JP2016121321A - Lignin derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel lignin derivative.SOLUTION: A lignin derivative has a structure in which a lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bound to each other through a divalent linking group.SELECTED DRAWING: None

Description

The present invention relates to a lignin derivative. More specifically, the present invention relates to a lignin derivative obtained from lignin obtained from a plant as a raw material and usable for applications such as a cement admixture.

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 oxidases such as laccase and peroxidase to form phenoxy radicals, which form radical couplings in an indefinite form, resulting in a complex three-dimensional network structure. 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 in order to industrially use lignin that can be obtained at low cost, for example, producing a derivative in which a structural unit having a polycarboxylic acid or polyalkylene glycol chain is introduced into lignin, It is disclosed that it is used as a cement dispersant (see Patent Documents 1 to 3).

Special table 2008-514402 gazette JP 2011-184230 A JP 2011-240224 A

As described above, derivatives using lignin as a raw material have been produced and are being studied for industrial use. However, lignin derivatives are not yet fully studied, and there is room for further development of derivatives. . There is great expectation for the use of lignin, which is a raw material derived from nature, and can be obtained at low cost, for industrial use, and it is preferable to develop a derivative having a new structure in consideration of future development for various uses.

The present invention has been made in view of the above-described present situation, and an object thereof is to provide a novel lignin derivative.

As a result of various studies on novel lignin derivatives, the present inventor has found a structure in which lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bonded via a divalent linking group. We succeeded in producing a novel lignin derivative. Furthermore, the present inventors have found that this lignin derivative is useful as a cement admixture, and have reached the present invention.

That is, the present invention is a lignin derivative having a structure in which lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bonded via a divalent linking group.
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.

In the lignin derivative of the present invention, lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain (hereinafter also referred to as (poly) alkylene glycol chain-containing amino group) are divalent linking groups. It has a structure connected through. The above lignin derivative disperses cement particles by adsorbing lignin sites to cement particles and causing steric repulsion between (poly) alkylene glycol chains bonded to the lignin adsorbed to the cement particles. The fluidity of can be improved. In addition, the cement composition has an effect such that workability is improved when air is mixed therein. On the other hand, when the amount of air is too large, the strength is lowered. Since the lignin derivative of the present invention has such a configuration, the hydrophilicity of the lignin is improved. In addition to the improvement of the fluidity of the cement composition, the entrained air amount of the cement composition is reduced. You can also.

As long as the lignin derivative of the present invention has such a structure, the position at which the lignin and the divalent linking group are bonded is not particularly limited. The lignin molecule is a large molecule with a complex three-dimensional network structure, and there are multiple reaction sites in one lignin molecule that can bind to a (poly) alkylene glycol chain-containing amino group via a divalent linking group. To do. For this reason, a plurality of (poly) alkylene glycol chain-containing amino groups can be bonded to one lignin molecule via a divalent linking group, but the lignin derivative of the present invention has at least one (poly) alkylene glycol chain. The number of the (poly) alkylene glycol chain-containing amino group bonded to the lignin is not particularly limited as long as the containing amino group is bonded via a divalent linking group. In addition, the position at which the (poly) alkylene glycol chain-containing amino group is bonded via a divalent linking group at the reaction site in the lignin molecule is not particularly limited, and divalent linking is performed at the same position at all reaction sites. The (poly) alkylene glycol chain-containing amino group may be bonded via a group, or may be bonded at different positions.

In the structure of the lignin derivative of the present invention, a reaction site in which an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain is bonded via a divalent linking group is represented by the following formula (1). It is preferable that it is a structure represented.

(In the formula, R ¹ represents a hydrogen atom or an alkoxy group, and a plurality of them may be bonded to the benzene ring. X represents a divalent linking group. Y represents 1 having a (poly) alkylene glycol chain. Represents an amino group derived from a secondary or secondary amine compound, and Z represents a hydrogen atom or a monovalent functional group.)
The lignin derivative having a (poly) alkylene glycol chain disclosed in Patent Documents 1 and 3 is manufactured by a method of introducing a (poly) alkylene glycol chain into a lignin-derived thiol group. Since the number is not large, the number of (poly) alkylene glycol chains that can be introduced is limited. Moreover, since the lignin derivative having a (poly) alkylene glycol chain of Patent Document 2 is produced by a method of introducing a (poly) alkylene glycol chain into a hydroxyl group derived from lignin, it is accompanied by the introduction of the (poly) alkylene glycol chain. Thus, the hydroxyl groups derived from lignin are reduced, and the ability of the lignin derivative to adsorb to cement particles is reduced. In contrast, the lignin derivative in which the structure of the reaction site in which the (poly) alkylene glycol chain-containing amino group is bonded via a divalent linking group is represented by the above formula (1) retains the lignin-derived hydroxyl group. Since the (poly) alkylene glycol chain-containing amino group is introduced, it is a derivative having further improved dispersibility without reducing the inherent adsorption ability of lignin.

In the above formula (1), the position at which the lignin-derived benzene ring at the reaction site of the lignin derivative is bonded to the divalent linking group represented by X is not particularly limited, but among the multiple reaction sites of the lignin derivative At least one is preferably bonded to a divalent linking group represented by X at the ortho position of the hydroxyl group.

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 lignin derivative has a plurality of structures represented by the above formula (1), and R ¹ , X and Y in the plurality of structures may be the same or different.

The divalent linking group in the lignin derivative of the present invention is not particularly limited, and may be a hydrocarbon group or a group containing atoms other than carbon and hydrogen. Examples of the group containing atoms other than carbon and hydrogen include nitrogen atom-containing groups. As a nitrogen atom containing group, following formula (2-1) and (2-2);

(R ² and R ³ are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group. Q represents a trivalent hydrocarbon group having 1 to 5 carbon atoms.) Can be mentioned. When R < ² >, R < ³ > is a monovalent hydrocarbon group, a C1-C5 hydrocarbon group is preferable.
Among these, 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.
It is preferable that the divalent linking group represented by X in the above formula (1) also has such a structure.

In the above formula (1), the amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain represented by Y is a primary or secondary amine compound having the following (poly) alkylene glycol chain: The amino group is preferably derived from.

In the present invention, the primary or secondary amine compound having a (poly) alkylene glycol chain is not particularly limited as long as it is a compound having at least one (poly) alkylene glycol chain and one primary or secondary amino group.
Examples of the primary or secondary amine compound having the (poly) alkylene glycol chain include the following formula (3);

(R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom, a (poly) alkylene glycol chain-containing group, or a hydrocarbon group having a C 1-8 main chain which may have a substituent. It is preferable that at least one of R ⁴ and R ⁵ is a (poly) alkylene glycol chain-containing group.

The (poly) alkylene glycol chain-containing group is a substituent containing a (poly) alkylene glycol chain in the structure, and includes a substituent consisting only of a (poly) alkylene glycol chain.
The (poly) alkylene glycol chain-containing group has the following formula (4);

_{^{-A- (R 6 O) n -B}} (4)

(In the formula, A represents a direct bond or a divalent linking group. B represents a hydrogen atom or a monovalent organic group. R ⁶ is the same or different and represents an alkylene group. N represents oxy. It represents an average added mole number of an alkylene group and is a number of 1 to 300).

In the above formula (4), the alkylene group represented by R ⁶ 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 (4), R ⁶ represents an alkylene group “same or different”, and this is represented by n R ⁶ O alkylene groups present in the (poly) alkylene glycol chain-containing group. It means that they may all be the same or different.

In the above formula (4), when A is a divalent linking group, examples of the divalent linking group include a hydrocarbon group having a main chain having 1 to 8 carbon atoms. The hydrocarbon group having a main chain having 1 to 8 carbon atoms may have a substituent, and the substituent is not particularly limited, but is an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a carboxylic acid group. Etc. Moreover, the carbon atom of the hydrocarbon group having a main chain of 1 to 8 carbon atoms may be substituted with a hetero atom such as a sulfur atom.

In the above formula (4), when B is a monovalent organic group, examples of the monovalent organic group include hydrocarbon groups having 1 to 30 carbon atoms. Among these, a C1-C4 hydrocarbon group is preferable.
In the above formula (4), n is preferably 1 to 300. More preferably, it is 2-250, More preferably, it is 5-200.

The hydrocarbon group having a main chain of 1 to 8 carbon atoms which may have a substituent in R ⁴ or R ⁵ is not particularly limited, but is preferably an alkyl group having a main chain of 1 to 8 carbon atoms. , An alkenyl group. More preferably, it is an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, or a tert-butyl group, and more preferably an alkyl group having 1 to 3 carbon atoms such as an ethyl group. It is an alkyl group.

Although it does not restrict | limit especially as said substituent, A hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, an amide group, a thiol group etc. are mentioned. The substituent is preferably a hydroxyl group, an amino group, or a thiol group.

The primary or secondary amine compound having a (poly) alkylene glycol chain in the present invention may be a primary amine compound in which one (poly) alkylene glycol chain-containing group is bonded to an amino group, and (poly) alkylene. A secondary amine compound in which two glycol chain-containing groups are bonded to an amino group may be used, and a (poly) alkylene glycol chain-containing group and a main chain having 1 to 8 carbon atoms which may have the above substituents. A secondary amine compound in which each hydrocarbon group is bonded to an amino group may be used.
The primary or secondary amine compound having the (poly) alkylene glycol chain is preferably a primary amine compound in which one (poly) alkylene glycol chain-containing group is bonded to an amino group.

When A in the above formula (4) is a direct bond, for example, as a primary amine compound having a (poly) alkylene glycol chain, the following formula (5);

(Wherein, ^{R 6} is .R ⁷ is the same as ^{R 6} in formula (4) is a hydrogen atom, .m representing a hydrocarbon group or an amino group having 1 to 30 carbon atoms, the average oxyalkylene group Represents the number of added moles, and is a number of 1 to 300.).
The primary amine compound having the (poly) alkylene glycol chain is preferably the following formula (6);

(Wherein, ^{R 7} and m are the (5 .R ⁸ is the same as ^{R 7} and m is in) the same or different and each represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms.) Table with And the like. The hydrocarbon group for R ⁷ is not particularly limited, and examples thereof include an alkyl group and an aromatic hydrocarbon group. R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms. When m R ⁸ in the compound represented by the above formula (6) is all the same, R ⁸ is preferably a hydrogen atom.

When m R ⁸ in the compound represented by the above formula (6) is different, the compound represented by the above formula (6) is preferably the following formula (7);

(In the formula, x is a number of 1 to 200. y is a number of 1 to 100. R ⁹ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.) It is a compound represented by these. As said R < ⁹ >, a C1-C6 alkyl group is preferable, More preferably, it is a methyl group.
As x, 1-200 are preferable, More preferably, it is 1-180, More preferably, it is 1-160.
As y, 1-100 are preferable, More preferably, it is 1-70, More preferably, it is 1-40.
Most preferably, the primary amine compound having the (poly) alkylene glycol chain is Jeffamine (registered trademark) in which R ⁹ is a methyl group, x is 19 and y is 3 in the compound represented by the formula (7). In the compound represented by M-1000 and the above formula (7), R ⁹ is a methyl group, x is 31, and y is 10, which is Jeffamine (registered trademark) M-2070.

When the primary amine compound having the (poly) alkylene glycol chain is a compound represented by the above formula (5), a commercially available product may be used. For example, as described in JP-T-8-505082, An alkylene oxide addition reaction to an amine compound similar to the method, or a product prepared by a reaction of a (poly) alkylene glycol with an amine compound similar to the method described in JP-T-2008-543955 may be used. .

Although it does not restrict | limit especially as an amine compound used for manufacture of the primary or secondary amine compound which has the said (poly) alkylene glycol chain | strand, C1-C8 monoalkylamines, such as ethylamine, dimethylamine, diethylamine Dialkylamines having 2 to 16 carbon atoms such as: monoalkanolamines having 1 to 8 carbon atoms such as 2-aminoethanol and 2-propanolamine; dialkanolamines having 2 to 16 carbon atoms such as diethanolamine and diisopropanolamine; 2 A C2-C16 alkyl alkanolamine such as (methyl) aminoethanol; a C2-C8 diaminoalkanol such as 1,3-diamino-2-propanol; 1- (2-hydroxyethyl) piperazine; _{-C 2 H 4 -NH-C 2} H 4 -N ₂ or _{HO-C 2 H 4 - (} NHC 2 H 4) Compounds satisfying the n-NH _2; ethylenediamine, having 2 to 16 carbon atoms, such as N- methyl-ethylenediamine alkylenediamines; bis (2-aminoethyl) such as an amine Examples thereof include dialkylene triamines having 2 to 16 carbon atoms; carbamide compounds having 1 to 8 carbon atoms such as urea; and aminoalkanethiols having 1 to 8 carbon atoms such as cysteamine.

The (poly) alkylene glycols are not particularly limited, but (poly) alkylene glycols such as (poly) ethylene glycol; alkoxy (poly) alkylene glycols such as methoxy (poly) ethylene glycol; having an ethylenically unsaturated group (Poly) alkylene glycol; (Poly) alkylene glycol having an epoxy group and the like can be mentioned.

Although it does not restrict | limit especially as said alkylene oxide, The specific example and preferable example of an alkylene group are the same as that of the alkylene group in the above-mentioned formula (4).

When A in the above formula (4) is a hydrocarbon group having a main chain of 1 to 8 carbon atoms and a divalent linking group in which the carbon atom is substituted with a sulfur atom, (poly) alkylene glycol As the primary amine compound having a chain, the following formula (8);

^{(Wherein, R} 6, n is ^{.R 10, R 11} is the same as ^R 6, n of formula (4) may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a hydroxyl group, R ¹² represents a hydrogen atom or a monovalent organic group, p is a number from 1 to 4, and q is a number from 2 to 5. Preferably there is. In R ¹⁰ and R ¹¹ , “same or different” means that a plurality of R ¹⁰ and R ¹¹ present in the compound represented by the formula (8) may be the same or different. In addition, it means that R ¹⁰ and R ¹¹ may be the same or different. Examples of the monovalent organic group for R ¹² include a hydrocarbon group having 1 to 30 carbon atoms.
Among the compounds represented by the above formula (8), the following formula (9);

^{(Wherein, R 6, R 12, n} , p, q is the formula ^{(8), R 6, R} 12, n, p, is the same as the q ^{.R 13} is a hydrogen atom, 1 to carbon atoms 2 represents an alkyl group and a hydroxyl group.).
R ¹² is preferably a hydrogen atom. R ¹³ is preferably a hydrogen atom, a methyl group or a hydroxyl group, more preferably a hydrogen atom or a methyl group. As said p, it is preferable that it is the number of 1-2. The q is preferably a number from 2 to 4.

When the primary amine compound having the (poly) alkylene glycol chain is a compound represented by the above formula (8), for example, an amine compound having a thiol group and (poly) alkylene glycols having an ethylenically unsaturated group A primary amine compound having a (poly) alkylene glycol chain can be produced by an ene-thiol reaction with or a reaction of an amine compound having a thiol group with a (poly) alkylene glycol having an epoxy group.

As an amine compound which has the said thiol group, C1-C8 amino alkane thiol etc. which may have substituents, such as carboxylic acid groups, such as cysteamine and cysteine, etc. are mentioned, for example.
Examples of the (poly) alkylene glycols having an ethylenically unsaturated group include (poly) ethylene glycol monovinyl ether, (poly) propylene glycol monovinyl ether, (poly) ethylene glycol mono (meth) allyl ether, (poly) Propylene glycol mono (meth) allyl ether, (poly) ethylene glycol mono (3-methyl-3-butenyl) ether, (poly) propylene glycol mono (3-methyl-3-butenyl) ether, methoxy (poly) ethylene glycol ( Formula (10) below, such as (meth) allyl ether;

(Wherein, r is the number a is ^{.R 6, R 12,} n of 0-3, ^{R 6, R 12,} is similar to the n ^{.R 14} is a hydrogen atom or a carbon atoms of the formula (8) Represents an alkyl group of 1 to 2).

Examples of the (poly) alkylene glycol having an epoxy group include the following formula (11) such as (poly) ethylene glycol monoglycidyl ether and (poly) propylene glycol monoglycidyl ether;

(Wherein, s ^{is, .R} 6, ^{R 12} is the number of 1 to 4, n ^{is, R} 6, ^{R 12,} is the same as n. Of formula (8)), and compounds represented by the .

In the lignin derivative of the present invention, the weight of the primary or secondary amine compound having a (poly) alkylene glycol chain bonded to 1000 g of lignin via a divalent linking group is preferably 10 to 100,000 g. By adding a primary or secondary amine compound having a (poly) alkylene glycol chain having such a weight, a hydroxyl group derived from a lignin site having adsorbability and a (poly) alkylene glycol chain-containing amino group having dispersibility Becomes a preferred ratio, and the fluidity to the cement composition can be more sufficiently improved. The weight of the primary or secondary amine compound having a (poly) alkylene glycol chain is more preferably 50 to 50000 g, still more preferably 100 to 10000 g, particularly preferably 250 to 4000 g, and most preferably 400. ~ 2500g.

The lignin derivative 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 described later. The weight average molecular weight of the lignin derivative is more preferably 1500 to 80000, and still more preferably 2000 to 60000.
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 used as a raw material for the lignin derivative of the present invention is not particularly limited, and may be a woody lignin derived from coniferous trees or hardwoods, 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. . In the lignin derivative of the present invention, instead of introducing a (poly) alkylene glycol chain-containing amino group using a functional group such as a lignin-derived hydroxyl group or sulfonic acid group, the type of lignin-derived functional group used as a raw material Since the amino group can be introduced without depending on the amount, lignin obtained by various cooking methods can be used. The lignin used as the raw material for the lignin derivative is preferably alkaline lignin, kraft lignin, or acetic acid lignin.

Although the weight average molecular weight of the lignin used as the raw material of the lignin derivative of this invention is not specifically limited, For example, it is preferable to use a lignin with a weight average molecular weight of 1000-80000. More preferred is a lignin having a weight average molecular weight of 1500 to 60000, and still more preferred is a lignin having a weight average molecular weight of 2000 to 40000.
The weight average molecular weight can be measured by the GPC analysis method under the conditions described in Examples described later.

The present invention is also a lignin derivative obtained by reacting lignin, a primary or secondary amine compound having a (poly) alkylene glycol chain, and an aldehyde compound as raw materials.
By reacting lignin, a primary or secondary amine compound having a (poly) alkylene glycol chain and an aldehyde compound as raw materials, lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain; A lignin derivative bound to can be obtained. In addition, the above reaction is preferably a reaction in which lignin and a primary or secondary amine compound having a (poly) alkylene glycol chain are combined by a condensation reaction using an aldehyde compound. A lignin derivative obtained by such a reaction and having a structure in which a (poly) alkylene glycol chain-containing amino group is bound to a lignin via a divalent linking group is a compound that has not been known so far, as described above. It is.
A method capable of producing such a new lignin derivative, that is, a method of producing a lignin derivative using lignin, a primary or secondary amine compound having a (poly) alkylene glycol chain and an aldehyde compound as raw materials, is also provided. It is one of the present inventions. The structure of the reaction site of the lignin derivative produced by the production method of the present invention is preferably a structure represented by the above formula (1).
The lignin and primary or secondary amine compound having a (poly) alkylene glycol chain used in the method for producing a lignin derivative are the same as those described above, and the primary or secondary amine having a (poly) alkylene glycol chain. Preferred compounds are the same as those described above.

The aldehyde compound is represented by the following formula (12);
R ¹⁵ —CHO (12)
(Wherein R ¹⁵ represents a hydrogen atom or a monovalent hydrocarbon group). When a compound having such a structure is used as the aldehyde compound, a primary or secondary amine compound having a lignin or (poly) alkylene glycol chain is represented by the following formula (13);

(Wherein, R ¹⁵ is the same as R ¹⁵ is of formula (12).) Through an intermediate group introduced represented by, primary or secondary with lignin and (poly) alkylene glycol chain A lignin derivative having a structure in which an amino group derived from an amine compound is bonded via a divalent hydrocarbon group can be produced.
In this case, a lignin derivative having a structure in which lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bonded via a divalent hydrocarbon group having 1 more carbon than R ¹⁵ It becomes.

In the formula (12), R ¹⁵ 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 lignin derivative having a structure in which lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bonded via a methylene group can be produced.
When R ^{15 in} formula (12) is a hydrogen atom, the aldehyde compound in formula (12) is formaldehyde. When R ^{15 in} Formula (12) is a hydrocarbon group having 1 to 3 carbon atoms, the aldehyde compound in Formula (12) is acetaldehyde, propionaldehyde, or butanal, respectively.

More preferably, the method for producing a lignin derivative of the present invention further comprises a step of producing a primary or secondary amine compound having a (poly) alkylene glycol chain.
That is, a first step for producing a primary or secondary amine compound having a (poly) alkylene glycol chain, and lignin, a primary or secondary amine compound having a (poly) alkylene glycol chain obtained by the first step. And the manufacturing method of a lignin derivative including the 2nd process of manufacturing a lignin derivative using an aldehyde compound as a raw material is also one of this invention.

The first step is not particularly limited, but is a step of producing a primary or secondary amine compound having a (poly) alkylene glycol chain using an amine compound and an alkylene oxide or (poly) alkylene glycol as raw materials. It is preferable.

The amine compound and the (poly) alkylene glycol are not particularly limited, but specific examples include the amine compound and (poly) used for the production of the primary or secondary amine compound having the (poly) alkylene glycol chain. The same as alkylene glycols.
In the first step, when a primary or secondary amine compound having a (poly) alkylene glycol chain is produced using an amine compound and an alkylene oxide as raw materials, the amine compound is preferably an amino alcohol.
Examples of the amino alcohol include the monoalkanolamine, dialkanolamine, diaminoalkanol, 1- (2-hydroxyethyl) piperazine, and the chemical formula HO—C ₂ H ₄ —NH—C ₂ H ₄ —NH ₂ or HO—C. _{2 H 4 - (NHC 2 H} 4) compounds satisfying n-NH ₂ are preferred.

In the first step, when alkylene oxide is used as a raw material, the amount of alkylene oxide added depends on the number of moles of alkylene oxide added in the primary or secondary amine compound having a (poly) alkylene glycol chain, but is an amine compound. It is preferable that it is 100-30000 mol% with respect to 100 mol%.

In the first step, when an amino alcohol is used as the amine compound, the hydroxyl group is preferably changed to an alcoholate group and reacted with an alkylene oxide.
The reaction for changing the hydroxyl group to an alcoholate group is preferably performed using a base.
The base is not particularly limited, and examples thereof include alkali metal salts of diphenylmethane, alkali metal hydrides, alkali metal amides or finely divided alkali metals, alkali metal hydroxides, alkali metal alcoholates, and the like. . The base is preferably an alkali metal salt of diphenylmethane, an alkali metal hydride, an alkali metal amide or a finely divided alkali metal, more preferably diphenylmethyl potassium, potassium hydride, potassium amide or finely divided potassium. is there.

In the first step, when the reaction is performed using an amine compound and an alkylene oxide as raw materials, the solvent is not particularly limited, and examples thereof include diethyl ether, tetrahydrofuran, dimethyl sulfoxide and the like.
In the first step, when an amino alcohol having a hydroxyl group changed to an alcoholate group is used as the amine compound, the reaction between the amine compound and the alkylene oxide is preferably performed using an aprotic solvent or an anhydrous solvent. More preferred is tetrahydrofuran, diglyme (diethylene glycol dimethyl ether), dimethyl sulfoxide or hexamethylphosphoramide.
The reaction temperature is not particularly limited, but is preferably 0 to 200 ° C. More preferably, it is 20-120 degreeC.

When producing the compound represented by the above formula (5) as the primary or secondary amine compound having a (poly) alkylene glycol chain in the first step, it is preferable to use ammonia as the amine compound.
When producing the compound represented by (5) above, the (poly) alkylene glycols are preferably alkoxy (poly) alkylene glycols. Specific examples and preferred examples of the alkylene group are the same as the alkylene group in the above formula (4).
As said alkoxy group, a C1-C30 alkoxy group is preferable, More preferably, it is a C1-C4 alkoxy group, More preferably, it is a methoxy group.

When ammonia is used as the amine compound in the first step, it is preferable to use a metal catalyst for the reaction between the (poly) alkylene glycol and ammonia.
The metal catalyst is preferably a transition metal, more preferably cobalt.
Although the usage-amount of ammonia in the said reaction is not restrict | limited in particular, It is preferable that it is 100-1000 mol% with respect to 100 mol% of alkoxy (poly) alkylene glycol.

The reaction temperature in the above reaction is preferably 50 to 250 ° C.
The reaction pressure in the above reaction is preferably 1 to 300 bar.

When producing the compound represented by the above formula (8) as a primary or secondary amine compound having a (poly) alkylene glycol chain in the first step, an aminoalkanethiol having 1 to 8 carbon atoms as the amine compound, It is preferable to use a (poly) alkylene glycol having an ethylenically unsaturated group as the (poly) alkylene glycol. Specific examples of the (poly) alkylene glycol having an aminoalkanethiol and an ethylenically unsaturated group have an amine compound having a thiol group and an ethylenically unsaturated group in the production of the compound represented by the above formula (8) (poly ) Same as alkylene glycols.
As the aminoalkanethiol, cysteamine and cysteine are preferable.
The (poly) alkylene glycol having an ethylenically unsaturated group is preferably a compound represented by the above formula (10). More preferred is a compound wherein R ¹² in the above formula (10) is an alkyl group having 1 to 3 carbon atoms and r is 1, and more preferred is methoxy (poly) ethylene glycol allyl ether.

The method for producing the (poly) alkylene glycol having an ethylenically unsaturated group is not particularly limited, but it is preferably produced by reacting (poly) alkylene glycol with an allyl halide such as allyl bromide. The pH of the reaction is not particularly limited, but the reaction is preferably performed under basic conditions, and the reaction system can be made basic using a base such as an alkali metal hydroxide.

The amount of aminoalkanethiol used in the reaction between the aminoalkanethiol and the (poly) alkylene glycol having an ethylenically unsaturated group is not particularly limited, but is 100 mol% of the (poly) alkylene glycol having an ethylenically unsaturated group. It is preferable that it is 100-5000 mol% with respect to it.

The solvent in the reaction between the aminoalkanethiol and the (poly) alkylene glycol having an ethylenically unsaturated group is not particularly limited, but methanol and ethanol are preferable.
The reaction temperature in the above reaction is not particularly limited, but is preferably 5 to 90 ° C.
The reaction time in the above reaction is not particularly limited, but is preferably 1 to 10 hours.

The reaction between the aminoalkanethiol and the (poly) alkylene glycol having an ethylenically unsaturated group is preferably performed in the presence of a radical initiator.
The radical initiator is not particularly limited, but a photo radical initiator such as 2,2-dimethoxy-2-phenylacetophenone is preferable. When using such a photoradical initiator, it is preferable to carry out the reaction by irradiating the reaction solution with ultraviolet rays.

The second step in the production method of the present invention is a step of producing a lignin derivative using a primary or secondary amine compound having a (poly) alkylene glycol chain obtained in the first step and an aldehyde compound as raw materials. If there is no particular limitation, a step of reacting a primary or secondary amine compound having a (poly) alkylene glycol chain and an aldehyde compound, a primary or secondary amine compound having a (poly) alkylene glycol chain and an aldehyde It is preferable to include a step of reacting a reaction product of the compound with lignin.
A structure in which lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bonded via a divalent linking group by a condensation reaction using an aldehyde compound in such two steps. A lignin derivative having can be produced.
Thus, the efficiency of introducing a primary or secondary amine compound having a (poly) alkylene glycol chain (excluding amino acids) into lignin can be further improved by producing a lignin derivative through a two-step process. it can.
Such a production method comprises a lignin derivative having a structure in which a lignin and an amino group derived from a primary or secondary amine compound (excluding amino acids) having a (poly) alkylene glycol chain are bonded via a divalent linking group. Is a preferable production method.

In the second step of the production method of the present invention, the weight of the primary or secondary amine compound having a (poly) alkylene glycol chain bonded to 1000 g of lignin via a divalent linking group is 10 to 100,000 g. It is preferable. A structure derived from a primary or secondary amine compound having a (poly) alkylene glycol chain is obtained by adding a primary or secondary amine compound having such a weight of a (poly) alkylene glycol chain. The effect of having can be more fully exhibited. The weight of the primary or secondary amine compound having a (poly) alkylene glycol chain is more preferably 50 to 50000 g, still more preferably 100 to 10000 g, particularly preferably 250 to 4000 g, most preferably. Is 400-2500 g.

Primary having a (poly) alkylene glycol chain used in the step of reacting a primary or secondary amine compound having a (poly) alkylene glycol chain and an aldehyde compound in the second step (hereinafter also referred to as step a). Or it is preferable that the quantity of a secondary amine compound is 10-300 mol% with respect to 100 mol% of aldehyde compounds. More preferably, it is 50-200 mol%, More preferably, it is 80-120 mol%.

The solvent used in the step of reacting the primary or secondary amine compound having the (poly) alkylene glycol chain and the aldehyde compound is not particularly limited as long as the reaction proceeds. In addition to water, methanol, propanol, ethylene glycol, Organic solvents such as dioxane, ethyl acetate and dimethyl sulfoxide can also be used.

The reaction between the primary or secondary amine compound having the (poly) alkylene glycol chain and the aldehyde compound may be performed under either acidic or basic conditions as long as the reaction proceeds, preferably basic conditions. It is below. When performing the said reaction on basic conditions, it is preferable to carry out pH of the reaction solution as 8-14. More preferably, the reaction solution is adjusted to pH 9-13.
When the primary or secondary amine compound having the (poly) alkylene glycol chain is an acidic compound, the pH can be adjusted using a basic substance.
When the primary or secondary amine compound having the (poly) alkylene glycol chain is a basic compound, the pH of the reaction solution can be adjusted by adding the primary or secondary amine compound having the (poly) alkylene glycol chain. The basic region can be used, but the pH may be adjusted by using a basic substance other than the primary or secondary amine compound having a (poly) alkylene glycol chain. The basic substance other than the primary or secondary amine compound having the (poly) alkylene glycol chain 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.).

The reaction temperature in the step of reacting the primary or secondary amine compound having the (poly) alkylene glycol chain with the aldehyde 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 lignin used in the step of reacting a reaction product of a primary or secondary amine compound having an (poly) alkylene glycol chain with an aldehyde compound and lignin (hereinafter also referred to as step b) is the same as described above. It is.
The amount of the reaction product of the primary or secondary amine compound having a (poly) alkylene glycol chain and the aldehyde compound used in the above step is preferably 10 to 100,000 g with respect to 1000 g of lignin. More preferably, it is 50-50000g, More preferably, it is 100-10000g.

The solvent used in the step of reacting the reaction product of the primary or secondary amine compound having the (poly) alkylene glycol chain with the aldehyde compound and lignin is not particularly limited as long as the reaction proceeds. Organic solvents such as methanol, propanol, ethylene glycol, dioxane, ethyl acetate and dimethyl sulfoxide can also be used. Preferably, it is water.

The step of reacting the reaction product of the primary or secondary amine compound having the (poly) alkylene glycol chain with the aldehyde compound and lignin is carried out under either acidic or basic conditions as long as the reaction proceeds. However, it is preferably performed under basic conditions. When performing the said reaction on basic conditions, it is preferable to carry out pH of the reaction solution as 8-14. More preferably, the reaction solution is adjusted to pH 9-13. Moreover, the process of neutralizing the reaction solution as needed after reaction may be included.
Although it does not restrict | limit especially as a pH adjuster of a reaction solution, For example, the hydroxide of alkali metals, such as sodium, etc. are mentioned. Sodium hydroxide is preferable.

The reaction temperature in the step of reacting the reaction product of the primary or secondary amine compound having an (poly) alkylene glycol chain with an aldehyde compound and lignin is preferably 20 to 120 ° C. More preferably, it is 50-90 degreeC.
The reaction time is preferably 0.5 to 40 hours. More preferably, it is 1 to 20 hours.

The lignin derivative of the present invention has a lignin-derived structure, an amino group, and a (poly) alkylene glycol chain, and can be added to the cement composition to increase the fluidity of the cement composition. It can be suitably used as an 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, the lignin derivative of the present invention has an amino group and a (poly) alkylene glycol chain, whereby the hydrophilicity of lignin 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 lignin derivative of the present invention is a lignin derivative having a new structure in which an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain is bonded to lignin. It can be suitably used as an admixture.

FIG. 3 is a diagram showing the results of capillary electrophoresis of lignin derivative 1 obtained in Example 1.

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 obtained lignin derivative 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 50 cm) (manufactured by Beckman Coulter)
Column temperature: 25 ° C
Voltage: 20kV
Solvent: 50 mM boric acid aqueous solution Sample concentration: 2% by mass
Detector: UV, Hg lamp 210nm

<High performance liquid chromatography (LC)>
Confirmation of the residual amount of the amine compound used as a reaction raw material was measured by the following measuring method.
Apparatus: Waters Alliance 2695 (manufactured by Waters)
Analysis software: Empower Professional (manufactured by Waters)
Column: CAPCELL PAK SCX UG80 5 μm (inner diameter 4.6 mm × length 250 mm, manufactured by Shiseido Co., Ltd.)
Column temperature: 40 ° C
Solvent: 156 g of sodium dihydrogen phosphate dihydrate dissolved in 100 mM phosphoric acid aqueous solution Flow rate: 1.0 ml / min
Sample introduction amount: 100 μl
Detector: differential refractometer (RI) detector (Waters 2414)

<Example 1>
(Process a)
Charge 145.6 g of Jeffamine M-1000 and 69.0 g of deionized water to a separable flask, heat the separable flask to 40 ° C., and stir it with 11.8 g of 37% formaldehyde aqueous solution and 23. deionized water. The liquid mixture with 6g was dripped over 1 hour. The pH of the reaction system was 11.3. After completion of the dropping, the mixture was further stirred at 40 ° C. for 1 hour to obtain a methylolated product (PAG chain-containing amine compound) of Jeffamine M-1000.
(Process b)
Next, 9.0 g of kraft lignin (weight average molecular weight 17700, manufactured by ALDRICH), 68.1 g of deionized water, 2.6 g of 30% NaOH aqueous solution, and a solution of the methylolated product of Jeffamine M-1000 obtained in step a. 10.3 g 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 the lignin derivative 1 of this invention.
The weight average molecular weight of the lignin derivative 1 was 18900. The result of capillary electrophoresis of lignin derivative 1 is shown in FIG. In addition to the obtained lignin derivative 1, FIG. 1 also shows the results of electrophoresis of lignin. Thiourea is an uncharged reference material. It means that anionic property is so high that holding time is long by electrophoresis measurement. The obtained product was shifted to a side having a lower anionic property than the lignin before the reaction, and from this result, it was confirmed that Jeffamine M-1000 having no charge was added to the lignin. The consumption rate of the methylolated product of Jeffamine M-1000 determined from LC measurement was 96%.

<Examples 2 to 4>
Except having changed the preparation amount of each raw material as shown in Table 1, the lignin derivatives 2-4 of Examples 2-4 were manufactured by the prescription similar to Example 1. FIG.

<Production Example 1: Production of primary amine compound having polyalkylene glycol chain>
1.6 g of potassium hydroxide was mixed with 100 g of a 10% polyethylene glycol methyl ether toluene solution (average added mole number of ethylene oxide: 80), and the mixture was refluxed for 2 hours. The resulting solution was cooled to 50 ° C., 3.4 g of allyl bromide was slowly added, and the mixture was allowed to react overnight with stirring. The resulting solution was filtered through celite, after which the celite was washed with dichloromethane (DCM) and the solvent was removed under reduced pressure. The resulting residue was redissolved with DCM. Methoxypolyethyleneglycol allyl ether (hereinafter also referred to as MeO-PEG-Allyl) was precipitated by adding dropwise an ether / hexane (1: 1 v / v) mixed solvent to the resulting solution. Drying under reduced pressure gave MeO-PEG-Allyl as a white solid.
7 g of MeO-PEG-Allyl was dissolved in 35 mL of methanol, and 8.9 g of cysteamine hydrochloride and 0.1 g of 2,2-dimethoxy-2-phenylacetophenone (DMPA) were added. The solution was purged with nitrogen for 15 minutes and irradiated with 365 nm UV light for 2 hours. The solution was then evaporated to dryness and the crude mixture was dissolved in 1N sodium hydroxide. The aqueous layer was extracted 3 times with DCM, and then the organic layer was filtered through Celite and evaporated under reduced pressure. The obtained residue was redissolved with DCM, and a mixed solvent of ether / hexane (1: 1 v / v) was added dropwise to precipitate a primary amine compound having a white polyalkylene glycol chain. The precipitated primary amine compound having a polyalkylene glycol chain was filtered, washed with ether, then washed with hexane, and dried under reduced pressure. The weight average molecular weight of the obtained primary amine compound having a polyethylene glycol chain was 3600.

<Example 5>
Kraft lignin (weight average molecular weight 17700, manufactured by ALDRICH) 7.5 g, deionized water 34.4 g, 30% NaOH aqueous solution 2.6 g, 37% formaldehyde aqueous solution 0.5 g and the polyethylene glycol chain obtained in Production Example 1 A primary amine compound (5.0 g) was charged into a separable flask, and the separable flask was heated to 40 ° C. and stirred for 6 hours. The pH of the reaction system was 11.5. Then, it cooled and the lignin derivative 5 was obtained. The obtained product (lignin derivative 5) had a weight average molecular weight of 22,800.

<Comparative Example 1>
The lignin similar to the lignin used in Examples 1 to 5 was used as the lignin of Comparative Example 1.

A mortar test was conducted on the lignin derivatives produced in Examples 1 to 4 and the lignin of Comparative Example 1 by the following method. The results are shown in Table 2.

<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 2, 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 dispersion performance is excellent, so that a numerical value is large.

<Measurement of mortar air volume>
The mortar air amount (initial air amount) was measured by the method of JIS-A-1128 (revised in 2005). About 200 mL of mortar was packed in a 500 mL glass graduated cylinder, struck with a round bar having a diameter of 8 mm, and gently bubbled by hand to remove coarse bubbles. Further, about 200 mL of mortar was added and air bubbles were similarly removed. Then, the volume and mass of the mortar were measured, and the amount of air was calculated from the density of each material.

Examples 1-4 have a larger mortar flow value than Comparative Example 1 of lignin having no amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain. Therefore, since the lignin derivative 5 also has an amino group derived from a primary amine compound having a (poly) alkylene glycol chain, it is expected to exhibit excellent dispersion performance in a mortar test.

Claims (7)

A lignin derivative having a structure in which lignin and an amino group derived from a primary or secondary amine compound having a (poly) alkylene glycol chain are bonded via a divalent linking group. The lignin derivative according to claim 1, wherein the divalent linking group is a divalent hydrocarbon group. A lignin derivative obtained by reacting lignin, a primary or secondary amine compound having a (poly) alkylene glycol chain, and an aldehyde compound as raw materials. A cement admixture comprising the lignin derivative according to any one of claims 1 to 3. A cement composition comprising the cement admixture according to claim 4 and cement. A method for producing a lignin derivative, comprising producing a lignin derivative using lignin, a primary or secondary amine compound having an (poly) alkylene glycol chain, and an aldehyde compound as raw materials. A method for producing a lignin derivative comprising:
The production method includes a first step of producing a primary or secondary amine compound having a (poly) alkylene glycol chain;
A lignin, a primary or secondary amine compound having a (poly) alkylene glycol chain obtained in the first step, and a second step of producing a lignin derivative using an aldehyde compound as a raw material. A method for producing a lignin derivative.

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