cement admixture of the present invention, is used as a blending ratio with respect to the total amount of cement mass of 100% by mass in terms of solid content. Therefore, it is preferable to set it to be 0.01 to 10% by mass. If it is less than 0.01% by mass, the performance may not be sufficient. On the other hand, if it exceeds 10% by mass, the effect will substantially reach its peak, which may be disadvantageous in terms of economy. More preferably, it is 0.02-8 mass%, More preferably, it is 0.05-6 mass%.

The method for producing a lignin derivative of the present invention has the above-described configuration, and is a lignin derivative in which two or more organic compounds are introduced into lignin, and a lignin derivative with a controlled structure is obtained. It can be suitably used industrially as a production method.

FIG. 2 is a diagram showing the results of capillary electrophoresis of amine-modified lignin (1) and lignin derivative (1) obtained in Example 1. It is the figure which showed the result of the capillary electrophoresis of the amine modified lignin (2) and lignin derivative (2) obtained in Example 2.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Gel permeation chromatography (GPC)>
The weight average molecular weight of the lignin derivative was measured by the following measuring method.
Apparatus: Waters Alliance 2695 (manufactured by Waters)
Analysis software: Empower Professional + GPC option (manufactured by Waters)
Column: TSKgel guard column α (inner diameter 6.0 × 40 mm) + α5000 + α4000 + α3000 (each inner diameter 7.8 × length 300 mm) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Solvent: Solution of 29 g of sodium hydroxide and 3600 g of acetonitrile mixed with 14371 g of 100 mM boric acid aqueous solution Flow rate: 1.0 ml / min
Sample introduction amount: 100 μl
Sample concentration: 0.5% by mass
Detector: differential refractometer (RI) detector (Waters 2414, manufactured by Waters)
Calibration curve: Tosoh's polyethylene glycol (Mp = 300000, 200000, 107000, 50000, 27700, 11840, 6450, 1470, 1010, 400) is used as a standard substance, and a cubic equation is created based on Mp and elution time.

<Capillary electrophoresis>
The charge characteristics of the amine-modified lignin and lignin derivatives obtained in the examples were measured by the following measuring method.
Equipment: P / ACE system MDQ (manufactured by Beckman Coulter)
Analysis software: 32 Karat (Beckman Coulter)
Column: Fused silica capillary column P / N = 338454 (inner diameter 75 μm × length 500 mm) (Beckman Coulter, Inc.)
Column temperature: 25 ° C
Voltage: 20kV
Solvent: 50 mM boric acid aqueous solution Sample concentration: 2% by mass
Detector: UV, Hg lamp 210nm

<Example 1>
[Reaction 1-1]: Reaction of 2-aminoethanol with formaldehyde
181.0 g of 2-aminoethanol and 28.5 g of deionized water were charged into a separable flask, the temperature of the separable flask was raised to 40 ° C., and 240.5 g of 37% formaldehyde solution was added dropwise over 1 hour with stirring. The pH of the reaction system was 10.8. After completion of the dropwise addition, the mixture was further stirred at 40 ° C. for 1 hour to obtain 2- (hydroxymethyl) aminoethanol (2HMAE).

[Reaction 1-2]: Reaction of 2HMAE with lignin sulfonic acid 6.0 g of sodium lignin sulfonate (weight average molecular weight 48830, manufactured by ALDRICH), 32.8 g of deionized water, 0.4 g of 30% NaOH aqueous solution, and reaction 1 0.8 g of the 2- (hydroxymethyl) aminoethanol solution obtained in 1 was charged into a separable flask, and the separable flask was heated to 70 ° C. and stirred for 6 hours. The pH of the reaction system was 11.0. Then, it cooled and the amine modified lignin (1) was obtained. The obtained product (amine-modified lignin (1)) had a weight average molecular weight of 45600.

[Reaction 1-3]: Reaction of amine-modified lignin with PhO-EO20 36.0 g of an amine-modified lignin (1) aqueous solution obtained in reaction 1-2, PhO-EO20 (20-mol phenol oxide addition product of phenol) 3. 6 g and a 37% formaldehyde aqueous solution 0.9 g were charged into a separable flask, and 1.1 g of sulfuric acid was added thereto to adjust the inside of the reaction system to pH = 1. Next, the separable flask was heated to 100 ° C. and stirred for 6 hours. Thereafter, the separable flask was cooled to room temperature, and the reaction solution was adjusted to pH = 10 using a 30% aqueous sodium hydroxide solution to obtain a lignin derivative (1). The weight average molecular weight of the obtained product (lignin derivative (1)) was 51200.

<Example 2>
[Reaction 2-1]: Reaction of 2HMAE with Kraft Lignin Obtained from Kraft lignin (weight average molecular weight 17700, manufactured by ALDRICH) 48.0 g, deionized water 138.8 g, 30% NaOH aqueous solution 16.8 g and Reaction 1-1. 36.4 g of the obtained 2- (hydroxymethyl) aminoethanol solution was charged into a separable flask, and the separable flask was heated to 70 ° C. and stirred for 6 hours. The pH of the reaction system was 11.0. Then, it cooled and the amine modified lignin (2) was obtained. The weight average molecular weight of the obtained product (amine-modified lignin (2)) was 24800.

[Reaction 2-2]: Reaction of amine-modified lignin (2) with PhO-EO20 26.7 g of an aqueous solution of amine-modified lignin (2) obtained in reaction 2-1 and PhO-EO20 (20 mol of ethylene oxide adduct of phenol) ) 12.4 g and 37 g of a 37% aqueous formaldehyde solution were charged into a separable flask, and 3.0 g of sulfuric acid was added thereto to adjust the inside of the reaction system to pH = 1. Next, the separable flask was heated to 100 ° C. and stirred for 6 hours. Thereafter, the separable flask was cooled to room temperature, and the reaction solution was adjusted to pH = 10 using a 30% aqueous sodium hydroxide solution to obtain a lignin derivative (2). The weight average molecular weight of the obtained product (lignin derivative (2)) was 35100.

The results of capillary electrophoresis of the amine-modified lignin (1) obtained in the above reaction 1-2 and the lignin derivative (1) obtained in the reaction 1-3 are shown in FIG. 1, and the amine-modified lignin obtained in the reaction 2-1 is shown in FIG. FIG. 2 shows the results of capillary electrophoresis of the lignin (2) and the lignin derivative (2) obtained in the reaction 2-2. In addition to these, FIGS. 1 and 2 also show the results of electrophoresis of sodium lignin sulfonate and kraft lignin, respectively. Thiourea is an uncharged reference material. It means that anionic property is so high that holding time is long by electrophoresis measurement. The amine-modified lignins (1) and (2) obtained in the reaction 1-2 and the reaction 2-1 are shifted to a side having a lower anionic property than the sodium lignin sulfonate or kraft lignin before the reaction. From this, it was confirmed that 2-aminoethanol having no charge was added to lignin. In addition, the lignin derivatives (1) and (2) obtained in the reaction 1-3 and the reaction 2-2 are shifted to the side of lower anionicity than the amine-modified lignin (1) or (2), respectively. From this result, it was confirmed that PhO-EO20 having no charge was added to the amine-modified lignins (1) and (2).

About the lignin derivative manufactured in Examples 1-2, the mortar test was done with the following method. A test was conducted in the same manner as Comparative Example 1 except that no lignin derivative was added. The results are shown in Table 1.

<Mortar test>
The mortar test was performed in an environment where the temperature was 20 ° C. ± 1 ° C. and the relative humidity was 60% ± 15%.
The mortar formulation was C / S / W = 500/1350/250 (g).
However,
C: Ordinary Portland cement (manufactured by Taiheiyo Cement)
S: Standard sand for cement strength test (Cement Association)
W: An ion exchange aqueous solution of a sample and an antifoaming agent. For W, an antifoaming agent MA-404 (manufactured by BASF Japan) is added in an amount of 40% by mass based on the solid content of each sample, and ion exchange water is further added The amount was fixed and dissolved sufficiently uniformly. In Table 1, the addition amount of each sample is represented by mass% of the solid content of each sample with respect to the cement mass.
The mortar was prepared as follows in accordance with JIS-R5201-1997. Using a Hobart mixer (model number N-50; manufactured by Hobart), C and W were added and kneaded at a first speed for 30 seconds. Further, S was added over 30 seconds while kneading at a first speed.
After the completion of S addition, after kneading for 30 seconds at the second speed, the mixer was stopped, the mortar was scraped off for 15 seconds, and then allowed to stand for 75 seconds. The mixture was allowed to stand for 75 seconds and then kneaded at a second speed for 60 seconds to prepare mortar.
The obtained mortar was transferred from a kneading container to a polyethylene 1L container, and after stirring 10 times each left and right with a spatula, immediately followed by a mini slump cone (JIS micro concrete slump cone, top inner diameter). 50mm, inner diameter 100mm, height 150mm), squeezed 15 times with butt stick, mortar filled to the full size of mini slump cone, struck with 15 butt stick, finally compensated for shortage, mini slump cone Leveled the surface. Then, 5 minutes and 30 seconds after starting the mixer for the first time, the mini slump cone was pulled up vertically, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter of the part forming 90 degrees with respect to the major axis) ) Was measured at two locations, and the average value was taken as the mortar flow value. In addition, a mortar flow value shows that fluidity | liquidity is so high that a numerical value is large, ie, workability is favorable, and it shows that dispersion performance is excellent in evaluation as a dispersing agent.

From the above results, by using the lignin derivative obtained by the method of the present invention as a cement additive, the fluidity of the cement composition is improved and good workability can be provided.

Claims (3)

A method for producing a lignin derivative, comprising:
The production method includes a first step of reacting lignin with an organic compound, and a second step of reacting a reaction product of the first step with an organic compound different from the organic compound of the first step,
In the first step and the second step, one is carried out under acidic conditions and the other is carried out under alkaline conditions. The organic compound in the first step is at least one compound selected from the group consisting of an amine compound, a carboxylic acid group-containing compound, a sulfonic acid group-containing compound, a phosphoric acid group-containing compound, and a (poly) alkylene glycol compound. ,
The organic compound in the second step is at least one selected from the group consisting of amine compounds, carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, (poly) alkylene glycol compounds, and phenols. It is a compound, The manufacturing method of the lignin derivative | guide_body of Claim 1 characterized by the above-mentioned. The method for producing a lignin derivative according to claim 1 or 2, wherein the lignin is water-soluble lignin under acidic and alkaline conditions.

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