WO2014196618A1 - Additif à ciment - Google Patents

Additif à ciment Download PDF

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Publication number
WO2014196618A1
WO2014196618A1 PCT/JP2014/065032 JP2014065032W WO2014196618A1 WO 2014196618 A1 WO2014196618 A1 WO 2014196618A1 JP 2014065032 W JP2014065032 W JP 2014065032W WO 2014196618 A1 WO2014196618 A1 WO 2014196618A1
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Prior art keywords
lignin
cement
cement additive
acid
mass
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PCT/JP2014/065032
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English (en)
Japanese (ja)
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真美 服部
森本　正和
山田　竜彦
史帆 ▲高▼橋
Original Assignee
株式会社日本触媒
独立行政法人森林総合研究所
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Publication of WO2014196618A1 publication Critical patent/WO2014196618A1/fr

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    • 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
    • C04B24/24—Macromolecular compounds
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

Definitions

  • the present invention relates to a cement additive containing lignin. More specifically, the present invention relates to a cement additive useful for cement compositions such as cement and gypsum and other hydraulic materials.
  • Lignin is one of the three major components of plant biomass such as wood (three major components: cellulose, hemicellulose, lignin), and is the most abundant on the earth as a natural aromatic polymer. .
  • lignin among the phenylpropanoids synthesized by carbon compounds assimilated by photosynthesis (primary metabolism) undergoing further metabolism (secondary metabolism), p-coumaryl alcohol, coniphenyl alcohol, Lignin monomer, the three basic skeletons of pill alcohol, is one-electron-oxidized by oxidase such as laccase and peroxidase to form phenoxy radical, which forms a complex three-dimensional network structure by radical coupling in an amorphous form. ing.
  • Lignins are classified into woody lignins obtained from woody plants and herbaceous lignins obtained from herbaceous plants, and these differ in the types of basic skeletons that comprise lignin, their proportions and bonding forms. Depending on the structure. In addition, lignin is isolated by chemical treatment of the raw material, but it cannot be isolated as it is in the original structure present in the plant, and the resulting lignin structure is also different depending on the isolation method. Change.
  • lignin As described above, the molecular structure of lignin is complex, and the chemical properties of lignin vary greatly depending on the isolation method used for isolation from plant bodies, so the use of lignin as an industrial material is limited. ing. Furthermore, lignin is basically a hydrophobic substance and is poorly water-soluble, which is one reason that its use is limited.
  • a chemical pulping method called a sulfite cooking method is conventionally known.
  • sulfite and sulfite are used as cooking liquor, and lignin in the cooking black liquor is converted to lignin sulfonic acid.
  • lignin sulfonate is used as a cement additive, and a dispersant containing a sulfite pulp waste liquid modified product having a structural unit derived from a water-soluble monomer (see, for example, Patent Document 1) And a dispersant containing a lignin derivative that is a reaction product of a lignin sulfonic acid compound and a water-soluble monomer (see, for example, Patent Document 2).
  • the sulfite cooking method is problematic in that it is restricted by the plant species of the raw material and the chemical recovery of the cooking solution is inferior, so there are currently only a few plants that are conducting the sulfite cooking method. As a result, the supply of lignin sulfonic acid as a by-product is not sufficient.
  • Kraft lignin obtained by this method has a thioether bond or the like.
  • Kraft lignin is also disclosed as a dispersant, and is characterized by containing a lignin derivative having a structural unit derived from kraft lignin and / or a salt thereof and a structural unit derived from a water-soluble monomer.
  • An agent see, for example, Patent Document 3 is disclosed.
  • alkali cooking method only sodium hydroxide is used as the cooking solution.
  • the lignin obtained by this method is called alkaline lignin and does not contain sulfur in the lignin structure.
  • the use of such alkaline lignin as a dispersant is also disclosed, and a concrete admixture mainly composed of a lignin derivative produced by a reaction between lignin and a hydrophilic compound (see, for example, Patent Document 4).
  • a mortar additive using alkaline lignin isolated from a herbaceous plant as a raw material for example, see Non-Patent Document 1.
  • the sulfite cooking method currently has a small number of factories due to various limitations, and as a result, the supply of lignin sulfonic acid as a by-product is not sufficient.
  • conventional dispersants and admixtures that use lignin as a raw material, those using lignin other than lignin sulfonic acid are used as cement dispersants after derivatizing lignin to make them hydrophilic.
  • a cement additive such as a cement dispersant using lignin as a raw material can be obtained with fewer steps.
  • problems such as a problem that a lot of water-soluble sugar components are mixed in the obtained lignin, and there are a small number of factories for producing pulp from herbs.
  • the present invention has been made in view of the above-mentioned present situation, and uses a woody plant as a raw material, does not use lignin sulfonic acid, and can be obtained in fewer steps than conventional additives using lignin as a raw material.
  • An object is to provide an additive.
  • the present inventor has made various studies on means for solving the above problems. As a result, when a lignin is isolated by alkali digestion using a woody plant as a raw material, the resulting lignin does not have to be derivatized by reacting with a hydrophilic compound. It was found that it can be used as a cement additive as it is.
  • the present inventor further examined lignin that can be used as a cement additive without derivatization, and the content of elemental sulfur is in the range of 0.1 to 4% by mass with respect to 100% by mass of lignin,
  • the inventors have found that lignin that is insoluble in an aqueous solution having a pH of 2.0 can be used as a cement additive as it is, and conceived that the above-mentioned problems can be solved brilliantly, and the present invention has been achieved.
  • the cement additive of the present invention used as it is without derivatizing lignin, which is removed by digestion in the process of obtaining pulp from wood and has not been found to have enough effective use, is an effective and simple use of forestry resources.
  • the method is proposed and has great technical significance in that it contributes to the activation of forestry.
  • the present invention is a cement additive containing lignin
  • the lignin is a cement additive mainly composed of alkaline lignin obtained from woody plants.
  • the present invention is described in detail below. A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
  • the cement additive of the present invention is a cement additive containing lignin, the lignin being a cement additive mainly composed of alkali lignin obtained from woody plants (hereinafter referred to as the first of the present invention). And a lignin-containing cement additive having a sulfur element content in the range of 0.1 to 4% by mass with respect to 100% by mass of lignin. And a cement additive (hereinafter also referred to as a second cement additive of the present invention) characterized by being insoluble in an aqueous solution having a pH of 2.0.
  • the cement additive corresponding to both the first cement additive and the second cement additive of the present invention naturally corresponds to the cement additive of the present invention.
  • the first cement additive of the present invention will be described, and then the second cement additive of the present invention will be described.
  • the description of “the cement additive of the present invention” corresponds to both the first cement additive and the second cement additive of the present invention.
  • the 1st cement additive of this invention contains the lignin which has as a main component the alkaline lignin obtained from a woody plant as a raw material.
  • the alkali lignin obtained from the woody plant contained in the first cement additive of the present invention as a raw material means the lignin itself (unmodified lignin) obtained from the woody plant by alkali digestion, and the lignin is obtained by alkali digestion. After that, the lignin derivative obtained by reacting with another compound is not included in the “alkaline lignin obtained using woody plants as a raw material” herein.
  • This alkaline lignin is insoluble in an aqueous solution having a pH of 2.0, and lignin derivatives having structural units derived from lignin and hydrophilic or water-soluble compounds that have been conventionally used as cement additives A distinction is made in this respect.
  • the lignin contained in the first cement additive of the present invention is mainly composed of alkaline lignin obtained from woody plants as a raw material.
  • the main component is alkali lignin obtained from woody plants, alkali lignin obtained from materials other than woody plants, kraft lignin, acetate lignin, organosolv lignin, explosive lignin, sulfate lignin, etc.
  • the other lignin and the lignin derivative obtained by reacting lignin with another compound may contain one or more kinds.
  • the main component is alkali lignin obtained from a woody plant as a raw material, but 50% by mass or more of 100% by mass of lignin is an alkaline lignin obtained from a woody plant as a raw material.
  • the alkali lignin obtained using woody plants as a raw material is preferably 80% by mass or more. More preferably, it is 90% by mass or more, and particularly preferably 100% by mass, that is, the cement additive contains only alkali lignin obtained from woody plants as lignin.
  • the woody plant that is the raw material of the above alkaline lignin is a plant classified into the woody system among the wood from which lignin can be extracted, and conifers such as cedar, fir, cypress and pine, eucalyptus, acacia, birch, beech, This applies to broadleaf trees such as oak.
  • the woody plant is a conifer or a hardwood.
  • the alkali lignin may be obtained from a softwood as a raw material, may be obtained from a hardwood as a raw material, or may be a mixture thereof.
  • it is obtained using conifer as a raw material.
  • the alkali cooking can be performed by a commonly performed method, and the conditions of the alkali cooking are not particularly limited.
  • a method of cooking the plant is preferred. By digesting the woody plant by such a method, lignin can be efficiently extracted.
  • any alkali metal hydroxide can be used, but lithium hydroxide, sodium hydroxide, or potassium hydroxide is preferable. More preferably, it is sodium hydroxide (caustic soda).
  • the method of pulping with caustic soda is called soda cooking, and wood is digested with hot caustic soda and then washed and bleached to obtain pulp. It is a simple method using only caustic soda as the cooking solution, and lignin is eluted by lowering the molecular weight by cleavage of phenyl ether under the action of caustic soda. Lignin obtained from soda cooking is superior in that it does not contain sulfur components derived from cooking liquor and has no problems with sulfur-derived odors.
  • the cooking method is preferably a method using an alkali metal hydroxide and further a cooking aid.
  • a cooking aid is an agent added to cooking liquor to promote delignification and prevent carbohydrate elution, anthraquinone, dihydroanthraquinone, tetrahydroanthraquinone, methylanthraquinone, methyldihydroanthraquinone, methyltetrahydroanthraquinone, benzoquinone, naphthoquinone, A quinone compound such as phenanthroquinone; a hydroquinone compound such as anthrahydroquinone, methylanthrahydroquinone, dihydroanthrahydroanthraquinone or an alkali metal salt thereof; a precursor of anthrone, anthranol, methylanthrone, methylanthranol, or one of polysulfides; Two or more kinds can
  • anthraquinone is an excellent cooking aid that contributes to promoting delignification and stabilizing carbohydrates, and is used in an amount of about 0.1% with respect to the chip.
  • Anthraquinone oxidizes and stabilizes the terminal aldehyde groups of cellulose and hemicellulose in wood, and itself becomes an anthrahydroquinone.
  • the anthrahydroquinone then acts as a reducing agent to reduce the molecular weight of the lignin in the chip while returning to anthraquinone. Therefore, there is an advantage that the amount of alkali necessary for obtaining a pulp having the same kappa number (an index of the amount of lignin in the pulp) can be reduced.
  • anthraquinone is widely used as an excellent cooking aid.
  • Polysulfide is produced by adding sulfur to white liquor (sodium hydroxide and sodium sulfide) to prevent carbohydrate elution and improve pulp yield, but it increases sulfur content in the chemical recovery system and increases the degree of sulfidation. There are problems such as rising.
  • the cooking aid is preferably used in a proportion of 0.001 to 1.0% by mass relative to the absolute dry mass of the raw wood.
  • the alkaline lignin is preferably obtained by purification under a condition where the pH is 8.5 or less.
  • purifying on such conditions the obtained alkali lignin has a suitable molecular weight for exhibiting the function as a cement additive.
  • the purification is preferably performed under conditions where the pH is 0.1 or more.
  • the pH at the time of alkali lignin purification can be measured with a pH meter.
  • the cooking solution can be purified by a conventional method used for purification, such as a method of precipitating lignin by adding an acid to the solution obtained by cooking to obtain a solution having a predetermined pH.
  • the alkali lignin preferably has a weight average molecular weight of 1,000 to 30,000. When alkali lignin has such a weight average molecular weight, the function as a cement additive can be more fully exhibited.
  • the weight average molecular weight of the alkali lignin is more preferably 1000 to 15000, and still more preferably 1000 to 7000.
  • the weight average molecular weight of alkali lignin can be measured using GPC under the conditions described in the examples described later.
  • the lignin contained in the second cement additive of the present invention also means lignin itself (unmodified lignin) obtained by extraction from a plant. After obtaining lignin by extraction from a plant, other compounds and It does not mean a lignin derivative obtained through a process for reacting.
  • Lignin having a sulfur element content in such a range and insoluble in an aqueous solution having a pH of 2.0 can be suitably used as a cement additive.
  • it may contain one type of lignin or may contain two or more types of lignin.
  • the second cement additive of the present invention has an elemental sulfur content in the range of 0.1 to 4% by mass relative to 100% by mass of lignin, and is insoluble in an aqueous solution having a pH of 2.0. As long as it contains a certain lignin, it may contain a lignin derivative obtained by reacting lignin with another compound, but the content of the lignin derivative is the same as the lignin contained in the second cement additive. It is preferable that it is 20 mass% or less with respect to a total of 100 mass% with a lignin derivative. More preferably, it is 10 mass% or less, and it is especially preferable not to contain a lignin derivative.
  • the woody material the above-mentioned conifers and hardwoods can be used.
  • herbaceous materials rice straw, cereal, bagasse, bamboo, kenaf, straw and the like can be used. Among these, woody materials are preferable in terms of dispersion performance, softwoods and hardwoods are more preferable, and coniferous materials are particularly preferable.
  • alkali lignin, kraft lignin, acetic acid lignin, organosolv lignin, explosive lignin and the like may be used.
  • alkali lignin, acetic acid lignin, organosolv lignin, and explosive lignin are advantageous in that no sulfur odor is generated because no sulfur-containing compound is used for cooking.
  • the lignin contained in the second cement additive of the present invention has a sulfur element content of 0.1 to 4% by mass with respect to 100% by mass of lignin, but the sulfur element content is 0%. It is preferably in the range of 1 to 3% by mass. More preferably, it is in the range of 0.1 to 2% by mass, and still more preferably in the range of 0.1 to 1% by mass.
  • the content of sulfur element in lignin can be measured by elemental analysis with the measuring equipment and measurement conditions described in the examples described later.
  • the lignin contained in the second cement additive of the present invention preferably has a weight average molecular weight of 1000 to 30000. When lignin has such a weight average molecular weight, the function as a cement additive can be more fully exhibited.
  • the weight average molecular weight of lignin is more preferably 1000 to 15000, and still more preferably 1000 to 7000.
  • the weight average molecular weight of lignin can be measured by the same method as the weight average molecular weight of alkali lignin described above.
  • cement additive of the present invention Hereinafter, contents corresponding to both the first cement additive and the second cement additive of the present invention will be described.
  • the cement additive of the present invention can also be used in combination with other cement additives, and an oxycarboxylic acid compound can be used in combination.
  • an oxycarboxylic acid compound By using the oxycarboxylic acid-based compound in combination, higher dispersion retention performance can be exhibited even in a high temperature environment.
  • an oxycarboxylic acid compound an oxycarboxylic acid having 4 to 10 carbon atoms or a salt thereof is preferable. Specifically, for example, gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid, and sodium thereof Inorganic salts or organic salts such as potassium, calcium, magnesium, ammonium and triethanolamine. These oxycarboxylic acid compounds may be used alone or in combination of two or more.
  • gluconic acid or a salt thereof is particularly suitable.
  • a lignin sulfonate-based dispersant is used as a sulfonic acid-based dispersant having a sulfonic acid group in the molecule, and gluconic acid or a salt thereof is used as an oxycarboxylic acid-based compound. It is preferable.
  • the cement additive of the present invention can also be used in combination with the following as other cement additives.
  • An aminosulfonic acid-based compound such as JP-A-7-267705, as a component (a), a polyalkylene glycol mono (meth) acrylic acid ester compound and a (meth) acrylic acid compound A copolymer and / or a salt thereof, and as a component (b), a copolymer of a polyalkylene glycol mono (meth) allyl ether compound and maleic anhydride and / or a hydrolyzate thereof, and / or a salt thereof, (C
  • Copolymer consisting of various monomers, salts thereof, or esters thereof; polyalkylene glycol mono (meth) acrylate ester monomers as described in JP-B-59-18338, (meta ) A copolymer of acrylic acid monomers and monomers copolymerizable with these monomers; having a sulfonic acid group as described in JP-A-62-1119147 (meta ) A copolymer comprising an acrylate ester and, if necessary, a monomer copolymerizable therewith, or a salt thereof; alkoxy as described in JP-A-6-271347 Esterification reaction product of copolymer of realkylene glycol monoallyl ether and maleic anhydride and polyoxyalkylene derivative having an alkenyl group at the terminal; alkoxy polyalkylene as described in JP-A-6-298555 Esterification reaction product of a copolymer of glycol monoallyl ether and maleic anhydride and a polyoxyal
  • Water-soluble polymer substances polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), unsaturated carboxylic acid polymer such as sodium salt of acrylic acid / maleic acid copolymer; polyethylene Polymers of polyoxyethylene or polyoxypropylene such as glycol and polypropylene glycol or copolymers thereof; Nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxypropylcellulose, etc.
  • Yeast glucan, xanthan gum, ⁇ -1,3 glucans (both linear and branched), for example, curdlan, paramylon, pachyman, Polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; copolymer of acrylic acid having an amino group in the molecule and its four Grade compounds and the like.
  • Retardant Gluconic acid, malic acid or citric acid, and oxycarboxylic acids such as inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, and salts thereof; glucose , Fructose, galactose, saccharose; sugar alcohols such as sorbitol; magnesium silicate; phosphoric acid and its salts or borate esters; aminocarboxylic acid and its salts; alkali-soluble protein; humic acid; tannic acid; Polyhydric alcohols such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and alkali metal salts thereof, al Phosphonic acids and derivatives thereof such as Li earth metal
  • Early strengthening agent / accelerator soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; thiosulfate; formic acid and formic acid Formates such as calcium; alkanolamine; alumina cement; calcium aluminate silicate.
  • Mineral oil-based antifoaming agent cocoon oil, liquid paraffin, etc.
  • Fat and oil-based antifoaming agents animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like.
  • Fatty acid-based antifoaming agent oleic acid, stearic acid, and these alkylene oxide adducts.
  • Fatty acid ester antifoaming agent glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.
  • Oxyalkylene antifoaming agents polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene -2-Ethylhexyl ether, (poly) oxyalkyl ethers such as oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) oxy such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1 - Acetylene ethers obtained by addition polymerization of alkylene oxide
  • Alcohol-based antifoaming agent octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like.
  • Amide antifoaming agent acrylate polyamine and the like.
  • Phosphate ester antifoaming agent tributyl phosphate, sodium octyl phosphate, etc.
  • Metal soap type antifoaming agent aluminum stearate, calcium oleate, etc.
  • Silicone antifoaming agent dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.
  • AE agent resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenylsulfosuccinic acid, ⁇ -olefin sulfonate, and the like.
  • aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol
  • Intramolecular monohydric alcohols such as alicyclic monohydric alcohol, dodecyl mercaptan, etc.
  • Intramolecular such as monohydric mercaptans having 6-30 carbon atoms in the molecule such as nonylphenol, alkylphenols having 6-30 carbon atoms in the molecule, dodecylamine, etc.
  • an alkylene oxide such as ethylene oxide or propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid.
  • Waterproofing agent fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt, wax and the like.
  • Rust preventive nitrite, phosphate, zinc oxide and the like.
  • Crack reducing agent polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol.
  • Expansion material Ettlingite, coal, etc.
  • cement additives include, for example, cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancing agents, self-leveling agents, rust preventives, colorants, antifungal agents , Blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum and the like.
  • the blending ratio is lignin which is an essential component of the cement additive of the present invention (in the case of the first cement additive of the present invention, woody plant
  • the content of sulfur element is in the range of 0.1 to 4% by mass with respect to 100% by mass of lignin, and difficult.
  • the mass ratio of the solid content of lignin that is water-soluble) and the solid content of other cement additives is 1 to 99/99 to 1. More preferably, it is 5 to 95/95 to 5, still more preferably 10 to 90/90 to 10, and particularly preferably 20 to 80/80 to 20.
  • another cement additive, and an oxycarboxylic acid compound, lignin that is an essential component of the cement additive of the present invention another cement additive, and an oxycarboxylic acid compound Is preferably 1 to 98/1 to 98/1 to 98. More preferably, it is 5 to 90/5 to 90/5 to 90, still more preferably 10 to 90/5 to 85/5 to 85, and particularly preferably 20 to 80/10 to 70/10 to 70.
  • an oxyalkylene antifoaming agent As the cement additive used in combination with the cement additive of the present invention, an oxyalkylene antifoaming agent, an accelerator, a separation reducing agent, and an AE agent are preferable, and an AE agent is used. In this case, it is preferable to use the three components of the cement additive of the present invention, the oxyalkylene antifoaming agent and the AE agent in combination.
  • the oxyalkylene antifoaming agent used in combination with the cement additive of the present invention among the above, (poly) oxyalkylene alkylamines are preferable.
  • the blending ratio of the oxyalkylene antifoaming agent is lignin (the first cement of the present invention) which is an essential component of the cement additive of the present invention.
  • lignin the first cement of the present invention
  • the sulfur element content is 0.1 to 4% by mass relative to 100% by mass of lignin.
  • lignin that is insoluble in an aqueous solution having a pH of 2.0 is preferably 0.01 to 20% by mass relative to the mass of the solid content.
  • the proportion of the oxyalkylene antifoaming agent is the same as described above, and the proportion of the AE agent is The amount is preferably 0.001 to 2% by mass based on the mass of the solid content of lignin, which is an essential component of the cement additive of the invention.
  • the mass ratio of lignin, which is an essential component of the cement additive of the present invention, and the accelerator is 10/90 to 99.9 / 0.1. Is preferred. More preferably, it is 20/80 to 99/1.
  • the separation reducing agent includes various thickening agents such as nonionic cellulose ethers and a hydrocarbon chain having 4 to 30 carbon atoms as a partial structure.
  • One or more compounds such as a compound having a hydrophobic substituent and a polyoxyalkylene chain obtained by adding 2 to 300 average addition moles of an alkylene oxide having 2 to 18 carbon atoms can be used.
  • the mass ratio of lignin, which is an essential component of the cement additive of the present invention, and the separation reducing agent is 10/90 to 99.99 / 0.01. Preferably there is. More preferably, it is 50/50 to 99.9 / 0.1.
  • the cement composition containing the cement additive of the present invention and the separation reducing agent can be suitably used as high-fluidity concrete, self-filling concrete, and self-leveling material.
  • the cement additive of the present invention can be used in addition to a cement composition such as cement paste, mortar, concrete, etc., and such a cement composition comprising the cement additive of the present invention is also one of the present inventions.
  • a cement composition such as cement paste, mortar, concrete, etc.
  • cement composition those containing cement, water, fine aggregate, coarse aggregate and the like are suitable.
  • Portland cement ordinary, early strength, very early strength, moderate heat, sulfate resistance, Various mixed cements (blast furnace cement, silica cement, fly ash cement); white Portland cement; alumina cement; super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement) ); Grout cement; oil well cement; low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high content of belite); ultra high strength cement; cement-based solidified material; ecocement (city waste) Cement produced from one or more of incineration ash and sewage sludge incineration ash G) other such, these blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and a film obtained by adding a fine powder and gypsum
  • Unit water amount per 1 m 3 of the cement composition, cement usage and water / cement ratio as (mass ratio), for example, the unit water amount 100 ⁇ 185 kg / m 3, use amount of cement 200 ⁇ 800 kg / m 3, water / Cement ratio (mass ratio) is preferably 0.1 to 0.7, more preferably unit water amount 120 to 175 kg / m 3 , cement amount used 250 to 800 kg / m 3 , water / cement ratio ( (Mass ratio) 0.2 to 0.65.
  • .5 (preferably 0.15 to 0.4) can be used even in a region where the water / cement ratio is low, and further, high-strength concrete with a large amount of unit cement and a small water / cement ratio, It is effective for any poor blended concrete of m 3 or less.
  • the cement additive of the present invention can exhibit fluidity, retention and workability in a well-balanced and high performance even in a high water reduction rate region and has excellent workability, ready-mixed concrete, concrete secondary products (precast) Concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, sprayed concrete, etc., and medium-fluidity concrete (slump value of 22-25cm) Range of concrete), high fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self-leveling material, etc. Is also effective.
  • the blending ratio is such that lignin, which is an essential component of the cement additive of the present invention, is 100% by mass of the total mass of cement in terms of solid content. , 0.01 to 10% by mass is preferable. If it is less than 0.01% by mass, the performance may not be sufficient. On the other hand, if it exceeds 10% by mass, the effect will substantially reach its peak, which may be disadvantageous in terms of economy. More preferably, it is 0.02 to 8% by mass, and still more preferably 0.05 to 6% by mass.
  • the cement additive of the present invention is a cement additive that has the above-described configuration, can contain a specific lignin extracted from a plant without derivatization, and can make the cement composition excellent in fluidity.
  • FIG. 3 is a graph showing the relationship between the pH at the time of purification of the cooking liquids of Production Examples 1 to 3 and the lignin recovery rate.
  • FIG. 6 is a graph showing the relationship between the amount of lignin (cement additive) added and the zero-stroke flow value in Examples 1-1 to 3-3 and Comparative Examples 1-1 and 2.
  • FIG. 6 is a graph showing the relationship between the amount of lignin (cement additive) added and the 15-stroke flow value in Examples 4-1 to 5-2 and Comparative Examples 3-1 to 5-1.
  • Production Examples 2 and 3 Purified lignin powders (isolated lignin manufactured by Forestry Research Institute) of Examples 2 and 3 were obtained in the same manner as in Production Example 1 except that the pH during purification of the cooking liquor was changed to 4.5 and 8.5.
  • Table 1 shows the lignin recovery rates obtained in Production Examples 1 to 3. A graph of the results in Table 1 is shown in FIG.
  • the lignin recovery rate was calculated as follows. ⁇ Lignin recovery rate> The lignin amount A in black liquor, which is a strong alkaline aqueous solution obtained by cooking, and the lignin amount B of purified lignin obtained by purifying the black liquor with about 30% sulfuric acid aqueous solution by the following quantitative methods, respectively.
  • Quantitate, Recovery rate (%) (Lignin amount B of purified lignin) / (Lignin amount A in black liquor) ⁇ 100 Calculated by ⁇ Lignin quantification method>
  • the lignin sample was dissolved in 1,4-dioxane: 0.2N NaOH (1: 1 v / v), adjusted to pH 5 with acetic acid, and UV absorption at 280 nm was measured.
  • the extinction coefficient was 30.3 L / g ⁇ cm.
  • Examples 1-1 to 3-3 Comparative Examples 1-1 to 2 Using the isolated lignin obtained in Production Examples 1 to 3, mortar was prepared as follows, and the initial air amount and zero stroke flow value were measured (Examples 1-1 to 3-3).
  • an example using lignin sulfonic acid (BASF Pozzolith Co., Pozzolith No. 8) (Comparative Examples 1-1 to 1-3) and plain (water only, no additive) (comparison) For Example 2), the initial air amount and zero stroke flow value were also measured. The results are shown in Table 2.
  • FIG. 2 shows a graph of the results in Table 2.
  • MA-404 manufactured by BASF Pozzolith
  • ⁇ Mortar preparation 1> The mortar test was performed in an environment where the temperature was 20 ° C. ⁇ 1 ° C. and the relative humidity was 60% ⁇ 10%.
  • C Ordinary Portland cement (manufactured by Taiheiyo Cement)
  • S Standard sand for cement strength test (Cement Association)
  • W Isolated lignin (Examples 1 to 3), Pozzolith no.
  • ⁇ 0-stroke flow value measurement> The mortar was transferred from the kneading container to a 1 L polyethylene container, stirred 20 times with a spatula, and immediately placed on a flow measuring plate (30 cm ⁇ 30 cm) (see JIS micro concrete slump cone, A-1173). 50mm upper end inner diameter, 100mm lower end inner diameter, 150mm height) Packed in half of a flow cone (described in JIS R5201-1997) with a stick with 15 strokes, and further packed with mortar until the flow cone is fully filled with a stick with 15 strokes. Finally, the shortage was compensated and the surface of the mini slump cone was smoothed.
  • the flow cone is pulled up vertically, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter of the part forming 90 degrees with respect to the major axis) is measured in two places, and the average value is zero.
  • the flow value was used.
  • the zero stroke flow value has a better dispersion performance as the numerical value is larger.
  • Examples 4-1 to 5-2 Comparative examples 3-1 to 5
  • a mortar was prepared as follows, and the initial air amount and the 15-stroke flow value were measured ( Examples 4-1 and 5-2).
  • FIG. 3 shows a graph of the results of Table 3.
  • MA-404 manufactured by BASF Pozzolith Co., Ltd.
  • an antifoaming agent was added to each component in an amount of 10% by mass to each component solid content.
  • ⁇ Mortar preparation 2> The mortar test was performed in an environment where the temperature was 20 ° C. ⁇ 1 ° C. and the relative humidity was 60% ⁇ 10%.
  • C Ordinary Portland cement (manufactured by Taiheiyo Cement)
  • S Standard sand for cement strength test (Cement Association)
  • W Reagent lignin (Example 4), black liquor (Example 5), sun extract P321 (lignin sulfonic acid), Pozzolith no.
  • each addition amount shown in Table 3 is weighed, and the antifoaming agent MA-404 is in solid form with respect to the solid content of each component. 10% by mass was added, and ion exchange water was further added to obtain a predetermined amount, which was sufficiently uniformly dissolved.
  • the addition amount of each component is represented by mass% of the solid content of each component with respect to the cement mass.
  • a stainless beater (stirring blade) was attached to a Hobart type mortar mixer (model No. N-50; manufactured by Hobart), C and W were added, and kneaded at a first speed for 30 seconds.
  • S was added over 30 seconds while kneading at a first speed. After the completion of S addition, after kneading for 30 seconds at the second speed, the mixer was stopped, the mortar was scraped off for 15 seconds, and then allowed to stand for 75 seconds. The mixture was allowed to stand for 75 seconds and then kneaded at a second speed for 60 seconds to prepare a mortar.
  • the flow cone is pulled up vertically, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter of the part forming 90 degrees with respect to the major axis) is measured in two places, and the average value is zero.
  • the flow value was used.
  • 15 falling motions were given in 15 seconds, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter of the part forming 90 degrees with respect to the major axis) was 2
  • the points were measured and the average value was taken as the 15-stroke flow value.
  • the 15-stroke flow value is superior in dispersion performance as the numerical value is larger.
  • Table 4 shows the weight average molecular weights and molecular weight distributions of the isolated lignins manufactured by Forestry Research Institute used in Examples 1 to 3 and the alkaline lignins 1 and 2 used in Examples 4 and 5.
  • the cement additive of the present invention exhibits a high cement dispersion effect with a smaller amount of use than cement additive using unmodified lignin lignin sulfonic acid or its salt. It was confirmed.

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Abstract

L'invention fournit un additif à ciment ayant pour matériau de base un végétal ligneux, ne mettant pas en œuvre de ligninesulfonate, et pouvant être obtenu à travers un processus au cours duquel les additifs ayant pour matériau de base une lignine, tels que dans l'art antérieur, sont peu nombreux. Plus précisément, l'invention concerne un additif à ciment comprenant une lignine. Cette lignine a pour composant principal une alcali-lignine obtenue avec un végétal ligneux pour matériau de base.
PCT/JP2014/065032 2013-06-07 2014-06-06 Additif à ciment WO2014196618A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016133177A1 (fr) * 2015-02-20 2016-08-25 日本製紙株式会社 Dispersant
WO2019112970A1 (fr) * 2017-12-04 2019-06-13 Hexion Research Belgium S.A. Additif de fluide de puits de forage multifonctionnel
US10487257B2 (en) 2016-07-20 2019-11-26 Hexion Inc. Materials and methods of use as additives for oilwell cementing

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JP6713256B2 (ja) * 2015-07-08 2020-06-24 株式会社日本触媒 （ポリ）アルキレングリコール鎖を有する１級又は２級アミン化合物の製造方法及び（ポリ）アルキレングリコール鎖を有する１級又は２級アミン化合物含有組成物
CN106431057A (zh) * 2016-08-31 2017-02-22 苏州市湘园特种精细化工有限公司 一种水泥助磨剂生产工艺
JP6831197B2 (ja) * 2016-09-07 2021-02-17 黒崎播磨株式会社 断熱不定形耐火物
KR102482686B1 (ko) * 2020-12-03 2022-12-28 김석균 혼합 분말 및 수용성 포장재를 포함하는 콘크리트용 분말형 혼화제 조성물

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JPH07224135A (ja) * 1994-02-09 1995-08-22 Nippon Paper Ind Co Ltd リグニン系縮合物及び該縮合物より成る分散剤
JPH09104819A (ja) * 1995-10-11 1997-04-22 Nippon Paper Ind Co Ltd リグニン組成物、その製造方法及びそれを用いたセメント分散剤
JP2011184230A (ja) * 2010-03-08 2011-09-22 Forestry & Forest Products Research Institute リグニン系コンクリート混和剤

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JPS63230546A (ja) * 1987-03-20 1988-09-27 山陽国策パルプ株式会社 セメント添加剤
JPH07224135A (ja) * 1994-02-09 1995-08-22 Nippon Paper Ind Co Ltd リグニン系縮合物及び該縮合物より成る分散剤
JPH09104819A (ja) * 1995-10-11 1997-04-22 Nippon Paper Ind Co Ltd リグニン組成物、その製造方法及びそれを用いたセメント分散剤
JP2011184230A (ja) * 2010-03-08 2011-09-22 Forestry & Forest Products Research Institute リグニン系コンクリート混和剤

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016133177A1 (fr) * 2015-02-20 2016-08-25 日本製紙株式会社 Dispersant
US10487257B2 (en) 2016-07-20 2019-11-26 Hexion Inc. Materials and methods of use as additives for oilwell cementing
WO2019112970A1 (fr) * 2017-12-04 2019-06-13 Hexion Research Belgium S.A. Additif de fluide de puits de forage multifonctionnel
US11643588B2 (en) 2017-12-04 2023-05-09 Hexion Inc. Multiple functional wellbore fluid additive

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