Lignin derivatives and additives for hydraulic compositions containing lignin derivatives

Abstract

To provide a lignin derivative that can be manufactured under industrially reasonable reaction conditions and that can stably exhibit high flowability by improving the initial material homogeneity of the hydraulic composition during mixing, as well as an additive for hydraulic compositions containing lignin derivatives. Technical Solution: A lignin derivative, which is a reaction product comprising a mixture of lignin sulfonate compounds, aromatic compounds, and aldehyde compounds, having terminally phosphorylated (poly)alkylene oxides.

Description

Technical Field

[0001] This invention relates to a lignin derivative and an additive for hydraulic compositions containing the lignin derivative. Background Technology

[0002] Lignin is a natural polymer compound found in trees. Lignin sulfonates, contained in sulfite pulp waste liquor discharged during the papermaking process, have traditionally been used as dispersants in cement and dyes. In recent years, lignin has gained attention as a renewable biomass feedstock derived from wood, and its applications have been further studied.

[0003] For example, Patent Document 1 discloses a dispersant containing a lignin derivative, which is composed of a reaction product of lignin sulfonate and a water-soluble monomer having a polyalkylene oxide chain. Patent Document 2 discloses a dispersant containing a lignin derivative compound, which is a reaction product of a lignin sulfonate compound and an aromatic water-soluble compound. Patent Document 3 discloses a dispersant containing a lignin derivative that satisfies specified conditions such as viscosity or surface tension.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2011-240224

[0007] Patent Document 2: International Publication No. 2019 / 039609

[0008] Patent Document 3: Japanese Patent Application Publication No. 2020-025935 Summary of the Invention

[0009] The technical problem that the invention aims to solve

[0010] However, depending on the type of lignin sulfonate available as a raw material or the ratio of lignin purity, conventional lignin derivatives have struggled to achieve the performance required for dispersants. For example, they may not be able to react sufficiently under industrially reasonable reaction conditions, or they may gel due to uncontrolled reactions.

[0011] Especially when using lignin derivatives as dispersants in hydraulic compositions, a technical problem arises: insufficient homogeneity of the mixed materials during the cement, mortar, or concrete mixing process results in the hydraulic composition's flowability failing to meet desired performance. Given the recent trends of energy conservation and decarbonization, this lack of homogeneity in the mixing process is a significant technical issue contributing to reduced productivity in hydraulic compositions during the research of biomass raw material applications. There is room for improvement in achieving a higher level of homogeneity in the mixed materials compared to previous methods.

[0012] The present invention was made in view of the above circumstances, and its technical problem is to provide a lignin derivative and an additive for hydraulic compositions containing lignin derivatives that can be manufactured under industrially reasonable reaction conditions and can stably exhibit high fluidity by improving the material uniformity at the initial mixing stage of the hydraulic composition.

[0013] Technical solutions for solving technical problems

[0014] After in-depth research, the inventors discovered that a specified lignin derivative with terminal phosphoesterified (poly)alkylene oxides can improve the material homogeneity at the initial mixing stage of a hydraulic composition, thereby enabling it to stably exhibit high fluidity relative to the hydraulic composition, thus completing the present invention.

[0015] That is, the present invention takes the following [1] to [6] as objects.

[0016] [1] A lignin derivative, which is a reaction product comprising a mixture of lignin sulfonate compounds, aromatic compounds (excluding the lignin sulfonate compounds) and aldehyde compounds.

[0017] It has terminally phosphorylated (poly)alkylene oxides.

[0018] [2] The lignin derivative according to [1], wherein the aromatic compound comprises compound A represented by the following formula (1).

[0019] [Chemical Formula 1]

[0020]

[0021] (In the formula, n represents 1 or 2,

[0022] When n represents 1,

[0023] R 1 Represents a hydrogen atom, or a hydrocarbon group having 1 to 24 carbon atoms.

[0024] A 1 O represents an alkylene oxide with 2 to 4 carbon atoms.

[0025] m is A 1 The average number of moles added to O, representing numbers from 1 to 300.

[0026] X 1 Indicates phosphate ester group,

[0027] When n represents 2,

[0028] R 1 It can represent -CH2-, -C(CH3)2-, or -SO2-.

[0029] A 1 O represents an alkylene oxide with 2 to 4 carbon atoms.

[0030] m is A 1 The average number of moles added to O, representing numbers from 1 to 300.

[0031] X 1 (This indicates a phosphate ester group.)

[0032] [3] According to the lignin derivative of [2], wherein the content of compound A is 3% by mass or more relative to the total mass of the aromatic compound.

[0033] [4] The lignin derivative according to [2], wherein the aromatic compound further comprises compound B represented by formula (2).

[0034] [Chemical Formula 2]

[0035]

[0036] (In the formula, q represents 1 or 2,

[0037] When q represents 1

[0038] R 3 Represents a hydrogen atom, or a hydrocarbon group having 1 to 24 carbon atoms.

[0039] A 2 O represents an alkylene oxide with 2 to 4 carbon atoms.

[0040] p is A 2 The average number of moles added to O, representing numbers from 1 to 300.

[0041] R 2 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

[0042] When q represents 2

[0043] R 3It can represent -CH2-, -C(CH3)2-, or -SO2-.

[0044] A 2 O represents an alkylene oxide with 2 to 4 carbon atoms.

[0045] p is A 2 The average number of moles added to O, representing numbers from 1 to 300.

[0046] R 2 (This refers to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.)

[0047] [5] According to the lignin derivative of [1], wherein the aldehyde compound is compound C represented by formula (3).

[0048] [Chemical Formula 3]

[0049]

[0050] (where R) 4 This refers to hydrogen atoms, carboxyl groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, phenyl groups, naphthyl groups, or heterocyclic groups.

[0051] (r represents a number from 1 to 100.)

[0052] [6] The lignin derivative according to [1], wherein the lignin derivative is a reaction product comprising a mixture of the lignin sulfonate compound and the aromatic compound, wherein the mass ratio of the lignin sulfonate compound to the aromatic compound is 20:80 to 35:65.

[0053] [7] An additive for hydraulic compositions, comprising any one of the lignin derivatives described in [1] to [6].

[0054] Invention Effects

[0055] The lignin derivative of the present invention can be manufactured under industrially reasonable reaction conditions, and when added as an additive for hydraulic compositions, it improves the initial material uniformity during mixing, thereby enabling the hydraulic composition to stably exhibit high fluidity. Detailed Implementation

[0056] The lignin derivatives of the present invention and additives for hydraulic compositions containing the lignin derivatives are described in detail below.

[0057] <Lignin Derivatives>

[0058] The lignin derivatives that are the subject of this invention are reaction products comprising a mixture of lignin sulfonate compounds, aromatic compounds and aldehyde compounds, and have terminally phosphorylated (poly)alkylene oxides.

[0059] "Terminal phosphate-esterified (poly)alkylene oxide" refers to a structure in which a phosphate ester group is introduced at the end of one of the (poly)alkylene oxide groups. Examples of phosphate esters constituting the phosphate ester group include monophosphate esters and their salts, diesters and their salts, triphosphate esters, and mixtures thereof. Among these, from the viewpoint of imparting high flowability to the hydraulic composition, phosphate ester groups composed of monophosphate esters and their salts represented by the following formula are preferred.

[0060] *-OP(=O)(-OM)2

[0061] (M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as calcium or magnesium; an ammonium group; an organic ammonium group such as an alkylammonium group or an alkanolammonium group. * indicates a bond end with other groups (structures).)

[0062] (Poly)alkylene oxides are composed of repeating units (alkylene oxide units) derived from alkylene oxides. The number of carbon atoms in these alkylene oxide units is not particularly limited, but is typically 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of alkylene oxides (alkylene oxide units) include ethylene oxide (ethylene oxide unit), propylene oxide (propylene oxide unit), and butene oxide (butyl oxide unit), with ethylene oxide and propylene oxide being preferred. These alkylene oxides can be used alone or in combination of two or more. When using two or more alkylene oxides to form (poly)alkylene oxides, the addition of these alkylene oxides can be either random addition or block addition. The average molar number of alkylene oxide units added is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less.

[0063] In terminally phosphated (poly)alkylene oxides, the terminal of the non-phosphated (poly)alkylene oxide can be directly or via a linking group bonded to structural units derived from lignin sulfonate compounds in lignin derivatives, or similarly bonded to structural units derived from aromatic compounds, or bonded to both, but preferably bonded to structural units derived from aromatic compounds.

[0064] <Lignosulfonic acid compounds>

[0065] In this invention, lignin sulfonate compounds refer to compounds in which a sulfonate skeleton is introduced by carbon cleavage at the α-position of the side chain having a lignin hydroxyphenylpropane structure.

[0066] Alternatively, the compound can be chemically modified by hydrolysis, alkoxylation, desulfonation, alkylation, etc.

[0067] Lignosulfonic acid compounds can be produced in the form of salts. Examples of salts include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts, with calcium salts, magnesium salts, and sodium salts being preferred.

[0068] There are no particular limitations on the manufacturing method and source of lignin sulfonate compounds; they can be either natural or synthetic. Lignosulfonate compounds are a major component of the waste liquor from sulfite pulp obtained by cooking wood under acidic conditions. Therefore, lignin sulfonate compounds derived from sulfite pulp waste liquor can be used. Alternatively, commercially available products can also be used as lignin sulfonate compounds. Examples of commercially available products include sodium lignin sulfonate manufactured by Tokyo Chemical Industry Co., Ltd., as well as Vanillex (registered trademark) HW, N, etc. (manufactured by Nippon Paper Co., Ltd.), San X (registered trademark) M, P321, P252, SCL, SCP, etc. (manufactured by Nippon Paper Co., Ltd.), Pearlex (registered trademark) NP, DP, etc. (manufactured by Nippon Paper Co., Ltd.), Sunflow (registered trademark) RH (manufactured by Nippon Paper Co., Ltd.), and Greensperse S9 (manufactured by Borregaard Co., Ltd.).

[0069] <Aromatic compounds>

[0070] In this invention, an aromatic compound refers to a compound having at least one aromatic skeleton, which is a compound other than the lignin sulfonate compound that undergoes a condensation reaction with a lignin sulfonate compound to form a copolymer.

[0071] As aromatic compounds, in addition to phenolic compounds with terminally phosphorylated (poly)alkylene oxides (compound A represented by formula (1) described later), alkylene oxide adducts of phenolic compounds or their derivatives (compound B represented by formula (2)), phenols and non-phenolic aromatic compounds without phenolic hydroxyl groups can also be listed.

[0072] <Compound A (aromatic compound A) represented by formula (1)>

[0073] Compound A is a phosphate ester derivative of an alkylene oxide adduct of phenolic compounds such as phenol or bisphenol A, and has a structure represented by the following formula (1).

[0074] The aromatic compounds of the present invention preferably contain at least compound A represented by formula (1).

[0075] [Chemical Formula 4]

[0076]

[0077] In the above formula, n represents 1 or 2. When n represents 1, R 1 R represents a hydrocarbon group containing 1 to 24 hydrogen atoms, where n represents 2. 1 It represents -CH2-, -C(CH3)2-, or -SO2-.

[0078] A 1 O represents an alkylene oxide with 2 to 4 carbon atoms, and m is an A 1 The average number of moles added to O, representing numbers from 1 to 300, X 1 It represents a phosphate ester group.

[0079] Compound A is a phosphate ester derivative of a compound having an alkylene oxide having 2 to 4 carbon atoms, which is formed by the addition of phenolic compounds such as phenol or bisphenol A or their substitutes.

[0080] Examples of alkylene oxides having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butene oxide. These alkylene oxides can be added individually or in combination. When two or more alkylene oxides are used, the addition can be either block addition or random addition.

[0081] That is, as A above 1 Alkyloxy groups with 2 to 4 carbon atoms in O can be exemplified by ethyleneoxy, propyleneoxy, and butyloxy. A 1 O can consist of only ethyleneoxy, propyleneoxy, or butyloxy groups, or it can contain two or more of these groups. When more than two groups are included, the addition can be either random addition or block addition.

[0082] Additionally, m is A 1 The average number of moles of O added is expressed as 1 to 300, preferably 2 to 200, and more preferably 3 to 150.

[0083] The above R as in the case where n is 1 1 Hydrocarbon groups with 1 to 24 carbon atoms can be listed as alkyl groups with 1 to 24 carbon atoms, alkenyl groups with 2 to 24 carbon atoms, unsaturated aliphatic hydrocarbon groups with 4 to 24 unsaturated bonds having 2 or more carbon atoms, aryl groups with 6 to 20 carbon atoms, and aralkyl groups with 7 to 24 carbon atoms.

[0084] Alkyl groups having 1 to 24 carbon atoms include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (palmityl), octadecyl (stearyl), eicosyl, dodecyl (benzyl), tetradecyl, etc. These can have branched structures (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc.) and / or cyclic structures (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, etc.).

[0085] Alkenyl groups having 2 to 24 carbon atoms can be listed as groups having one carbon-carbon double bond among the alkyl groups listed above that have 2 to 24 carbon atoms. Specifically, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, octadecenyl, eicoseneyl, dodecenyl, dodecenyl, dodecenyl, etc., which may have branched and / or cyclic structures.

[0086] In addition, unsaturated aliphatic hydrocarbon groups having 4 to 24 unsaturated bonds with 2 or more carbon atoms can be listed as decadienyl, undecadienyl, dodecadienyl, tridecadienyl, tetradecadienyl, pentadecadienyl, hexadecadienyl, heptadecadienyl, octadecadienyl, nonadecadienyl, eicosadienyl, icosyl, icosyl, icosyl, tridecadienyl, icosyl, icosyl, icosyl, decanetrienyl, undecanetrienyl, dodecatrienyl, tridecanetrienyl, tetradecanetrienyl, pentadecanetrienyl, hexadecanetrienyl, heptadecanetrienyl, octadecanetrienyl, nonadecanetrienyl, eicosyltrienyl, icosyl, icosyl, icosyl, icosyl, icosyl, icosyl, icosyl, icosyl, and icosyl, etc.

[0087] In addition, aryl groups with 6 to 20 carbon atoms can be exemplified by phenyl, naphthyl, anthracene, phenanthryl, etc., but are not limited to these.

[0088] Aryl alkyl is an alkyl group substituted with an aryl group. Specific examples of such aryl and alkyl groups can be listed as examples similar to those described above. Specific examples of aryl alkyl groups having 7 to 24 carbon atoms include phenylmethyl (benzyl), α-methylbenzyl, 2-phenylethyl, 1-methyl-1-phenylethyl (cumyl), 3-phenyl-propyl, 2-phenyl-2-propyl, etc., but are not limited to these.

[0089] Furthermore, when n is 2, the above R 1 It represents -CH2-, -C(CH3)2-, or -SO2-.

[0090] Furthermore, in the cases where n is 1 and n is 2, R in equation (1) 1 The bonding positions are not particularly limited, but in terms of facilitating the application of the present invention, it is preferred that the bonding be at the para position relative to the oxygen atom bonded to the aromatic ring.

[0091] For example, when n is 1, R is preferred. 1 The atoms are hydrogen atoms and tert-butyl groups. Furthermore, when n is 2, R is preferred. 1 It is -C(CH3)2-.

[0092] Additionally, compound A is a monophosphate and / or its salt, a diester and / or its salt, or a triphosphate or a mixture thereof.

[0093] Examples of phosphate salts include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium or magnesium; ammonium salts; and organic ammonium salts such as alkylammonium or alkanolammonium.

[0094] Compound A described above can also be synthesized using a phosphorylating agent, p-(poly)oxyalkylene alkylphenol, and by a known method. Examples of phosphorylating agents include phosphoric anhydrides, phosphoric acid, polyphosphoric acid, and phosphoryl chloride.

[0095] As a compound A represented by the above formula (1), for example as compound A when n is 1, compounds represented by the following formula can be listed.

[0096] Furthermore, in the formula, R 1 A 1 O and n represent the same definitions as in formula (1) above, and Ph represents phenylene. In addition, M represents hydrogen atom; alkali metal atom such as sodium or potassium; alkaline earth metal atom such as calcium or magnesium; ammonium group; organic ammonium group such as alkylammonium group or alkanolammonium group.

[0097] Additionally, Z represents a polyoxyalkylene alkyl ether residue represented by the formula: R”-O-(A'O)w- (where R” represents an alkyl group with 1 to 24 carbon atoms, A'O represents an alkylene group with 2 to 3 carbon atoms, i.e., ethyleneoxy or propyleneoxy, and w represents the average number of moles of alkylene group A'O, i.e., 1 to 300). When multiple Zs exist, they can be the same group or different groups.

[0098] • Phosphate monoesters and their salts

[0099] R 1 -Ph-O-[A 1 O] m -P(=O)(-OM)2

[0100] • Phosphate diesters and their salts

[0101] [R 1 -Ph-O-[A 1 O] m -]2P(=O)(-OM)

[0102] [R 1 -Ph-O-[A 1 O] m -](Z-)P(=O)(-OM)

[0103] • Triphosphate

[0104] [R 1 -Ph-O-[A 1 O] m -]3P(=O)

[0105] [R 1 -Ph-O-[A 1 O] m -]2(Z-)P(=O)

[0106] [R 1 -Ph-O-[A 1 O] m -](Z-)2P(=O)

[0107] Compound A, represented by the above formula (1), can be used alone or in combination with two or more.

[0108] Furthermore, from the viewpoint of consistently achieving high fluidity, the content ratio of compound A relative to the total mass of aromatic compounds is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The aromatic compounds may also consist solely of compound A (100% by mass). Moreover, when the content ratio of compound A in the aromatic compounds is 10% by mass or more, improved uniformity of the compounded material can be expected.

[0109] <Compound B (aromatic compound B) represented by formula (2)>

[0110] As an aromatic compound, in addition to compound A represented by the above formula (1), it may further include compound B, which has a structure represented by the following formula (2).

[0111] [Chemical Formula 5]

[0112]

[0113] In the above formula, q represents 1 or 2. When q represents 1, R 3 R represents a hydrocarbon group having 1 to 24 hydrogen or carbon atoms, where q represents 2.3 It represents -CH2-, -C(CH3)2-, or -SO2-.

[0114] A 2 O represents an alkylene group with 2 to 4 carbon atoms, and p represents an alkylene group. 2 The average number of moles added to O, i.e., the number from 1 to 300, R 2 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

[0115] Compound B is a compound formed by the addition of an alkylene oxide with 2 to 4 carbon atoms to a phenolic compound such as phenol or bisphenol A or its substitutes. In addition, derivatives of the alkylene oxide adduct (alkyl esters or fatty acid esters) are also included in compound B.

[0116] Examples of alkylene oxides having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butene oxide. These alkylene oxides can be added individually or in combination. When using two or more alkylene oxides, the addition can be either block addition or random addition.

[0117] That is, as A above 2 Alkyloxy groups with 2 to 4 carbon atoms in O can be exemplified by ethyleneoxy, propyleneoxy, and butyloxy. A 2 O can consist of only ethyleneoxy, propyleneoxy, or butyloxy groups, or it can contain two or more of these groups. When more than two groups are included, the addition can be either random addition or block addition.

[0118] Additionally, p represents the average number of moles of alkylene oxides added, i.e., 1 to 300, preferably 10 to 200, more preferably 20 to 150, by increasing A. 2 The number of moles of O added can be expected to improve water-reducing properties.

[0119] As mentioned above, R 2 The alkyl group having 1 to 10 carbon atoms can have a branched structure and / or a cyclic structure. Specifically, examples of the above-mentioned R groups can be listed. 1 The specific examples of alkyl groups having 1 to 24 carbon atoms are listed below, including alkyl groups having 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, 1-adamantyl, etc.

[0120] In addition, acyl groups with 2 to 24 carbon atoms can be saturated or unsaturated (R'(CO)- group, where R' is a hydrocarbon group with 1 to 23 carbon atoms). For example, saturated acyl groups with 2 to 24 carbon atoms can be derived from carboxylic acids and fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid (lanolinic acid), heptanoic acid, octanoic acid (lanolinic acid), nonanoic acid, decanoic acid (lanolinic acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid (pentadecanic acid), hexadecanoic acid (palmitic acid), heptadecanic acid (pearlitic acid), octadecanoic acid (stearic acid), nonadecanic acid, eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), and teicosanoic acid (creosotenic acid). As a monounsaturated acyl group, examples include acyl groups derived from monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, transoleic acid, isoleic acid, codoleic acid, eicosenoic acid, erucic acid, and nervonic acid. As a diunsaturated acyl group, examples include acyl groups derived from diunsaturated fatty acids such as linoleic acid, eicosapentaenoic acid, and docosahexaenoic acid. Furthermore, as a triunsaturated acyl group, examples include acyl groups derived from triunsaturated fatty acids such as linolenic acid, terpineic acid, tung oil acid, mideic acid, di-hypothalamic acid, and eicosatrienoic acid.

[0121] The above R as q=1 3 Specific examples of hydrocarbon groups with 1 to 24 carbon atoms can be listed, such as those related to R. 1 Same group.

[0122] When q is 2, the above R 3 It represents -CH2-, -C(CH3)2-, or -SO2-.

[0123] Furthermore, in the cases where q is 1 and q is 2, R in equation (2) 3 The bonding positions are not particularly limited, but in terms of facilitating the application of the present invention, it is preferred that the bonding be at the para position relative to the oxygen atom bonded to the aromatic ring.

[0124] For example, when q is 1, R is preferred. 3 The atoms are hydrogen atoms and tert-butyl groups. Furthermore, when q is 2, R is preferred. 3 It is -C(CH3)2-.

[0125] Compound B, represented by the above formula (2), can be used alone or in combination with two or more.

[0126] The proportion of compound B in the aromatic compound is not particularly limited, but it can be used to remove the residue of compound A.

[0127] Other aromatic compounds

[0128] In the lignin derivatives of the present invention, in addition to compounds A and B, the aromatic compounds may also include other aromatic compounds capable of reacting with these compounds, without affecting the effects of the present invention.

[0129] Other aromatic compounds include phenol, bisphenol A, isophthalic acid, hydroxynaphthoic acid, benzoic acid, hydroxybenzoic acid, naphthalene sulfonic acid, methylnaphthalene sulfonic acid, butylnaphthalene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, aniline sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, and hydroxyethylphenol.

[0130] Aldehyde compounds

[0131] As an aldehyde compound, compound C having the structure represented by the following formula (3) is preferred.

[0132] [Chemical Formula 6]

[0133]

[0134] In the formula, R 4 The r represents a hydrogen atom, a carboxyl group, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group, and r represents a number from 1 to 100.

[0135] Furthermore, these alkyl, alkenyl, phenyl, naphthyl, and heterocyclic groups can be substituted with any substituents having 1 to 10 carbon atoms, such as alkyl, phenyl, naphthyl, aryl, halogen atoms such as chlorine and bromine, sulfonic acid functional groups such as sulfonyl and sulfonic acid bases, acyl groups such as acetyl, hydroxyl, amino, and carboxyl groups.

[0136] The above R 4 Alkyl groups having 1 to 10 carbon atoms and alkenyl groups having 2 to 10 carbon atoms can have branched or cyclic structures. Specific examples include R in the compound A (formula (1)). 1 The specific examples of alkyl groups having 1 to 24 carbon atoms and alkenyl groups having 2 to 24 carbon atoms are listed as alkyl groups having 1 to 10 carbon atoms and alkenyl groups having 2 to 10 carbon atoms.

[0137] Furthermore, examples of heterocyclic groups include furanyl, thiophene, pyridinyl, piperidinyl, and morpholinyl.

[0138] In addition, r preferably represents a number from 2 to 100.

[0139] Compound C (aldehydes) can include, for example, formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, isononanal, decanal, dodecanal, acrolein, crotonaldehyde, pentanal, heptanal, heptanal, octanal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylaldehyde, benzylaldehyde [(C6H5)2C(OH)-CHO], naphthaldehyde, benzaldehyde, etc., but can be selected from the group consisting of formaldehyde, paraformaldehyde, benzaldehyde, or any mixture of two or more of these.

[0140] Compound C can be used as a pure crystal or powder or as a hydrate of these, or it can be used as an aqueous solution such as formaldehyde, in which case the measurement or mixing of the components can be simplified.

[0141] Compound C represented by the above formula (3) can be used alone or in combination of two or more.

[0142] <Reaction ratios of each compound>

[0143] In this invention, the reaction ratio of the lignin sulfonate compound to the aromatic compound is not particularly limited, but by mass ratio, the lignin sulfonate compound and the aromatic compound are preferably 1 / 99 to 99 / 1. From the viewpoint of balancing high biomass yield and the flowability of the hydraulic composition, a ratio of 10 / 90 to 90 / 10 is more preferred, 20 / 80 to 75 / 25 is even more preferred, and 20 / 80 to 55 / 45 is particularly preferred. Moreover, for example, when the lignin sulfonate compound / aromatic compound ratio is 20 / 80 to 40 / 60 (mass ratio), it is expected that a more stable high flowability can be obtained, and especially when it is 20 / 80 to 35 / 65, it is expected that a more stable high flowability can be obtained.

[0144] Furthermore, in the reaction product containing a mixture of lignin sulfonate compounds, aromatic compounds, and aldehyde compounds, even when unreacted components of the aforementioned compounds are included, the mass ratio (reaction ratio) of the total amount of structural units derived from lignin sulfonate compounds and unreacted lignin sulfonate compound components to the total amount of structural units derived from aromatic compounds and unreacted aromatic compound components is the same as the addition ratio of these.

[0145] Furthermore, the amount of aldehyde compound reacting is not particularly limited relative to the total amount of lignin sulfonate compounds and aromatic compounds, but the total amount and the amount of aldehyde compound are preferably 99 / 1 to 80 / 20 by mass ratio, more preferably 98 / 2 to 85 / 15, for example 98 / 2 to 90 / 10.

[0146] <Lignin Derivatives and Their Manufacturing Methods>

[0147] The lignin derivatives of the present invention are reaction products comprising a mixture of the above-mentioned lignin sulfonate compounds, aromatic compounds and aldehyde compounds, and are composed of copolymers obtained by polycondensation of these mixtures.

[0148] In the mixture containing the above-mentioned lignin sulfonate compounds, aromatic compounds, and aldehyde compounds used for the condensation polymerization, the ratio (addition ratio) of each compound is not particularly limited.

[0149] For example, the ratio of lignin sulfonate compounds to aromatic compounds in the mixture, by mass, can be lignin sulfonate compounds: aromatic compounds = 1:99 to 99:1. From the viewpoint of balancing high biomass yield and the flowability of the hydraulic composition, it is more preferably 10:90 to 90:10, and even more preferably 20:80 to 75:25, for example, 20:80 to 55:45, and even more preferably 20:80 to 40:60. In particular, from the viewpoint of stably obtaining high flowability, it can be 20:80 to 35:65.

[0150] Furthermore, there is no particular limitation on the ratio of the total amount of lignin sulfonate compounds and aromatic compounds to aldehyde compounds in the mixture, but for example, by mass ratio, it can be the total amount: aldehyde compounds = 99:1 to 80:20, more preferably 98:2 to 85:15, for example 98:2 to 90:10.

[0151] There are no particular limitations on the polymerization method used to obtain the above copolymer.

[0152] Furthermore, there are no particular limitations on the order or method of adding the aforementioned lignin sulfonate compounds, aromatic compounds, and aldehyde compounds during polycondensation. For example, the total amount of these raw material compounds can be added together before the polycondensation reaction; a portion of the raw material compounds can be added before the polycondensation reaction, followed by the remaining portion added dropwise in stages; or a portion of the raw material compounds can be added before the polycondensation reaction, followed by the remaining portion after a certain reaction time. For instance, by mixing aromatic compounds and aldehyde compounds before the polycondensation reaction and then adding lignin sulfonate compounds dropwise into the mixture in stages, it is expected that the molecular weight of the obtained copolymer can be easily controlled.

[0153] Lignin derivatives are obtained, for example, by polycondensation of lignin sulfonic acid compounds, aromatic compounds and aldehyde compounds in the presence of a dehydration catalyst, and in the absence of solvent or in a solvent, at a reaction temperature of 80°C to 150°C and at atmospheric pressure to pressurized pressure, for example at 0.001 to 1 MPa.

[0154] Examples of dehydration catalysts include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octyl sulfonic acid, dodecyl sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, phenol sulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, dimethyl sulfate, phosphoric acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvic acid, maleic acid, malonic acid, nitrobenzeneic acid, nitrosalicylic acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, mercaptoacetic acid, mercaptopropionic acid, and activated clay. These dehydration catalysts can be used alone or in combination of two or more.

[0155] Furthermore, when carrying out polycondensation reactions in a solvent, the solvent can be water, glycol ether compounds such as propylene glycol monomethyl ether (PGME), aromatic compounds such as toluene and xylene, cyclic aliphatic compounds such as methylcyclohexane, etc. Solvents that can be used as dehydration catalysts (acid catalysts) can also be used, such as acetic acid. When carrying out polycondensation reactions in a solvent, the concentration of the components used for the polycondensation reaction (lignin sulfonate compounds, aromatic compounds, and aldehyde compounds) in the reaction system can be appropriately selected. However, if the concentration is too high, gelation is likely to occur; if it is too low, the reaction may not proceed rapidly. For example, the components that can be used for polycondensation reactions are approximately 30% to 70%.

[0156] The reaction temperature can be carried out at, for example, 95°C to 130°C. In addition, the polycondensation reaction can be completed in about 3 to 25 hours.

[0157] Polycondensation reactions are preferably carried out under acidic conditions, and it is ideal for the pH of the reaction system to be below 4.

[0158] In addition, defoamers can be used during the manufacture of lignin derivatives (during the polycondensation reaction). This suppresses foaming during the reaction and allows for the construction of a homogeneous reaction system.

[0159] After the polycondensation reaction is completed, various known methods can be used to reduce the content of unreacted aldehyde components (compound C) in the reaction system. For example, methods such as making the pH of the reaction system alkaline and heating it at 60℃ to 140℃, reducing the pressure of the reaction system (-0.1 to -0.001 MPa) to volatilize and remove the aldehyde components, and further adding small amounts of sodium bisulfite, hydrogen peroxide, ethyl urea, and / or polyethyleneimine can be used.

[0160] The dehydration catalyst used in the reaction can also be neutralized after the reaction is complete and removed by filtration as a salt. However, even if the catalyst is not removed, the performance of the additive used in the hydraulic composition of the present invention, as described later, will not be affected. In addition to filtration as described above, methods for catalyst removal include phase separation, dialysis, ultrafiltration, and the use of ion exchangers.

[0161] Furthermore, by utilizing neutralization and dilution of the reactants with water, the operability, such as metering, in the use of additives in hydraulic compositions described later is improved. Examples of alkaline compounds used for neutralization include sodium hydroxide, potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, and organic amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine; one or more of these compounds can be used in combination. For example, sodium hydroxide and calcium hydroxide can be used together as alkaline compounds for neutralization.

[0162] From the viewpoint of exhibiting excellent dispersibility, the copolymer obtained is suitable in the range of 4,000 to 150,000 in terms of weight-average molecular weight Mw (converted from polyethylene glycol by gel permeation chromatography (hereinafter referred to as "GPC method")), more preferably in the range of 8,000 to 120,000, and especially in the range of 12,000 to 100,000.

[0163] Furthermore, the term "lignin derivative" in this invention refers to a copolymer that can be composed solely of a mixture of monomers containing lignin sulfonate compounds, aromatic compounds, and aldehyde compounds obtained by polycondensation, but typically also includes unreacted components and byproducts generated during various polymerization processes, alkylene oxide addition processes, etc.

[0164] <Additives for Hydraulic Compositions>

[0165] The additives for hydraulic compositions of the present invention contain the aforementioned lignin derivatives. Furthermore, depending on the application, known and commonly used additives for hydraulic compositions can be appropriately employed and combined, and used as a so-called mixing agent. Specifically, other additives selected from at least one group consisting of conventionally known cement dispersants, high-performance AE water-reducing agents, high-performance water-reducing agents, AE water-reducing agents, water-reducing agents, air-entraining agents (AE agents), foaming agents, defoaming agents, retarders, setting accelerators, separation reducing agents, thickeners, shrinkage reducing agents, curing agents, waterproofing agents, etc., can be mixed in.

[0166] Furthermore, in this invention, a hydraulic composition refers to a composition containing a powder (hydraulic powder) that has the property of hardening through a hydration reaction, such as cement, gypsum, fly ash, blast furnace slag, etc. Additionally, when the hydraulic powder is cement, the hydraulic composition is also referred to as a cement composition.

[0167] Generally, cement dispersants can be used in appropriate combinations depending on the manufacturing conditions and performance requirements of concrete. The same applies to the additives in the hydraulic compositions of this invention; they can be used alone as cement dispersants or as main agents, but they can also be used as modifiers for cement dispersants with large slump loss or in combination with cement dispersants with high initial water-reducing properties.

[0168] For example, known cement dispersants include salts of polycarboxylic acid copolymers as described in Japanese Patent Publication No. 59-18338, Japanese Patent Publication No. 2628486, and Japanese Patent Publication No. 2774445. Other examples include salts of naphthalenesulfonic acid formaldehyde condensate, salts of melaminesulfonic acid formaldehyde condensate, lignin sulfonate, sodium gluconate, and sugar alcohols. The mixing ratio of the condensate of the present invention to the known cement dispersant is, for example, 1:99 to 99:1 by mass.

[0169] If we were to give a specific example of an air-entraining agent, we could list anionic air-entraining agents, nonionic air-entraining agents, and amphoteric air-entraining agents.

[0170] If we are talking about retarders, we can list inorganic retarders and organic retarders. More specifically, we can list hydroxycarboxylic acids and their salts such as gluconic acid, glucocorticoid, tartaric acid, citric acid, malic acid, and arachidic acid; sugars such as sucrose; and inorganic compounds such as zinc oxide, zinc chloride, fluorosilicic acid, and fluorosilicates.

[0171] As accelerators, inorganic accelerators and organic accelerators can be listed.

[0172] If we are to list thickeners / separation reducing agents, examples include water-soluble cellulose polymers, water-soluble polyacrylamide polymers, biopolymer thickeners such as gluten gum, xanthan gum, and polyethylene glycol, and nonionic thickeners such as polyalkylene oxides.

[0173] If we take defoamers as an example, we can list nonionic defoamers, silicone defoamers, higher alcohols, and mixtures with these as the main components.

[0174] When the additive for hydraulic compositions of the present invention is applied to, for example, a cement composition, the components constituting the cement composition are conventional concrete components, such as cement (e.g., ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, low-heat / medium-heat Portland cement or blast furnace cement), aggregates (i.e., fine aggregates and coarse aggregates), blending materials (e.g., silica fume, calcium carbonate powder, blast furnace slag powder, fly ash, etc.), expansion materials, and water.

[0175] In addition, the additives for hydraulic compositions of the present invention can also be suitably used in hydraulic compositions (cement compositions) that contain fly ash or blast furnace slag powder as mixing materials.

[0176] Fly ash is composed of silicon dioxide (SiO2) and alumina (Al). l2 O3 is the main component, and standards are specified in JIS A 6201 for types I to IV based on particle size or flowability. Furthermore, it is believed that the amount of unburned carbon in fly ash is related to the amount of air-entraining agent used, with an increase in unburned carbon tending to lead to an increase in the amount of air-entraining agent used. This amount of unburned carbon is generally considered to be related to the amount of methylene blue adsorbed by fly ash.

[0177] Blast furnace slag powder is a byproduct of blast furnace ironmaking, with calcium oxide (CaO), silicon dioxide (SiO2), and aluminum oxide (Al2O3) as its main components. The standard is specified in JIS A 6206.

[0178] In addition, as a mixing agent that can be added during the preparation of the hydraulic composition of the present invention, other than additives, there are the aforementioned known and commonly used air-entraining agents, retarders, accelerators, separation reducing agents, thickeners, defoamers, shrinkage reducing agents, etc., which can also be appropriately mixed. The mixing ratio of these components can be appropriately determined according to the type of component selected or the intended use.

[0179] The amount of the additive for the hydraulic composition of the present invention can be varied according to the mixing conditions of the materials comprising the above-described concrete. However, relative to the mass of cement, or in the case of using fly ash or other pozzolanic material powders in combination, relative to the total mass of cement and fly ash or other powders, it is typically added at about 0.05% to 5.0% by weight (as a percentage of the lignin derivative itself) in terms of solid content. The amount added can be appropriately adjusted according to the desired initial flow value, but excessive addition can cause delayed setting and sometimes poor hardening, so caution is required. Furthermore, the additive for the hydraulic composition of the present invention can achieve higher flowability than existing products, that is, it can exhibit performance at a lower addition rate than existing products.

[0180] The usage method is the same as for general cement dispersants: add the undiluted solution during concrete mixing, or pre-dilute and add it to the mixing water. Alternatively, it can be added after mixing the concrete or mortar, and then mixed evenly again.

[0181] [Example]

[0182] The present invention will be described with reference to the following embodiments. However, the present invention is not limited to these embodiments and comparative examples.

[0183] The weight-average molecular weight of lignin derivatives was determined by the following method.

[0184] GPC (Gel Permeation Chromatography)

[0185] <Gel permeation chromatography (GPC) determination conditions>

[0186] Chromatographic columns: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko Co., Ltd.)

[0187] Eluent: A mixture of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80 / 20)

[0188] Detector: Differential refractometer; Calibration line: Polyethylene glycol

[0189] [Manufacturing Example 1]

[0190] (Preparation of aromatic compound A)

[0191] In a glass reaction vessel equipped with a stirrer, thermometer, and nitrogen inlet tube, 3 moles of the ethylene oxide (EO) 6-moles adduct of p-tert-butylphenol were added. While bubbling with nitrogen, 1 mole of phosphoric anhydride was added over 4 hours at 50°C. The reaction was then allowed to mature at 100°C for 3 hours to complete the phosphorylation reaction, yielding the phosphate ester of the p-tert-butylphenol EO adduct (A-1).

[0192] Similarly, phosphate esters of the EO 90 molar adduct of p-tert-butylphenol (A-2), phosphate esters of the EO 4 molar adduct of bisphenol A (A-3), and phosphate esters of the EO 3 molar adduct of p-tert-butylphenol (A-4) were obtained.

[0193] (Aromatic compound B)

[0194] As aromatic compound B, poly(ethylene oxide) monophenyl ethers, bisphenol A EO 60 molar adducts, and p-tert-butylphenol EO 44 molar adducts were prepared with various EO addition molar numbers.

[0195] [Example 1]

[0196] (Manufacturing of lignin derivative (L-1))

[0197] In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device, 106 g of water, 45 g of poly(ethylene oxide) monophenyl ether (EO addition molar number: 90) (aromatic compound B), 3.4 g of aromatic compound A (A-1) synthesized from Manufacturing Example 1, 27 g of sodium lignosulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.3 g of 92% paraformaldehyde, 18.1 g of 98% sulfuric acid aqueous solution, and 0.02 g of defoamer Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were added. The reaction vessel was heated to 105°C over 30 minutes with stirring. After the liquid temperature reached 105°C, the reaction was carried out for 7 hours. After the reaction was completed, 42 g of 250 g / L calcium hydroxide aqueous solution and 7 g of 48% sodium hydroxide aqueous solution were added to the reaction vessel, and the mixture was stirred for another hour. By filtering these mixtures and removing the gypsum produced during neutralization, a liquid (L-1) containing a lignin derivative of a copolymer with a weight average molecular weight of 43,200 was obtained.

[0198] [Example 2]

[0199] (Manufacturing of lignin derivative (L-2))

[0200] 106 g of water, 2.3 g of aromatic compound A (A-1) synthesized in Manufacturing Example 1, 32.7 g of aromatic compound A (A-2), 38.6 g of sodium lignosulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.8 g of 92% paraformaldehyde, 18.1 g of 98% sulfuric acid aqueous solution, and 0.02 g of defoamer Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were added to a glass reaction vessel equipped with a thermometer, a stirring device, and a reflux device. The reaction vessel was heated to 105°C over 30 minutes with stirring. After the liquid temperature reached 105°C, the reaction was carried out for 7 hours. After the reaction was completed, 42 g of 250 g / L calcium hydroxide aqueous solution and 7 g of 48% sodium hydroxide aqueous solution were added to the reaction vessel, and the mixture was stirred for another hour. By filtering the mixture and removing the gypsum produced during neutralization, a liquid (L-2) containing a lignin derivative with a copolymer of weight average molecular weight of 53,000 was obtained.

[0201] [Example 3]

[0202] (Manufacturing of lignin derivative (L-3))

[0203] As aromatic compound A, except for using 3.4 g of the phosphate ester compound (A-3) synthesized by manufacturing example 1, a liquid (L-3) containing a lignin derivative of a copolymer with a weight average molecular weight of 61,000 was obtained under the same conditions and methods as in example 1.

[0204] [Examples 4-16]

[0205] (Manufacturing of lignin derivatives (L-4 to L-10, L-14 to L-19))

[0206] Except for changing the types of lignin sulfonate compounds and aromatic compounds (A, B) and the reaction ratios (addition ratios) of each compound as described in Table 1, liquid lignin derivatives (L-4) to (L-10) and (L-14) to (L-19) were obtained in the same manner as in Example 1. Furthermore, when obtaining liquid lignin derivatives (L-17) and (L-18), lignin sulfonate compounds were added dropwise.

[0207] [Comparative Example 1]

[0208] (Manufacturing of lignin derivative (L-11))

[0209] In a glass reaction vessel equipped with a thermometer, stirrer, and reflux device, 106 g of water, 41.2 g of poly(ethylene oxide) monophenyl ether (EO addition molar number: 100), 2.2 g of p-hydroxybenzoic acid, 4.9 g of aniline sulfonic acid, 26.9 g of sodium lignosulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.3 g of 92% paraformaldehyde, 18.1 g of 98% sulfuric acid aqueous solution, and 0.02 g of defoamer Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were added. The reaction vessel was heated to 105°C over 30 minutes with stirring. After the liquid temperature reached 105°C, the reaction was carried out for 7 hours. After the reaction was completed, 42 g of 250 g / L calcium hydroxide aqueous solution and 7 g of 48% sodium hydroxide aqueous solution were added to the reaction vessel, and the mixture was stirred for another hour. By filtering these mixtures and removing the gypsum produced during neutralization, a liquid (L-11) containing a lignin derivative with a copolymer of weight average molecular weight of 24,000 was obtained.

[0210] [Comparative Example 2]

[0211] (Manufacturing of lignin derivative (L-12))

[0212] Except for changing the types of lignin sulfonate compounds and aromatic compounds, and the reaction ratios (addition ratios) of each compound as described in Table 1, a liquid lignin derivative (L-12) was obtained in the same manner as in Example 1.

[0213] [Comparative Example 3]

[0214] Commercially available sodium lignosulfonate (L-13) was used directly in the experiment.

[0215] [Table 1]

[0216]

[0217] * Products from Tokyo Chemical Industry Co., Ltd., CAS RN 8061-51-6

[0218] ** Nippon Paper Co., Ltd. products

[0219] *** Borregaard products

[0220] ※1 During synthesis, lignin sulfonate compounds are added dropwise.

[0221] [Fresh Mortar Test]

[0222] Materials and Mixing

[0223] [Table 2] Mortar Mixing

[0224]

[0225] [Materials Used]

[0226] Water (W): Tap water

[0227] Cement (C): Ordinary Portland cement (manufactured by Pacific Cement, density 3.15)

[0228] Sand and gravel (S): Oi River soil and sand (surface dry saturated density 2.58, water absorption 2.1%, fineness modulus 2.55)

[0229] Mixing Methods

[0230] Sand and cement were added to a high-power mixer (manufactured by Marutō Corporation) in the amounts listed in Table 2, and the mixture was stirred dry for 10 seconds. Next, water containing sodium lignin sulfonate (L-3) (0.25% of cement) and Pronal 753W (0.01% of cement) manufactured by Toho Chemical Industry Co., Ltd., obtained from Examples 1-16, Comparative Examples 1-2, or Comparative Example 3, was added to the mixer and mixed at low speed for 30 seconds. The mixing state of the mortar was visually observed and scored while the mixer was temporarily stopped. After the mixer was stopped for 30 seconds, the mortar was further mixed at high speed for 60 seconds to prepare a flow test. Here, the mixing state of the mortar was scored out of 3 levels; a score of 0 or higher was considered good.

[0231] The results are shown in Table 3.

[0232] ◎: The materials are evenly mixed, and the mortar surface is very moist.

[0233] ○: The materials are uniformly mixed, and the mortar surface is visible as moist.

[0234] ×: The materials were not mixed evenly, and the mortar surface is not moist.

[0235] Methods for determining flow properties

[0236] The extensibility (flow value) of the test mortar was measured using a small slump cone (a conical cone with an upper inner diameter of 50 mm, a lower inner diameter of 100 mm, and a height of 150 mm) based on JIS A 1171 "Test method for polymer cement mortar".

[0237] The results are shown in Table 3.

[0238] [Table 3]

[0239]

[0240] ※2. The flow value cannot be measured due to lack of fluidity.

[0241] As shown in Table 3, the mortars of Examples 1 to 16 with the addition of the lignin derivative of the present invention showed good mixing condition and exhibited high fluidity 30 minutes after mixing was completed, and even 60 minutes later.

[0242] Furthermore, in the technical field of hydraulic compositions such as cement / mortar, a general requirement related to flowability is the ability to maintain flowability for approximately 30 to 60 minutes (retention performance). The results of Examples 1 to 16 above fully meet the requirements in this field. In particular, for the flowability of Examples 1, 3 to 6, 10, 12 to 14, and 16 with a lignin sulfonate compound / aromatic compound ratio of 20 / 80 to 40 / 60 (mass ratio), even after 60 minutes, there is little change from the initial state. Especially for Examples 12 and 16 with a lignin sulfonate compound / aromatic compound ratio of 20 / 80 to 35 / 65 (mass ratio), the difference between the flow value after 30 minutes and the flow value after 60 minutes is small, confirming that high flowability is maintained.

[0243] Furthermore, Examples 2, 7-9, 12, 13, and 15, in which the proportion of compound A in the aromatic compound is 10% by mass or more, confirmed excellent material uniformity at the initial stage of mixing.

[0244] Specifically, in Examples 1, 7, and 14, which used the same components as lignin sulfonate compounds, aromatic compounds, and aldehyde compounds, the lignin sulfonate compound / aromatic compound ratio of Examples 1 and 14, which was 20 / 80 to 40 / 60 (mass ratio), showed slightly worse initial flowability compared to Example 7 (which was outside the aforementioned range), but maintained high flowability. Furthermore, Example 14, in which lignin sulfonate compounds were added dropwise, maintained even higher flowability compared to Example 1. This is believed to be partly due to increased molecular weight uniformity of the polymer achieved through molecular weight control of the copolymer.

[0245] Except for changing the lignin sulfonate compounds, Examples 1, 4 to 6, which had the same composition and the same ratio of lignin sulfonate compounds to aromatic compounds, did not show significant differences in material homogeneity at the initial mixing stage. In addition, although there were slight variations in the initial fluidity, they tended to stabilize at approximately the same value after 60 minutes.

[0246] Similarly, in Examples 8, 15, and 16, where the three components described above were identical, it was confirmed that Example 16, with a lignin sulfonate compound / aromatic compound ratio of 20 / 80 to 35 / 65 (mass ratio), exhibited superior initial flowability and maintained high flowability compared to Examples 8 and 15, which were outside the aforementioned range. Furthermore, it was confirmed that Example 15, in which a lignin sulfonate compound was added dropwise, maintained even higher flowability compared to Example 8.

[0247] Similarly, in Examples 10 and 12 where the above three components were identical, it was confirmed that Example 12, with a lignin sulfonate compound / aromatic compound ratio of 20 / 80 to 35 / 65 (mass ratio), maintained high fluidity compared to Example 10, which was outside the above range.

[0248] Compared to Example 7 (90 moles of addition) and Example 8 (22 moles of addition), which mixed equal amounts of lignin sulfonic acid compounds and aromatic compounds and varied the number of moles of addition of alkylene oxides in compound B, although the initial flowability of Example 8 was slightly worse than that of Example 7, it was confirmed to have a tendency to maintain high flowability after 60 minutes.

[0249] On the other hand, the mortars of Comparative Examples 1-3, which did not use Compound A as an aromatic compound, could not be mixed evenly. In addition, the fluidity was poor immediately after mixing compared to the examples, and there was no fluidity after 60 minutes.

Claims

1. A lignin derivative, which is a reaction product comprising a mixture of a lignin sulfonate compound, an aromatic compound other than the lignin sulfonate compound, and an aldehyde compound. Having terminally phosphorylated (poly)alkylene oxides, The aromatic compound comprises either or both of compound A represented by formula (1) and compound B represented by formula (2). [Chemical Formula 1] In the formula, n represents 1 or 2. When n represents 1, R 1 represents a hydrogen atom, or a hydrocarbon group having 1 to 24 carbon atoms, A 1 O represents an alkylene oxide with 2 to 4 carbon atoms. m is A 1 The average number of moles added to O, representing numbers from 1 to 300. X 1 Indicates phosphate ester group, When n represents 2, R 1 It can represent -CH2-, -C(CH3)2-, or -SO2-. A 1 O represents an alkylene oxide with 2 to 4 carbon atoms. m is A 1 The average number of moles added to O, representing numbers from 1 to 300. X 1 Indicates phosphate ester group, [Chemical Formula 2] In the formula, q represents 1 or 2. When q represents 1 R 3 Represents a hydrogen atom, or a hydrocarbon group having 1 to 24 carbon atoms. A 2 O represents an alkylene oxide with 2 to 4 carbon atoms. p is A 2 The average number of moles added to O, representing numbers from 1 to 300. R 2 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms. When q represents 2 R 3 It can represent -CH2-, -C(CH3)2-, or -SO2-. A 2 O represents an alkylene oxide with 2 to 4 carbon atoms. p is A 2 The average number of moles added to O, representing numbers from 1 to 300. R 2 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

2. The lignin derivative according to claim 1, wherein, The content of compound A is 3% by mass or more relative to the total mass of the aromatic compounds.

3. The lignin derivative according to claim 1, wherein, The aldehyde compound is compound C represented by formula (3), [Chemical Formula 3] In the formula, R 4 This refers to hydrogen atoms, carboxyl groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, phenyl groups, naphthyl groups, or heterocyclic groups. r represents a number from 1 to 100.

4. The lignin derivative according to claim 1, wherein, The lignin derivative is a reaction product comprising a mixture of the lignin sulfonate compound and the aromatic compound, wherein the mass ratio of the lignin sulfonate compound to the aromatic compound is 20:80 to 35:

65.

5. An additive for hydraulic compositions, comprising the lignin derivative as described in any one of claims 1 to 4.

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