JP6534551B2 - Method for producing lignin derivative - Google Patents

Description

The present invention relates to a method for producing lignin derivatives. More particularly, the present invention relates to a method for producing lignin derivatives usable for applications such as cement admixtures.

Lignin is one of the three major components of plant biomass such as wood (three major components: cellulose, hemicellulose, lignin), and is most abundant on earth as a natural aromatic polymer . With regard to the structure of lignin, p-coumaryl alcohol / coniphenyl alcohol / cinina among the phenylpropanoids synthesized by the carbon compounds that are assimilated by photosynthesis (primary metabolism) undergo further metabolism (secondary metabolism) Lignin monomers, which are three basic frameworks of pill alcohol, are one-electron oxidized by oxidising enzymes such as laccase / peroxidase to become phenoxy radicals, which form an indeterminate radical coupling to form a complex three-dimensional network structure. ing.

As described above, the molecular structure of lignin is complicated, and the chemical properties of lignin are largely changed by the isolation method when isolated from a plant, and lignin is basically a hydrophobic substance. Until now, the use of lignin as an industrial material has been limited because of its poor water solubility and the like.

However, on the other hand, various studies have been made to industrially utilize inexpensively available lignin, for example, sulfonated lignin having a low electrolyte content suitable for use as a dye additive and a printing gel additive. (A) ionizing the phenolic component of lignin in an alkaline liquid medium, (b) methylolating the ionized phenolic component of lignin, (c) the medium And (d) washing the precipitated lignin with water to remove inorganic salts and reaction residues, and (e) washing the methylolated with water. And sulfonation of the lignin with a sodium salt of a sulfur and oxygen containing compound in a liquid medium. Process for the preparation of the sodium salt of a sulfonated lignin is disclosed that (see Patent Document 1.).

JP-A-61-97484

As mentioned above, the industrial use of lignin derivatives is being studied, and methods for preparing lignin derivatives are being considered. However, in the conventional method, when two or more organic compounds are introduced into lignin, lignin derivatives having various structures are generated because these compounds and lignin can be bound at various reaction sites. For this reason, a production method capable of producing a lignin derivative whose structure is controlled has been desired.

This invention is made in view of the said present condition, and when manufacturing the lignin derivative which introduce | transduced 2 or more types of organic compounds with respect to lignin, the manufacturing method of the lignin derivative in which the structure was controlled is provided. With the goal.

The inventors of the present invention examined various methods for producing lignin derivatives in which two or more organic compounds are introduced into lignin. According to the types of organic compounds, the reactivity to lignin makes the reaction solution acidic. It was found to be different from the case of alkalinity. Furthermore, when introducing two types of organic compounds to lignin by utilizing the difference in reactivity of such organic compounds, one of these organic compounds is acidic under the alkaline conditions and the other It has been found that the reaction under the conditions results in the formation of a controlled lignin derivative with a certain structure, and the present invention has been achieved with the expectation that the above-mentioned problems can be solved in a remarkable manner.

That is, the present invention is a method for producing lignin derivatives, wherein the production method is different from the first step of reacting lignin with an organic compound, and the reaction product of the first step and the organic compound in the first step. The first and second steps are a method of producing a lignin derivative in which one step is carried out under an acidic condition and the other step is under an alkaline condition, including a second step of reacting the compound.
The present invention will be described in detail below.
In addition, what combined two or more of each preferable form of this invention described below is also a preferable form of this invention.

The method for producing lignin derivatives of the present invention is characterized in that it is a production method capable of producing lignin derivatives having a controlled structure by reacting lignin with two kinds of organic compounds.
One of the two organic compounds to be introduced has sufficient reactivity to lignin under either acidic or alkaline conditions, and the other organic compound is sufficiently acidic under both acidic and alkaline conditions. When these organic compounds are reacted with lignin under conditions in which both of the two organic compounds have reactivity, the organic compounds are randomly bonded to lignin when the organic compounds have various reactivity. It will be done. On the other hand, in the first step, an organic compound having sufficient reactivity (hereinafter also referred to as a first organic compound) is reacted under only one of acidic and alkaline conditions, and thereafter, in the second step The other organic compound (hereinafter also referred to as a second organic compound) is added to the reaction system, and the reverse of the first step is liquid (that is, alkaline if the first step is acidic, the first step If the reaction is carried out under acidic conditions if it is alkaline, in the first step, the first organic compound binds to lignin, and in the second step, the reaction involving the unreacted first organic compound proceeds The reaction is promoted between the second organic compound and the product of the first step. Here, the reactivity of the structural part derived from the first organic compound and the second organic compound, which the product of the first step has, is higher than the reactivity of the structural part derived from lignin and the second organic compound For example, the second organic compound is bound mainly 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 can be controlled by two types of organic compounds, and a lignin derivative having a controlled structure can be obtained.
In addition, two types of organic compounds introduced to lignin have sufficient reactivity under either acidic or alkaline conditions, and the solutions having sufficient reactivity are opposite to each other. In the case of a liquid, it is possible to control the order in which the two organic compounds in the lignin derivative are combined by controlling which of the acidic and the alkaline conditions is performed first. This gives a lignin derivative whose structure is controlled.

The first step is a step of reacting lignin with a first organic compound, and the second step is a reaction of a reaction product of the first step with a second organic compound different from the first organic compound. Process.
The first and second steps are carried out under acidic conditions on one side and alkaline conditions on the other side. Which step of the first step or the second step is carried out under acidic conditions or alkaline conditions depends on the solubility of lignin under acidic or alkaline conditions, the reactivity of organic compounds and the first step, as described later. 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 the first step and the second step are included.

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

By performing the first step, the reaction product of the first step (hereinafter also referred to as modified lignin) to which the above-mentioned reaction site has a structure represented by the following formula (1) and to which an organic compound is bound 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 repetitions of -Y ¹ -X ^1- and is a number of 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 a plurality of benzene rings derived from lignin directly or via a divalent linking group one by one. A plurality of organic compounds may be bonded to at least one benzene ring derived from lignin directly or through a divalent linking group. When n is 1 or more, an organic compound is further bonded to a group derived from an organic compound directly or via a divalent linking group to a benzene ring, directly or via a divalent linking group. . Preferably it is 0-100 as n, More preferably, it is 0-50.

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

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. More preferably, it is a C1-C4 bivalent hydrocarbon group, More preferably, it is a C1 bivalent hydrocarbon group, ie, a methylene group.

As the ^{R 1,} a hydrogen atom, or an alkoxy group having 1 to 18 carbon atoms are preferred. More preferably, it is either a hydrogen atom or an alkoxy group having 1 to 2 carbon atoms.
The monovalent functional group for 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 a 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: monoalkyl amines having 1 to 8 carbon atoms such as ethylamine; dialkyl amines having 2 to 16 carbon atoms such as dimethylamine and diethylamine; C1-C8 monoalkanolamines such as aminoethanol and 2-propanolamine; C2-C16 dialkanolamines such as diethanolamine and diisopropanolamine; C2-C2 such as 2- (methyl) aminoethanol 16 alkyl alkanolamines; alkylene diamines having 2 to 16 carbon atoms such as ethylene diamine and N-methyl ethylene diamine; dialkylene triamines 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 with carbon atoms, such as a benzene ring, a naphthalene ring, and an anthracene ring; thiophene, imidazole, pyrazole, pyridine, indole, carbazole, etc. The heterocyclic ring having 4 to 13 carbon atoms of Among these, an aromatic ring having 6 to 10 carbon atoms and a sulfur atom having a carbon number of 4 to 9 or a nitrogen atom-containing heterocyclic ring composed only of carbon atoms are preferable. More preferably, it is an aromatic ring having 6 carbon atoms, a sulfur atom having 4 carbon atoms, or a nitrogen atom-containing heterocyclic ring composed only of carbon atoms. These may be used alone or in combination of two or more. In addition, said carbon number shall mean the number of carbon which the whole compound has.

The above-mentioned amine compounds are preferably mono-alkanolamines having 1 to 3 carbon atoms, dialkanolamines 2 to 6 carbons, ammonia, urea, amino acids, and aromatic amines. More preferably, they are C1-C3 monoalkanolamines, 2-6 dialkanolamines, ammonia, and urea. Since these compounds are relatively inexpensive, they can be suitably used for industrial production of lignin derivatives. Further, from the viewpoint of the introduction efficiency to lignin, more preferably 2-aminoethanol and diethanolamine, and still more preferably 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. Moreover, what the two molecules of these carboxylic acid group containing compounds couple | bonded and formed the acid anhydride can also be used as a raw material which manufactures the lignin derivative of this invention. In addition, amino acids, such as the above-mentioned glycine and glutamic acid, shall be contained in an amine compound. Further, as described later, compounds having a phenolic hydroxyl group such as salicylic acid, hydroxyphenylacetic acid, hydroxynaphthoic acid, hydroxynaphthaleneacetic acid, etc. are included in phenols.
As said carboxylic acid group containing compound, what has aromatic rings, such as benzoic acid, is preferable. The specific example and the preferable form of the said aromatic ring are as above-mentioned.

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 and the like. In addition, as it mentions later, the compound which has phenolic hydroxyl groups, such as hydroxy benzene sulfonic acid, shall be contained in phenols.
As said sulfonic-acid-group containing compound, what has aromatic rings, such as benzenesulfonic acid, is preferable. The specific example and the preferable form of the said aromatic ring are as above-mentioned.

The above-mentioned 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 phenyl phosphoric acid and the like. In addition, the compound which has phenolic hydroxyl groups, such as a hydroxyphenyl phosphoric acid, shall be contained in phenols so that it may mention later.
As said phosphate group containing compound, what has aromatic rings, such as a phenyl phosphoric acid, is preferable. The specific example and the preferable form of the said aromatic ring are as above-mentioned.

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 is represented by the following formula (2):
R ⁴ -X ² -[(R ² O) _q -R ³ ] _p (2)
(Wherein, 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 is an average added mole number of the oxyalkylene group, and is a number of 1 to 300. It can be represented by).

It is preferable that the alkylene group represented by R ² in said Formula (2) is a C2-C18 alkylene group. More preferably, it is a C2-C8 alkylene group, More preferably, it is a C2-C3 alkylene group. When the alkylene group has 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 “identical or different,” an alkylene group, which means that all of the alkylene groups of R ² O present in the (poly) alkylene glycol compound are the same. It may mean that it may be different.

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

(In the 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 the 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 the total carbon number of R ⁹ is 1 to 8.)
When X ² is a trivalent linking group, examples of the trivalent linking group include nitrogen atoms.

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

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

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

The (poly) alkylene glycol compound is preferably a compound having a (poly) alkylene glycol chain and an aromatic ring. The specific example and the preferable form of the said aromatic ring are as above-mentioned. 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 consisting only of a (poly) alkylene glycol chain and an aromatic ring, (poly) A substituent other than the alkylene glycol chain may be bonded to an aromatic ring.
Examples of the substituent other than the (poly) alkylene glycol chain include an alkoxy group, an amino group, a sulfonic acid group, a carboxylic acid group and the like, and one of these substituents may be bonded to the aromatic ring, Two or more may be combined. For example, although an aromatic (poly) alkylene glycol compound having a hydroxy group as a substituent other than a (poly) alkylene glycol chain will have a phenolic hydroxyl group, as described later, it has such a phenolic hydroxyl group The compounds are included in phenols.
An aromatic (poly) alkylene glycol compound having a benzene ring as an aromatic ring is represented by the following formula (4):

(Wherein, R ¹⁰ represents a hydrogen atom or a substituent other than -X ^2- (R ² O) _q -R ³ (hereinafter, also referred to as a (poly) alkylene glycol chain-containing group) X ² and R ² , R ³ and q are the same as 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), a (poly) alkylene glycol chain-containing group in which X ² is an oxygen atom or a sulfur atom is produced by reacting a (poly) alkylene glycol with a hydroxyl group of phenol or a thiol group of thiophenol be able to.
In the above formula (4), a (poly) alkylene glycol chain-containing group in which X ² is a divalent nitrogen atom-containing group represented by the formula (3-1) is a dialkylaminophenyl alkanol with (poly) alkylene glycol It can be manufactured by adding or the like.
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) is a (poly) alkylene glycol to N-alkylaniline It can be manufactured by adding or the like.
In the above 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 end with respect to the hydroxyl group of phenol. Can be manufactured by
In the above formula (4), the (poly) alkylene glycol chain-containing group having a structure in which X ² is a formula (3-4) can be produced by, for example, reacting benzyl alcohol with 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 above (poly) alkylene glycol compound is an aromatic (poly) alkylene glycol compound, lignin and the aromatic (poly) alkylene glycol compound are the ortho or para position of the (poly) alkylene glycol chain-containing group of the aromatic ring It is preferable to bind at

The phenol is not particularly limited as long as it is a compound having an aromatic ring and a hydrogen atom of the aromatic ring is substituted with a hydroxyl group. The specific example and the preferable form of the said aromatic ring are as above-mentioned. In addition, even if it is a compound applicable to any of the said 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 compound which has phenolic hydroxyl group is It shall be included in phenols.
Examples of the above-mentioned phenols include phenol, cresol, salicylic acid, hydroxyphenylacetic acid, hydroxynaphthoic acid, hydroxynaphthaleneacetic acid, hydroxybenzenesulfonic acid, hydroxyphenyl phosphoric acid, and (poly) alkylene glycol-containing phenolic compounds.
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, but, for example, an aromatic (poly) represented by the above formula (4) compound R ¹⁰ alkylene glycol compound is a hydroxy group, and the like.

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

Among the above non-phenolic compounds, organic compounds having reactivity with lignin under acidic conditions and extremely low reactivity under alkaline conditions include (non-phenolic) carboxylic acid group-containing compounds, Examples thereof include sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, and (poly) alkylene glycol compounds.
Among the above non-phenolic compounds, organic compounds having reactivity with lignin under alkaline conditions and having 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 is used under either acidic or alkaline conditions, a compound having a polar group is reacted under acidic or alkaline conditions in which the lignin becomes water soluble. As a result, in the second step, solubility can be imparted to the modified lignin under acidic or alkaline conditions reverse to the first step, and it 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 a compound having a polar group is reacted with such lignin, 10 g of the modified lignin obtained is dissolved in 100 g of an acidic aqueous solution of pH 1 or an alkaline aqueous solution of pH 12 at 25 ° C. It can be less than .5 g.
The above first organic compound is preferably an amine compound or a compound containing a carboxylic acid group.

The method for reacting lignin and the first organic compound in the first step is not particularly limited, and examples thereof include the methods of (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 via 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, lignin, the first organic compound and the reactive group-containing compound may be simultaneously reacted, or the reaction product obtained after the first organic compound or lignin and the reactive group-containing compound are reacted in advance The substance may be reacted with lignin or the first organic compound.

When the first step is performed under alkaline conditions, the pH of the reaction of lignin with the first organic compound is not particularly limited as long as it is in the alkaline region, but it is preferably pH 8 to 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 basic substance can be used to adjust the pH.
When the first organic compound is a basic compound, the pH of the reaction solution can be made a basic region by adding the first organic compound, but basicity other than the organic compound used for the reaction Substances may be used to adjust pH. The basic substance other than the first organic compound is not particularly limited, and examples thereof include hydroxides of alkali metals such as sodium and the like. The pH of the reaction solution can be measured by a pH meter (pH meter D-51: manufactured by Horiba, Ltd.).

When the first step is carried out under acidic conditions, the pH of the reaction of lignin with the first organic compound is not particularly limited as long as it is in the acidic region, but it is preferably pH 0.1 to 3. More preferably, it is pH 0.5-2. When the first organic compound is a basic or neutral compound, an acid such as sulfuric acid can be used to adjust the pH.
When the first organic compound is an acidic compound, the pH of the reaction solution can be made acidic by adding the first organic compound, but an acid other than the first organic compound used for the reaction The pH may be adjusted using The pH of the reaction solution can be measured by 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 way under acidic conditions. Even in this case, in the first step, the reaction between the lignin and the first organic compound proceeds because the reactivity between the second organic compound and the lignin is low.

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

When a reactive group-containing compound is used in the first step, the reactive group-containing compound is not particularly limited as long as lignin and an organic compound can be bound, but as a reactive group, an aldehyde group, a hydroxyl group, The compound which has an epoxy group etc. is mentioned.
As said 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, lignin or an organic compound is 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 linked structure can be produced. In this case, a modified lignin having a structure in which lignin and an organic compound are bonded via a divalent hydrocarbon group having one more carbon number than R ¹¹ is obtained. 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 It is an atom. When it is a hydrogen atom, modified lignin having a structure in which lignin and an organic compound are linked via a methylene group can be produced.
When R ^{11 in} Formula (6) is a hydrogen atom, the aldehyde compound of Formula (5) is formaldehyde. When R ^{11 in} Formula (5) is a hydrocarbon group having 1 to 3 carbon atoms, the aldehyde compound of Formula (5) becomes acetaldehyde, propionaldehyde, and butanal, respectively.

When the lignin, the organic compound and the reactive group-containing compound are simultaneously reacted in the first step, 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, in the case of reacting lignin or lignin in which a reactive group has been introduced in advance with an organic compound or an organic compound in which a reactive group has been introduced in advance, the reaction temperature is preferably 20 to 120 ° C. More preferably, it is 50-90 ° C. Moreover, it is preferable that the reaction time in this case is 0.5 to 40 hours. More preferably, it is 1 to 20 hours.
When the lignin, the organic compound and the reactive group-containing compound are simultaneously reacted in the first step, the reaction temperature is preferably 20 to 120 ° C. More preferably, it is 50-90 ° C.
Moreover, it is preferable that the reaction time in this case is 0.5 to 40 hours. More preferably, it is 1 to 20 hours.

In the reaction in the first step, lignin or lignin in which a reactive group has been introduced in advance with an organic compound or an organic compound in which a reactive group has been introduced in advance, or lignin, an organic compound and a compound containing a reactive group The solvent to be used is not particularly limited as long as the reaction proceeds, and 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 10000% 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 case where the organic compound or lignin and the reactive group-containing compound are reacted in advance in the method of the above (2), it is preferable to react the organic compound and the reactive group-containing compound in advance .

The reaction of the organic compound with the reactive group-containing compound may be carried out 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 above 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 that 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 of the organic compound with the reactive group-containing compound is as described for the pH in the first step.

The amount of the reactive group-containing compound to be used in the reaction of the organic compound and the reactive group-containing compound 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%.

It is preferable that the reaction temperature of reaction of the said organic compound and reactive group containing compound is 10-60 degreeC. More preferably, it is 20 to 50 ° C.
The reaction time is preferably 0.5 to 10 hours. More preferably, it is 1 to 4 hours.
The solvent used for the reaction of the organic compound and the reactive group-containing compound is not particularly limited, and specific examples and preferable 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 coniferous tree or a broadleaf tree, or may be a herbaceous lignin. In addition, the digestion method is also not particularly limited, and any of alkaline lignin obtained by alkaline digestion, kraft lignin obtained by kraft digestion, acetic acid lignin obtained by acetic acid digestion, and lignin sulfonic acid obtained by sulfite digestion may be used. . It is preferable to select the type of lignin to be used depending on the nature (acidic or alkaline) of the reaction solution of 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 it is water-soluble under alkaline conditions and extremely low in water-solubility under acidic conditions, as described above, acidic conditions can be obtained by introducing an organic compound or the like having a polar group in the first step. Under water 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 carried out under either acidic or alkaline conditions, and in view of the reactivity of the first organic compound, it is acidic or It is preferable because the alkaline conditions can be determined. Water-soluble lignin under such acidic and alkaline conditions includes lignin sulfonic acid.

Although the weight average molecular weight of the lignin is not particularly limited, for example, it is preferable to use lignin having a weight average molecular weight of 1000 to 80000. More preferably, it is lignin of the weight average molecular weight 1500-70,000, More preferably, it is a lignin of the weight average molecular weight 2000-60000.
The weight average molecular weight can be measured using GPC analysis under the conditions described in the examples described later.

The second step of the production method of the present invention is a step in which the reaction product in the first step and the organic compound (second organic compound) different from the organic compound in the first step are reacted. 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, for example, an amine compound And carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, (poly) alkylene glycol compounds, and phenols. Specific examples and preferable examples of the amine compound, the carboxylic acid group-containing compound, the sulfonic acid group-containing compound, the phosphoric acid group-containing compound and the (poly) alkylene glycol compound are as described above.

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

In the first step, 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 is used under acidic conditions When the reaction is performed below, it is preferable to use an amine compound or a phenol as the second organic compound.
The above amine compound has reactivity with lignin and modified lignin under alkaline conditions and has extremely low reactivity under acidic conditions, so at the start of the first step carried out under acidic conditions, the first amine compound The organic compound, lignin and the amine compound as the second organic compound can be added to the reaction system at one time.

In the first step, when the reaction is carried out 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 as the second organic compound, It is preferable to use any of a phosphoric acid group-containing compound, a (poly) alkylene glycol compound and a phenol.
The (non-phenolic) carboxylic acid group-containing compound, the sulfonic acid group-containing compound, the phosphoric acid group-containing compound and the (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 are collectively added to the reaction system at the start of the first step performed under alkaline conditions because the reactivity under the reaction is extremely low. Can.

Since the above-mentioned phenols have reactivity with lignin and modified lignin under acidic and alkaline conditions, the conditions of the second step may 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 to which the second organic compound is bonded is not particularly limited and is a carbon atom of a benzene ring derived from lignin to which the first organic compound is bonded in the first step Also, 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. Also, there are a plurality of reaction sites in one molecule of reaction product in the first step, and a plurality of second organic compounds may react with one molecule of reaction product in the first step, but in the second step The number of second organic compounds to be reacted with the reaction product of the first step is not particularly limited as long as at least one second organic compound can be reacted.

By performing the second step, the lignin derivative of the present invention has a structure in which the reaction site is represented by the following formula (7) or (8).

(Wherein, R ¹² represents a hydrogen atom, an alkoxy group, or a group derived from the first organic compound bonded to a benzene ring directly or via a divalent linking group, and a plurality of R ¹² may be bonded to a 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 M represents a number of repetition of -X ³ -W ^1- and is a number from 0 to 200. R ¹ , X ¹ , Y ¹ , Z and n each represent a group represented by the formula (II) It is the same as R ¹ , X ¹ , Y ¹ , Z and n in ¹ ).
The alkoxy group, divalent linking group and group derived from the first organic compound in R ¹² in the above formula (7) are the alkoxy group in the above formula (1), divalent linking group and the first organic compound derived group It is the same as the group.
When X ³ is a divalent linking group different from Y ¹ and W ¹ , specific and preferable examples of the divalent linking group are the same as the divalent linking group in X ¹ described above.
Preferably it is 0-100 as m, More preferably, it is 0-50.

In the second step, if the reactivity with the second organic compound is higher with respect to the group derived from the first organic compound introduced in the first step than the benzene ring derived from lignin, the above formula (8) A lignin derivative having a reaction site represented by) is mainly produced. The lignin derivative having a reaction site represented by the above formula (8) is a lignin whose structure is controlled because the first organic compound and the second organic compound are introduced at a specific position relative to lignin. It becomes a derivative.

As a combination of reaction conditions, lignin and organic compound in the first step and the second step of the present invention, for example, a combination of the following (a) and (b) is preferable.
(A) First step: Using at least one selected from the group consisting of lignin sulfonic acid, alkali lignin, kraft lignin and acetic acid lignin as lignin, using an amine compound as the first organic compound, under alkaline conditions Do the reaction with
Second step: a second organic compound 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: using lignin sulfonic acid as lignin and (non-phenolic) carboxylic acid group-containing compound, sulfonic acid group-containing compound, phosphoric acid group-containing compound and (poly) 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: A reaction is performed under alkaline conditions using an amine compound or a phenol as a second organic compound.

In the case of the above (a), the amine compound as the first organic compound has low reactivity under acidic conditions, so by making the reaction solution acidic, side reactions involving the amine compound in the second step It can be suppressed. That is, in the second step, it is possible to suppress that the first organic compound and the second organic compound are randomly bonded to the reaction product of the first step, and the lignin derivative whose structure is controlled. You can get
Further, as the second organic compound, since the reactivity under alkaline conditions is low, (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, at the start of the first step, the first organic compound, lignin and the second organic compound are collectively contained in the reaction system. Can be added to
Moreover, in the case of the above (a), by introducing a polar group into lignin with an amine compound, it is possible to impart water solubility to lignin under acidic conditions, so lignin having extremely low water solubility under acidic conditions Can even be used.

In the case of the above (b), the (non-phenolic) carboxylic acid group-containing compound, the sulfonic acid group-containing compound, the phosphoric acid group-containing compound and the (poly) alkylene glycol compound as the first organic compound are under alkaline conditions In the second step, by making the reaction solution alkaline, side reactions involving these compounds can be suppressed in the second step. That is, in the second step, it is possible to suppress that the first organic compound and the second organic compound are randomly bonded to the reaction product of the first step, and the lignin derivative whose structure is controlled. You can get
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, at the start of the first step, the first organic compound, lignin and the second organic compound are collectively contained in the reaction system. Can be added to

The pH of the reaction solution in the case where the second step is carried out under acidic or alkaline conditions is the same as the pH of the reaction solution in the first step.

The method for reacting the reaction product of the first step and the second organic compound in the second step is not particularly limited, and examples thereof include the methods (3) and (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 and the second organic compound may be used as they are. React. As a result, 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. In addition, the reaction product of the first step, the second organic compound and the reactive group-containing compound may be reacted simultaneously, and the second organic compound or the reaction product of the first step and the reactive group-containing compound The reaction product obtained 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 simultaneously.
The reactive group-containing compound is as described in the first step.
The other reaction conditions in the second step are the same as the reaction conditions in the first step.

The lignin derivative obtained by the production method of the present invention preferably has a weight average molecular weight of 1,000 to 100,000. When the lignin derivative has such a weight average molecular weight, it becomes more suitable as a cement admixture to be described later. The weight average molecular weight of the lignin derivative is more preferably 1,500 to 9,000, and still more preferably 2,000 to 8,000.
The weight average molecular weight of the lignin derivative can be measured using GPC under the conditions described in the examples described later.

The lignin derivative obtained by the production method of the present invention can enhance the fluidity of the cement composition by adding it to the cement composition by having a lignin-derived structure and an organic compound-derived structure. It can be suitably used as a cement admixture. Such a cement admixture containing the lignin derivative of the present invention is also one of the present invention, and a cement composition comprising the cement admixture and a cement is also one of the present invention. It is.
When a lignin-based 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 type of 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. The hydrophilicity is improved, and the amount of entrained air can be reduced.

As the above cement composition, one containing cement, water, fine aggregate, coarse aggregate and the like is preferable, and as cement, Portland cement (normal, early strength, super early strength, moderate heat, sulfate resistance, And each low alkali type; various mixed cement (blast furnace cement, silica cement, fly ash cement); white portland cement; alumina cement; super rapid curing cement (1 clinker rapid curing cement, 2 clinker rapid curing cement, magnesium phosphate cement ; Cement for grout; Oil well cement; Low heat generation cement (low heat generation blast furnace cement, low heat generation blast furnace cement mixed with fly ash, cement containing high belite), super high strength cement, cement-based solidifying material, eco cement (urban waste) Seme manufactured using one or more of incineration ash and sewage sludge incineration ash as raw materials 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-mentioned aggregate, in addition to gravel, crushed stone, granulated slag, regenerated aggregate and the like, silica, clay, zircon, high alumina, silicon carbide, graphitic, chromium, black, magnesia, etc. Fireproof aggregate etc. are mentioned.

The unit amount of water per 1 m ^{3 of} cement composition, the amount of cement used and the water / cement ratio (mass ratio) are, for example, a unit water amount of 100 to 185 kg / m ³ , a cement amount of 200 to 800 kg / m ³ , water / It is preferable to set the cement ratio (mass ratio) to 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 in a total amount of 100% by mass of the cement mass in terms of solid content. It is preferable to set so as to be 0.01 to 10% by mass. If the amount is less than 0.01% by mass, the performance may not be sufficient. If the amount is more than 10% by mass, the effect may be substantially stopped, which may be economically disadvantageous. More preferably, it is 0.02-8 mass%, More preferably, it is 0.05-6 mass%.

The process for producing lignin derivatives according to the present invention is a lignin derivative having the above-described constitution, wherein two or more organic compounds are introduced to lignin, and a lignin derivative having a controlled structure is obtained. It can be used industrially suitably as a manufacturing method.

FIG. 2 is a view showing the results of capillary electrophoresis of the amine-modified lignin (1) and lignin derivative (1) obtained in Example 1. FIG. 6 is a view showing the results of capillary electrophoresis of the amine-modified lignin (2) and lignin derivative (2) obtained in Example 2.

EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited to these examples. In addition, unless there is particular notice, "part" shall mean "weight part" and "%" shall mean "mass%."

<Gel permeation chromatography (GPC)>
The weight average molecular weight of the lignin derivative was measured by the following measurement method.
Device: Waters Alliance 2695 (manufactured by Waters)
Analysis software: Empower Professional + GPC option (made by Waters)
Column: TSK gel guard column α (internal diameter 6.0 × 40 mm) + α5000 + α4000 + α3000 (each internal diameter 7.8 × length 300 mm) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Solvent: Solution obtained by mixing 29 g of sodium hydroxide and 3600 g of acetonitrile in 14371 g of 100 mM boric acid aqueous solution: 1.0 ml / min
Sample introduction amount: 100 μl
Sample concentration: 0.5 mass%
Detector: Differential Refractometer (RI) Detector (Waters, Waters 2414)
Calibration curve: Tosoh polyethylene glycol (Mp = 300000, 200,000, 107000, 50000, 27700, 11840, 6450, 1470, 1010, 400) is used as a standard substance, and is created in a cubic equation based on Mp and elution time

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

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 separable flask was heated to 40 ° C., and 240.5 g of a 37% formaldehyde solution was added dropwise over 1 hour while 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 2 HMAE 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% aqueous NaOH solution, and reaction 1- 0.8 g of the solution of 2- (hydroxymethyl) aminoethanol 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. Thereafter, it was cooled to obtain amine-modified lignin (1). The weight average molecular weight of the obtained product (amine-modified lignin (1)) was 45,600.

[Reaction 1-3]: Reaction of amine-modified lignin with PhO-EO 20 36.0 g of an aqueous solution of amine-modified lignin (1) obtained in 1-2, PhO-EO 20 (20 molar adduct of phenol with ethylene oxide) 3. 6 g and 0.9 g of 37% aqueous formaldehyde solution were charged in a separable flask, and 1.1 g of sulfuric acid was added thereto to adjust 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 with a 30% aqueous sodium hydroxide solution to obtain lignin derivative (1). The weight average molecular weight of the obtained product (lignin derivative (1)) was 51,200.

Example 2
[Reaction 2-1]: Reaction of 2HMAE with Kraft lignin 48.0 g of kraft lignin (weight-average molecular weight 17700, manufactured by ALDRICH), 138.8 g of deionized water, 16.8 g of a 30% aqueous solution of NaOH and reaction 1-1 The solution (36.4 g) of the solution of 2- (hydroxymethyl) aminoethanol 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 obtained amine modification | denaturation lignin (2). The weight average molecular weight of the obtained product (amine-modified lignin (2)) was 24,800.

[Reaction 2-2]: Reaction of amine-modified lignin (2) with PhO-EO 20 26.7 g of an aqueous solution of amine-modified lignin (2) obtained in 2-1, PhO-EO 20 (20 moles of ethylene oxide adduct of phenol 1) 12.4 g and 3.1 g of 37% aqueous formaldehyde solution were charged in a separable flask, and 3.0 g of sulfuric acid was added thereto to adjust 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 with 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 35,100.

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 modification obtained in the reaction 2-1 The results of capillary electrophoresis of lignin (2) and the lignin derivative (2) obtained in reaction 2-2 are shown in FIG. 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. The longer the retention time in electrophoresis measurement, the higher the anionicity. The amine-modified lignin (1) and (2) obtained in Reaction 1-2 and Reaction 2-1 is shifted to a lower anionic side than sodium lignin sulfonate before reaction or Kraft lignin, and this result From these results, it was confirmed that uncharged 2-aminoethanol was added to lignin. In addition, lignin derivatives (1) and (2) obtained in Reaction 1-3 and Reaction 2-2 respectively shift to a lower side of anionicity than amine-modified lignin (1) or (2). It was confirmed from this result that uncharged PhO-EO20 was added to amine-modified lignin (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 with no lignin derivative added. The results are shown in Table 1.

Mortar test
The mortar test was performed under the environment of a temperature of 20 ° C. ± 1 ° C. and a relative humidity of 60% ± 15%.
The mortar composition was C / S / W = 500/1350/250 (g).
However,
C: Ordinary portland cement (made by Pacific Cement Co., Ltd.)
S: Standard sand for cement strength test (made by Cement Association)
W: Ion exchange aqueous solution of sample and antifoaming agent is added. For W, 40% by mass of antifoaming agent MA-404 (manufactured by BASF Japan Ltd.) is added to the solid content of each sample, and ion exchange water is further added. It was determined quantitatively 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.
Preparation of the mortar was performed as follows according to JIS-R5201-1997. C and W were charged using a Hobart type mixer (Model No. N-50; manufactured by Hobart Co., Ltd.), and kneading was performed for 30 seconds at one speed. Further, while kneading at one speed, S was charged over 30 seconds.
After the addition of S, after kneading for 30 seconds at 2nd speed, the mixer was stopped, the mortar was scraped off for 15 seconds, and then left to stand for 75 seconds. After standing for 75 seconds, kneading was further carried out at 2nd speed for 60 seconds to prepare a mortar.
The obtained mortar is transferred from the kneading container to a 1-L polyethylene container, and after stirring 10 times each with the spatula, a mini slump cone (JIS micro concrete slump cone) immediately placed on a flow measurement plate (30 cm × 30 cm), upper end inner diameter 50mm, lower end inner diameter 100mm, height 150mm) half stuffing and thrusting with 15 sticks, mortar is further stuffed until the fullness of mini slump cones and pokes with 15 sticks, finally compensates for the shortage, mini slump cones Smoothed the surface of the. Then, 5 minutes and 30 seconds after the mixer was first started, the mini slump cone is pulled up vertically, and the diameter of the spread mortar (the diameter of the longest portion (long diameter) and the diameter of the portion 90 ° to the long diameter 2) was measured, and the average value was made into the mortar flow value. The mortar flow value indicates that the larger the numerical value, the higher the fluidity, that is, the better the workability, and the evaluation as a dispersant indicates that the dispersion performance is excellent.

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 (2)

A method for producing lignin derivatives, 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.
First step and the second step, one under acidic conditions, are performed by the alkaline conditions of the other,
A method for producing a lignin derivative, wherein the combination of reaction conditions, lignin and organic compound in the first step and the second step is any combination of the following (a) or (b) :
(A) First step: Using at least one selected from the group consisting of lignin sulfonic acid, alkali lignin, kraft lignin and acetic acid lignin as lignin, using an amine compound as the first organic compound, under alkaline conditions Do the reaction with
Second step: at least one compound selected from the group consisting of carboxylic acid group-containing compounds, sulfonic acid group-containing compounds, phosphoric acid group-containing compounds, (poly) alkylene glycol compounds and phenols as the second organic compound The reaction is carried out under acidic conditions using
(B) First step: A group comprising a 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 using lignin sulfonic acid as lignin The reaction is carried out under acidic conditions using at least one compound selected from the group consisting of
Second step: A reaction is performed under alkaline conditions using an amine compound or a phenol as a second organic compound. The method for producing a lignin derivative according to claim 1, wherein the lignin is a water-soluble lignin under acidic and alkaline conditions.

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