Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/16—Sulfur-containing compounds
  • C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids

Definitions

• the present invention relates to a lignin derivative and an additive for hydraulic compositions containing the same.
• Lignin is a natural polymeric compound found in trees, and lignin sulfonate, which is contained in sulfite pulp waste liquor discharged from the papermaking process, has long been used as a dispersant for cement, dyes, and other products. In recent years, it has been attracting attention as a renewable wood-derived biomass material, and further utilization is being considered.
• Patent Document 1 discloses a dispersant containing a lignin derivative consisting of a reaction product of a lignin sulfonate salt 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 which meets certain conditions such as viscosity and surface tension.
• JP 2011-240224 A International Publication No. 2019/039609 JP 2020-025935 A
• the present invention was made in consideration of the above-mentioned current situation, and aims to provide a lignin derivative and an additive for hydraulic compositions containing the same, which can be produced under industrially reasonable reaction conditions and can exhibit stable high fluidity by increasing the material uniformity of the hydraulic composition at the initial stage of mixing.
• a lignin derivative which is a reaction product of a mixture containing a lignosulfonic acid compound, an aromatic compound (excluding the lignosulfonic acid compound), and an aldehyde compound, A lignin derivative having a (poly)alkyleneoxy group whose terminal is phosphated.
• n 1 or 2
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms
• a 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms
• m is the average number of moles of A 1 O added and is a number from 1 to 300
• X1 represents a phosphate group
• R 1 represents —CH 2 —, —C(CH 3 ) 2 —, or —SO 2 —
• a 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms
• m is the average number of moles of A 1 O added and is a number from 1 to 300
• X1 represents a phosphate group.
• q represents 1 or 2
• R3 represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms
• a 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms
• p is the average number of moles of A 2 O added and is a number from 1 to 300
• R2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms
• R 3 represents —CH 2 —, —C(CH 3 ) 2 —, or —SO 2 —
• a 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms
• p is the average number of moles of A 2 O added and is a number from 1 to 300
• R2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.
• the lignin derivative of the present invention can be produced under industrially reasonable reaction conditions, and when added as an additive to a hydraulic composition, it can improve the uniformity of the material at the initial stage of mixing, thereby enabling the hydraulic composition to exhibit stable, high fluidity.
• the lignin derivative of the present invention is a reaction product of a mixture containing a lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, and has a (poly)alkyleneoxy group whose terminal is phosphated.
• the term "(poly)alkyleneoxy group having a phosphate ester at one end” refers to a structure in which a phosphate ester group is introduced at one end of a (poly)alkyleneoxy group.
• Examples of phosphate esters constituting the phosphate ester group include phosphate monoesters and their salts, phosphate diesters and their salts, phosphate triesters, and mixtures thereof.
• a phosphate ester group composed of a phosphate monoester represented by the following formula and its salt.
• the (poly)alkyleneoxy group is composed of repeating units (alkyleneoxy units) derived from alkylene oxide, and the number of carbon atoms in the alkyleneoxy unit is not particularly limited, but is usually 2 to 18, preferably 2 to 4, and more preferably 2 to 3.
• alkylene oxide (alkyleneoxy unit) include ethylene oxide (ethyleneoxy unit), propylene oxide (propyleneoxy unit), and butylene oxide (butyleneoxy unit), and ethylene oxide and propylene oxide are preferred.
• These alkylene oxides can be used alone or in combination of two or more.
• the addition form of the alkylene oxides may be either random addition or block addition.
• the average number of moles of the 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.
• the terminal of the (poly)alkyleneoxy group that is not phosphated may be bonded directly or via a linking group to a structural unit derived from a lignin sulfonate compound of a lignin derivative, or may be bonded similarly to a structural unit derived from an aromatic compound, or may be bonded to both, but is preferably bonded to a structural unit derived from an aromatic compound.
• the lignin sulfonic acid compound refers to a compound having a skeleton in which a carbon atom at the ⁇ -position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group.
• the above compounds may be chemically modified by hydrolysis, alkoxylation, desulfonation, alkylation, or the like.
• the lignin sulfonic acid compound may be in the form of a salt.
• salts include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts. Of these, calcium salts, magnesium salts, sodium salts, etc. are preferred.
• the manufacturing method and origin of the lignin sulfonate compound are not particularly limited, and it may be either a natural product or a synthetic product.
• Lignin sulfonate compounds are one of the main components of the waste liquor of sulfite pulp obtained by cooking wood under acidic conditions. Therefore, lignin sulfonate compounds derived from sulfite pulp waste liquor may be used.
• commercially available products may be used as the lignin sulfonate compound. Examples of commercially available products include sodium lignin sulfonate manufactured by Tokyo Chemical Industry Co., Ltd., Vanilex (registered trademark) HW, Vanilex N, etc.
• the aromatic compound refers to a compound having at least one aromatic skeleton, other than the lignosulfonic acid compound, which undergoes a condensation reaction with the lignosulfonic acid compound to form a copolymer.
• the aromatic compound include a phenolic compound having a (poly)alkyleneoxy group whose terminal is phosphoric esterified (compound A represented by formula (1) described below), an alkylene oxide adduct of a phenolic compound or a derivative thereof (compound B represented by formula (2)), as well as phenols and non-phenolic aromatic compounds having no phenolic hydroxy group.
• Compound A is a phosphate derivative of an alkylene oxide adduct of a phenolic compound such as phenol or bisphenol A, and has a structure represented by the following formula (1).
• the aromatic compound of the present invention preferably contains at least compound A represented by formula (1).
• 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; when n represents 2, R 1 represents -CH 2 -, -C(CH 3 ) 2 -, or -SO 2 -.
• a 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms; m is the average number of moles of A 1 O added and is a number of 1 to 300; and X 1 represents a phosphate group.
• the compound A is a phosphate derivative of a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a phenolic compound such as phenol or bisphenol A or the like, which is a substituted compound.
• a phenolic compound such as phenol or bisphenol A or the like
• alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide. These alkylene oxides can be added singly or in combination. When two or more alkylene oxides are used, they may be added in either a block or random form.
• examples of the alkyleneoxy group having 2 to 4 carbon atoms in A 1 O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group.
• a 1 O may be composed of only an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or may contain two or more of these groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.
• m is the average number of moles of A 1 O added, and is a number of 1 to 300, preferably 2 to 200, and more preferably 3 to 150.
• examples of the hydrocarbon group having 1 to 24 carbon atoms in R 1 include an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group having 4 to 24 carbon atoms and having two or more unsaturated bonds, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 24 carbon atoms.
• alkyl group having 1 to 24 carbon atoms examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group (a lauryl group), a tetradecyl group (a myristyl group), a hexadecyl group (a palmityl group), an octadecyl group (a stearyl group), an icosyl group, a docosyl group (a behenyl group), a tetracosyl group, and the like, which may have a branched structure (for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopen
• alkenyl group having 2 to 24 carbon atoms examples include the above-mentioned alkyl groups having 2 to 24 carbon atoms, each of which has one carbon-carbon double bond. Specific examples include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, octadecenyl, eicosenyl, docosenyl, and tetracosenyl groups, each of which may have a branched structure and/or a cyclic structure.
• Examples of the unsaturated aliphatic hydrocarbon group having 4 to 24 carbon atoms and two or more unsaturated bonds include a decadienyl group, an undecadienyl group, a dodecadienyl group, a tridecadienyl group, a tetradecadienyl group, a pentadecadienyl group, a hexadecadienyl group, a heptadecadienyl group, an octadecadienyl group, a nonadecadienyl group, an icosadienyl group, a henicosadienyl group, a docosadienyl group, a tricosadienyl group, Examples of such groups include a tetracosadienyl group, a decatrienyl group, an undecatrienyl group, a dodecatrienyl group, a tridecatrienyl
• aryl group having 6 to 20 carbon atoms examples include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
• An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those mentioned above.
• aralkyl groups having 7 to 24 carbon atoms include, but are not limited to, a phenylmethyl group (benzyl group), an ⁇ -methylbenzyl group, a 2-phenylethyl group, a 1-methyl-1-phenylethyl group (cumyl group), a 3-phenyl-propyl group, a 2-phenyl-2-propyl group, and the like.
• R 1 represents —CH 2 —, —C(CH 3 ) 2 —, or —SO 2 —.
• the bonding position of R 1 in formula (1) is not particularly limited, but it is preferable that R 1 be bonded to the para position with respect to the oxygen atom bonded to the aromatic ring, in terms of easily exerting the effects of the present invention.
• R 1 is preferably a hydrogen atom or a tert-butyl group, and when n is 2, R 1 is preferably --C(CH 3 ) 2 --.
• Compound A is a phosphoric acid monoester and/or a salt thereof, a phosphoric acid diester and/or a salt thereof, a phosphoric acid triester, or a mixture thereof.
• the phosphate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium.
• the compound A may be synthesized by a known method using a phosphorylating agent on a (poly)oxyalkylene alkylphenol.
• the phosphorylating agent include phosphoric anhydride, phosphoric acid, polyphosphoric acid, and phosphorus oxychloride.
• the compound A represented by the above formula (1) for example, when n is 1, the compound A may be represented by the following formula:
• R 1 , A 1 O, and n are the same as those defined in the above formula (1)
• Ph is a phenylene group
• M is 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, or an organic ammonium group such as an alkylammonium group or an alkanolammonium group.
• Z represents a polyoxyalkylene alkyl ether residue represented by the formula: R′′-O-(A′O)w- (wherein R′′ represents an alkyl group having 1 to 24 carbon atoms, A′O represents an alkyleneoxy group having 2 to 3 carbon atoms, i.e., an ethyleneoxy group or a propyleneoxy group, and w represents the average molar number of alkyleneoxy groups A′O added, which is 1 to 300), and when there are a plurality of Z's, they may be the same group or different groups.
• the compound A represented by the above formula (1) can be used either alone or in combination of two or more.
• the content ratio of compound A to the total mass of the aromatic compounds is preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 5 mass% or more, and the aromatic compounds may be composed only of compound A (100 mass%).
• the content ratio of compound A in the aromatic compounds is 10 mass% or more, it is expected that the uniformity of the kneaded material will be improved.
• the aromatic compound may further include, in addition to compound A represented by formula (1) above, compound B having a structure represented by formula (2) below.
• q represents 1 or 2; when q represents 1, R3 represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; when q represents 2, R3 represents -CH2- , -C( CH3 ) 2- , or -SO2- .
• a 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms
• p is the average number of moles of A 2 O added and is a number of 1 to 300
• R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.
• the above-mentioned compound B is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a phenolic compound such as phenol or bisphenol A, or a substituted compound thereof, and derivatives of the alkylene oxide adduct (alkyl ester or fatty acid ester) are also included in compound B.
• a phenolic compound such as phenol or bisphenol A
• derivatives of the alkylene oxide adduct alkyl ester or fatty acid ester
• alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide. These alkylene oxides can be added singly or in combination. When two or more alkylene oxides are used, they may be added in either a block or random form.
• examples of the alkyleneoxy group having 2 to 4 carbon atoms in A 2 O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group.
• a 2 O may be composed of only an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or may contain two or more of these groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.
• p is the average number of moles of alkyleneoxy groups added and represents a number from 1 to 300, preferably from 10 to 200, and more preferably from 20 to 150.
• the alkyl group having 1 to 10 carbon atoms in R 2 may have a branched structure and/or a cyclic structure, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms among the groups given as specific examples of the alkyl group having 1 to 24 carbon atoms in R 1.
• Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, and a 1-adamantyl group.
• acyl group having 2 to 24 carbon atoms examples include saturated or unsaturated acyl groups (R'(CO)- group, where R' is a hydrocarbon group having 1 to 23 carbon atoms).
• saturated acyl group having 2 to 24 carbon atoms include carboxylic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid (pentadecylic acid), hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, eicosa
• R 3 represents —CH 2 —, —C(CH 3 ) 2 —, or —SO 2 —.
• the bonding position of R3 in formula (2) is not particularly limited, but it is preferable that R3 be bonded to the para position with respect to the oxygen atom bonded to the aromatic ring, in terms of easily exerting the effects of the present invention.
• R 3 is preferably a hydrogen atom or a tert-butyl group, and when q is 2, R 3 is preferably --C(CH 3 ) 2 --.
• the compound B represented by the above formula (2) can be used either alone or in combination of two or more.
• the content ratio of compound B in the aromatic compound is not particularly limited, but may be the remainder excluding compound A.
• the aromatic compound may contain, in addition to the above-mentioned compound A and compound B, other aromatic compounds capable of reacting with these compounds, within a range that does not impair the effects of the present invention.
• aromatic compounds include phenol, bisphenol A, isophthalic acid, oxynaphthoic acid, benzoic acid, hydroxybenzoic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, aniline sulfonic acid, benzenesulfonic acid, toluenesulfonic acid, and hydroxyethylphenol.
• aldehyde compounds As the aldehyde compound, a compound C having a structure represented by the following formula (3) can be preferably used.
• R 4 represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group; r represents a number from 1 to 100.
• alkyl groups, alkenyl groups, phenyl groups, naphthyl groups and heterocyclic groups may be substituted with any substituent, such as an alkyl group having 1 to 10 carbon atoms; an aryl group such as a phenyl group or a naphthyl group; a halogen atom such as a chlorine atom or a bromine atom; a sulfonic acid functional group such as a sulfo group or a sulfonate group; an acyl group such as an acetyl group; a hydroxy group; an amino group; or a carboxyl group.
• substituent such as an alkyl group having 1 to 10 carbon atoms; an aryl group such as a phenyl group or a naphthyl group; a halogen atom such as a chlorine atom or a bromine atom; a sulfonic acid functional group such as a sulfo group or a s
• the alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms in R4 may have a branched structure or a cyclic structure, and specific examples thereof include the alkyl group having 1 to 10 carbon atoms and the alkenyl group having 2 to 10 carbon atoms among the groups given as specific examples of the alkyl group having 1 to 24 carbon atoms and the alkenyl group having 2 to 24 carbon atoms in R1 in the compound A (formula (1)).
• examples of the heterocyclic group include a furyl group, a thienyl group, a pyridyl group, a piperidyl group, and a morpholino group.
• r preferably represents a number from 2 to 100.
• Examples of the compound C (aldehydes) include formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexylaldehyde, heptanal, octylaldehyde, nonylaldehyde, isononylaldehyde, decylaldehyde, dodecanal, acrolein, crotonaldehyde, pentenal, hexenal, heptenal, octenal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylaldehyde
• Compound C represented by the above formula (3) can be used alone or in combination of two or more.
• the mass ratio of the lignin sulfonic acid compound/aromatic compound is 20/80 to 40/60, it is expected to obtain a more stable and high fluidity, and particularly when the mass ratio is 20/80 to 35/65, it is expected to obtain an even more stable and high fluidity.
• reaction ratio the mass ratio of the total amount of structural units derived from lignosulfonic acid compounds and unreacted lignosulfonic acid compound components to the total amount of structural units derived from aromatic compounds and unreacted aromatic compound components is the same as the feeding ratio thereof.
• reaction amount of the aldehyde compound relative to the total amount of the lignosulfonic acid compound and the aromatic compound is not particularly limited, but the mass ratio of the total amount to the aldehyde compound is preferably 99/1 to 80/20, more preferably 98/2 to 85/15, for example 98/2 to 90/10.
• the lignin derivative of the present invention is a reaction product of a mixture containing the above-mentioned lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, and comprises a copolymer obtained by polycondensation of this mixture.
• the ratio of each compound is not particularly limited.
• the polymerization method for obtaining the copolymer is not particularly limited.
• the order and method of adding the lignin sulfonic acid compound, aromatic compound, and aldehyde compound in the polycondensation are not particularly limited, and may be, for example, adding all of the raw material compounds at once before the polycondensation reaction, adding a portion of the raw material compounds before the polycondensation reaction and then adding the remainder in portions by dropwise addition, or adding a portion of the raw material compounds before the polycondensation reaction and then adding the remainder after a certain reaction time has elapsed, etc.
• the lignin derivative can be obtained, for example, by polycondensing a lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound in the presence of a dehydration catalyst, either without a solvent or with a solvent, at a reaction temperature of 80° C. to 150° C. under normal pressure to elevated pressure, for example, 0.001 to 1 MPa.
• Examples of the dehydration catalyst include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octyl sulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic 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, nitrobenzoic acid, nitrosalicylic acid, paratoluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, activated clay, and the like
• dehydration catalysts may be used alone or in combination of two or more.
• the solvent may be water, a glycol ether compound such as propylene glycol monomethyl ether (PGME), an aromatic compound such as toluene or xylene, or a cyclic aliphatic compound such as methylcyclohexane.
• PGME propylene glycol monomethyl ether
• an aromatic compound such as toluene or xylene
• a cyclic aliphatic compound such as methylcyclohexane.
• a solvent that can be used as the dehydration catalyst such as acetic acid, may be used.
• the concentration of the components (lignin sulfonic acid compound, aromatic compound, and aldehyde compound) to be subjected to the polycondensation reaction in the reaction system may be appropriately selected, but if the concentration is too high, gelation may easily occur, and if the concentration is too low, the reaction may not proceed quickly.
• the components to be subjected to the polycondensation reaction may be about 30 to 70%.
• the reaction temperature may be, for example, 95° C. to 130° C., and the polycondensation reaction can be completed by carrying out the reaction for about 3 to 25 hours.
• the polycondensation reaction is preferably carried out under acidic conditions, and it is preferable to adjust the pH of the reaction system to 4 or less.
• a defoaming agent may be used during the production of the lignin derivative (polycondensation reaction), which can suppress foaming during the reaction and create a uniform reaction system.
• various known methods can be used to reduce the content of the unreacted aldehyde component (compound C) in the reaction system.
• various known methods can be used to reduce the content of the unreacted aldehyde component (compound C) in the reaction system.
• the dehydration catalyst used in the reaction can be neutralized after completion of the reaction and removed in the form of a salt by filtration, but even in an embodiment in which the catalyst is not removed, the performance of the additive for hydraulic compositions of the present invention described below is not impaired.
• Methods for removing the catalyst include, in addition to the above-mentioned filtration, phase separation, dialysis, ultrafiltration, and the use of an ion exchanger. Neutralizing the reaction product and diluting it with water or the like improves the workability of measurement and the like when it is used as an additive for hydraulic compositions, which will be described later.
• examples of basic compounds used for neutralization include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, ammonia, and organic amines such as monoethanolamine, diethanolamine, and triethanolamine, and one or more of these may be used in combination.
• alkali hydroxides such as sodium hydroxide and potassium hydroxide
• alkaline earth hydroxides such as calcium hydroxide
• ammonia such as calcium hydroxide
• organic amines such as monoethanolamine, diethanolamine, and triethanolamine
• the finally obtained copolymer suitably has a weight average molecular weight Mw (measured by gel permeation chromatography (hereinafter referred to as "GPC"), calculated as polyethylene glycol) in the range of 4,000 to 150,000, and more preferably has a weight average molecular weight in the range of 8,000 to 120,000, and particularly preferably in the range of 12,000 to 100,000, from the viewpoint of exhibiting excellent dispersion performance.
• Mw measured by gel permeation chromatography
• the "lignin derivative” may consist only of a copolymer obtained by polycondensation of a monomer mixture containing a lignin sulfonic acid compound, an aromatic compound, and an aldehyde compound, but generally includes components including unreacted components and by-products generated in each polymerization step, alkylene oxide addition step, etc.
• the additive for hydraulic compositions of the present invention contains the above-mentioned lignin derivative, and can be appropriately combined with known additives for hydraulic compositions according to various applications to produce so-called admixtures.
• At least one other additive selected from the group consisting of defoamers, setting retarders, setting accelerators, separation reducing agents, thickeners, shrinkage reducing agents, curing agents, water repellents, etc. may be blended. can.
• the hydraulic composition refers to a composition containing a powder having a property of hardening by a hydration reaction (hydraulic powder), such as cement, gypsum, fly ash, blast furnace slag, etc.
• a hydration reaction such as cement, gypsum, fly ash, blast furnace slag, etc.
• cement the hydraulic composition is also called a cement composition.
• cement dispersants are used in appropriate combinations depending on the manufacturing conditions and performance requirements of concrete, etc.
• the additive for hydraulic compositions of the present invention which is used alone as a cement dispersant or as a main agent, but can also be used as a modification aid for cement dispersants with large slump loss, or in combination with cement dispersants with high initial water reduction properties.
• known cement dispersants include salts of polycarboxylic acid copolymers described in JP-B-59-18338, JP-A-2628486, JP-A-2774445, etc., as well as salts of naphthalenesulfonic acid-formalin condensates, salts of melaminesulfonic acid-formalin condensates, ligninsulfonates, sodium gluconate, and sugar alcohols.
• the blending ratio of the polycondensate of the present invention to the known cement dispersants is, for example, 1:99 to 99:1 mass%.
• air entraining agents include anionic air entraining agents, nonionic air entraining agents, and amphoteric air entraining agents.
• the setting retarder include inorganic setting retarders and organic setting retarders. More specifically, examples include oxycarboxylic acids such as gluconic acid, glucoheptonic acid, tartaric acid, citric acid, malic acid, and arabinic acid, and salts thereof; sugars such as sucrose; and inorganic compounds such as zinc oxide, zinc chloride, silicofluorides, and silicofluoride salts.
• the accelerator may be an inorganic accelerator or an organic accelerator.
• thickeners/separation reducing agents examples include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymer-based thickeners such as diutan gum, welan gum, and xanthan gum, and non-ionic thickeners such as polyethylene glycol and polyalkylene oxide.
• examples of the antifoaming agent include nonionic antifoaming agents, silicone antifoaming agents, higher alcohols, and mixtures containing these as main components.
• the components constituting the cement composition are conventionally used components for concrete, such as cement (e.g., ordinary Portland cement, high-early-strength Portland cement, ultra-high-early-strength Portland cement, low-heat/moderate-heat Portland cement, blast-furnace cement, etc.), aggregate (i.e., fine aggregate and coarse aggregate), admixture (e.g., silica fume, calcium carbonate powder, ground granulated blast-furnace slag, fly ash, etc.), expansive agent, and water.
• cement e.g., ordinary Portland cement, high-early-strength Portland cement, ultra-high-early-strength Portland cement, low-heat/moderate-heat Portland cement, blast-furnace cement, etc.
• aggregate i.e., fine aggregate and coarse aggregate
• admixture e.g., silica fume, calcium carbonate powder, ground granulated blast-furnace slag, fly ash,
• the additive for hydraulic compositions of the present invention can also be suitably used in hydraulic compositions (cement compositions) containing fly ash or ground granulated blast furnace slag as admixtures.
• Fly ash is composed mainly of silica (SiO 2 ) and alumina (Al 2 O 3 ), and is categorized into types I to IV (JIS A6201) based on particle size and flow value. It is said that the amount of unburned carbon contained in fly ash is related to the amount of air entraining agent used, and that an increase in the amount of unburned carbon tends to increase the amount of air entraining agent used. The amount of unburned carbon is generally said to be correlated with the amount of methylene blue adsorbed by fly ash.
• Ground granulated blast furnace slag is a by-product produced when refining iron in a blast furnace, and is composed mainly of calcium oxide (CaO), silica (SiO 2 ), and alumina (Al 2 O
• admixtures other than the additive for hydraulic compositions of the present invention that can be added separately during mixing include the above-mentioned publicly known and publicly used air entraining agents, setting retarders, accelerators, separation reducing agents, thickeners, defoamers, shrinkage reducing agents, etc., which can also be mixed appropriately.
• the mixing ratio of each of these components can be determined appropriately depending on the type of component selected and the purpose of use.
• the amount of the additive for hydraulic compositions of the present invention to be added varies depending on the mixing conditions including the above-mentioned concrete materials, but is usually added in an amount of about 0.05 to 5.0 mass% (as the amount of the lignin derivative itself) calculated as solid content based on the mass of cement, or based on the total mass of cement and powder such as fly ash when pozzolanic fine powder such as fly ash is used in combination.
• the amount added is appropriately adjusted according to the desired initial flow value, but care should be taken because adding too much may cause delay in setting and, in some cases, cause hardening failure.
• the additive for hydraulic compositions of the present invention can achieve higher fluidity than conventional products, that is, it can exhibit its performance at a lower addition rate than conventional products.
• the method of use is the same as that of a general cement dispersant, and it can be added as a stock solution when mixing concrete, or diluted in mixing water beforehand and added, or it can be added after mixing concrete or mortar, and then mixed uniformly again.
• the weight average molecular weight of the lignin derivative was measured by the following measurement method.
• GPC Gel Permeation Chromatography
• ⁇ Gel permeation chromatography (GPC) measurement conditions> Column: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko K.K.) Eluent: a mixture of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80/20)
• Detector differential refractometer, calibration curve: polyethylene glycol
• a phosphate ester of an EO 90 mol adduct of p-tert-butylphenol (A-2), a phosphate ester of an EO 4 mol adduct of bisphenol A (A-3), and a phosphate ester of an EO 3 mol adduct of p-tert-butylphenol (A-4) were obtained.
• aromatic compound B poly(ethylene oxide) monophenyl ethers having various EO addition mole numbers, an EO 60 mole adduct of bisphenol A, and an EO 44 mole adduct of p-tert-butylphenol were prepared.
• Example 1 (Production of lignin derivative (L-1))
• 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 mole number: 90) (aromatic compound B), 3.4 g of aromatic compound A (A-1) synthesized in Production Example 1, 27 g of sodium lignin sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.3 g of 92% paraformaldehyde, 18.1 g of 98% aqueous sulfuric acid solution, and 0.02 g of antifoaming agent Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were charged, and the reaction vessel was heated to 105 ° C.
• Example 2 (Production of lignin derivative (L-2))
• a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux device 106 g of water, 2.3 g of aromatic compound A (A-1) synthesized in Production Example 1, 32.7 g of aromatic compound A (A-2), 38.6 g of sodium ligninsulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.8 g of 92% paraformaldehyde, 18.1 g of 98% aqueous sulfuric acid solution, and 0.02 g of defoamer Pronal 753W (manufactured by Toho Chemical Industry Co., Ltd.) were charged, and the reaction vessel was heated to 105 ° C.
• Example 3 (Production of lignin derivative (L-3)) A liquid (L-3) of a lignin derivative containing a copolymer having a weight average molecular weight of 61,000 was obtained under the same conditions and by the same method as in Example 1, except that 3.4 g of the phosphate ester compound (A-3) synthesized in Production Example 1 was used as the aromatic compound A.
• Examples 4 to 16 (Production of lignin derivatives (L-4 to L-10, L-14 to L-19)) Lignin derivative liquids (L-4) to (L-10) and (L-14) to (L-19) were obtained in the same manner as in Example 1, except that the types of lignin sulfonate compound and aromatic compound (A, B) and the reaction ratio (feed ratio) of each compound were changed as shown in Table 1.
• the lignin sulfonate compound was added dropwise.
• the mortar was prepared by additionally mixing at high speed for 60 seconds, and the mortar was subjected to flow measurement.
• the mixed state of the mortar was evaluated in the following three stages, and if it was ⁇ or higher, it could be judged to be good.
• the results obtained are shown in Table 3.
• the mortars of Examples 1 to 16 to which the lignin derivative of the present invention was added had a good mixed state and exhibited high fluidity from immediately after mixing until 30 minutes later and even 60 minutes later.
• the performance required for fluidity in general can be the ability to maintain fluidity for about 30 to 60 minutes (retention performance).
• Examples 1 to 16 above fully satisfy the performance required in the industry, and in particular, Examples 1, 3 to 6, 10, 12 to 14, and 16, in which the lignin sulfonate compound/aromatic compound ratio was 20/80 to 40/60 (mass ratio), showed little change from the initial state in terms of fluidity even after 60 minutes had elapsed, and in particular, Examples 12 and 16, in which the lignin sulfonate compound/aromatic compound ratio was 20/80 to 35/65 (mass ratio), showed little difference between the flow value after 30 minutes and the flow value after 60 minutes, confirming that high fluidity was maintained. Moreover, it was confirmed that Examples 2, 7 to 9, 12, 13, and 15, in which the proportion of compound A in the aromatic compounds was 10 mass % or more, had excellent material uniformity at the initial stage of mixing.
• Examples 1, 7, and 14 in which the same components were used as the lignin sulfonate compound, aromatic compound, and aldehyde compound it was confirmed that Examples 1 and 14, in which the lignin sulfonate compound/aromatic compound was 20/80 to 40/60 (mass ratio), maintained high fluidity, although the initial fluidity was somewhat inferior to that of Example 7, which was outside the above range.
• Example 16 in which the lignosulfonic acid compound/aromatic compound was 20/80 to 35/65 (mass ratio), had excellent initial fluidity and maintained high fluidity compared to Examples 8 and 15, which were outside the above range.
• Example 15 in which the lignosulfonic acid compound was added dropwise, maintained higher fluidity than Example 8.
• Example 12 in which the above three components were the same, it was confirmed that Example 12, in which the lignin sulfonic acid compound/aromatic compound was 20/80 to 35/65 (mass ratio), maintained a higher fluidity than Example 10, which was outside the above range.
• Example 7 (number of moles added: 90) and Example 8 (number of moles added: 22), in which the blending amounts of lignin sulfonic acid compound/aromatic compound were the same and the number of moles of alkyleneoxy groups added in compound B was changed, it was confirmed that although the initial fluidity of Example 8 was somewhat inferior to that of Example 7, it tended to maintain high fluidity after 60 minutes had elapsed.

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