WO2019221002A1 - Copolymère contenant du (poly)alkylèneglycol - Google Patents

Copolymère contenant du (poly)alkylèneglycol Download PDF

Info

Publication number
WO2019221002A1
WO2019221002A1 PCT/JP2019/018551 JP2019018551W WO2019221002A1 WO 2019221002 A1 WO2019221002 A1 WO 2019221002A1 JP 2019018551 W JP2019018551 W JP 2019018551W WO 2019221002 A1 WO2019221002 A1 WO 2019221002A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer
copolymer
poly
peak
group
Prior art date
Application number
PCT/JP2019/018551
Other languages
English (en)
Japanese (ja)
Inventor
太一朗 新井
坂本　登
Original Assignee
株式会社日本触媒
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日本触媒 filed Critical 株式会社日本触媒
Priority to JP2020519594A priority Critical patent/JPWO2019221002A1/ja
Publication of WO2019221002A1 publication Critical patent/WO2019221002A1/fr

Links

Images

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
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a (poly) alkylene glycol-containing copolymer. More specifically, the present invention relates to a (poly) alkylene glycol-containing copolymer useful for applications such as a dispersant and a cement admixture.
  • a polymer containing a (poly) alkylene glycol chain (hereinafter, also referred to as a (poly) alkylene glycol polymer) has a hydrophilicity, hydrophobicity, flexibility, etc. by appropriately adjusting the chain length and the alkylene oxide constituting the polymer. Since characteristics such as steric repulsion are imparted, it is used in cement admixture applications added to cement compositions such as cement paste, mortar, and concrete. Such a cement admixture is usually used as a water reducing agent or the like, and exerts an effect of improving the strength and durability of the cured product by reducing the cement composition by increasing the fluidity of the cement composition. Used for that purpose.
  • a water reducing agent such as naphthalene type has been conventionally used.
  • a (poly) alkylene glycol chain can act as a dispersing group for dispersing cement particles due to its steric repulsion
  • (poly) alkylene A polycarboxylic acid-based water reducing agent containing a glycol chain has been proposed as exhibiting a high water reducing action, and has recently been used as a high-performance AE water reducing agent.
  • Patent Document 1 discloses a cement dispersant mainly composed of a polycarboxylic acid polymer (A) or a salt thereof.
  • the weight average molecular weight of the polymer (A) is in the range of 10,000 to 500,000 in terms of polyethylene glycol by gel permeation chromatography, and the value obtained by subtracting the peak top molecular weight from the weight average molecular weight is 0.
  • a cement dispersant characterized by ⁇ 8,000 is disclosed.
  • Patent Documents 2 to 5 also disclose polycarboxylic acid polymers containing a (poly) alkylene glycol chain.
  • Patent Document 6 discloses a polymer (A ) And polymer (B) as an essential component, a cement admixture, wherein the polymer (A) and the polymer (B) are unsaturated ( The structural unit (I) derived from the poly) alkylene glycol ether monomer (a) and the structural unit derived from the unsaturated carboxylic acid monomer (b) having a carboxyl group and / or a salt thereof as an adsorbing group (II) ) As an essential structural unit, and the polymer (A) further includes, as an essential structural unit, a structural unit (III) derived from an unsaturated carboxylic acid ester monomer (c) having a hydrophobic group.
  • This invention is made
  • the inventor conducted various studies on copolymers having a structural unit derived from a (poly) alkylene glycol monomer and a structural unit derived from a hydrophobic monomer. As a result, the ratio of the high molecular weight in the copolymer was determined. As a result of the reduction, it was found that the separation in the copolymer solution was sufficiently suppressed and the storage stability was excellent, and it was conceived that the above problems could be solved brilliantly, and the present invention has been achieved.
  • the present invention is a copolymer containing a (poly) alkylene glycol chain, wherein the copolymer is represented by the following formula (1);
  • R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or a methyl group.
  • R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • (AO) are the same or different and each represents an oxyalkylene group, n represents the average number of moles added of the oxyalkylene group, and is a number from 1 to 300.
  • y represents a number from 0 to 4.
  • z Represents a structural unit (a) derived from the (poly) alkylene glycol-containing monomer (A) and a structural unit (b) derived from the hydrophobic monomer (B).
  • the hydrophobic monomer (B) has an ethylenically unsaturated group and has an octanol / water partition coefficient value (Log P value) of 1.0 to 8.0; Gel Permeation Chromatography (GPC) Differential Refractive Index Detector Chromatography In the ram, a (poly) alkylene glycol-containing copolymer satisfying the following formula (2), the areas of the peak ⁇ and the peak ⁇ defined below. ⁇ ⁇ 100 / ( ⁇ + ⁇ ) ⁇ 3.0 (2) ⁇ Peak ⁇ and ⁇ > Peak ⁇ : A peak having a weight average molecular weight (Mw) larger than 200,000. Peak ⁇ : A peak having Mw of 200,000 or less.
  • Mw weight average molecular weight
  • the hydrophobic monomer (B) is an ester of an unsaturated carboxylic acid and an alcohol, an aromatic vinyl monomer, an olefin monomer, a (meth) acrylamide monomer, or a maleimide monomer. And at least one selected from the group consisting of esters of unsaturated alcohols and carboxylic acids.
  • the (poly) alkylene glycol-containing copolymer preferably has a structural unit (c) derived from an unsaturated carboxylic acid monomer (C).
  • z in the formula (1) is preferably 0.
  • the proportion of the structural unit (a) is preferably 50% by mass to 99% by mass with respect to 100% by mass of all structural units.
  • the proportion of the structural unit (b) is preferably 1% by mass to 30% by mass with respect to 100% by mass of all structural units.
  • the proportion of the structural unit (c) is preferably 0% by mass to 30% by mass with respect to 100% by mass of all structural units.
  • the (poly) alkylene glycol-containing copolymer includes other (poly) alkylene glycol-containing monomer (A), hydrophobic monomer (B), and unsaturated carboxylic acid monomer (C).
  • the structural unit (e) derived from the monomer (E) may be included, and the proportion of the structural unit (e) is 0% by mass or more and 30% by mass or less with respect to 100% by mass of all the structural units. It is preferable.
  • the present invention is also a cement admixture containing the (poly) alkylene glycol-containing copolymer.
  • the present invention is also a cement composition comprising the (poly) alkylene glycol-containing copolymer and cement.
  • the present invention is further a method for producing a cement composition, wherein the production method is also a method for producing a cement composition including a step of adding the (poly) alkylene glycol-containing copolymer to a hydraulic material.
  • the (poly) alkylene glycol-containing copolymer of the present invention has the above-described structure, and is sufficiently suppressed in the copolymer solution and excellent in storage stability. Therefore, it can be suitably used as a cement admixture or the like. .
  • the (poly) alkylene glycol-containing copolymer of the present invention (hereinafter also referred to as the copolymer of the present invention) is a gel-permeation chromatography (GPC) differential refractive index detector measured for the copolymer.
  • GPC gel-permeation chromatography
  • the areas of peak ⁇ and peak ⁇ defined below satisfy the following formula (2).
  • Peak ⁇ A peak having Mw of 200,000 or less.
  • the copolymer by reducing the proportion of the high molecular weight substance having Mw greater than 200,000 corresponding to the peak ⁇ , separation can be sufficiently suppressed in the copolymer and its solution. By suppressing separation in the copolymer solution, the separated product can be prevented from adhering to and contaminating the reactor and the storage container. Further, in the copolymer and its solution, it is possible to suppress the occurrence of non-uniform concentration, and to fully exhibit desired performance during use.
  • the high molecular weight product has a relatively high content of structural units derived from the hydrophobic monomer (B) and / or the unsaturated carboxylic acid monomer (C), and the (poly) alkylene glycol-containing monomer ( It is estimated that the content of the structural unit derived from A) is a (co) polymer having a relatively low content. This is because the UV / RI ratio (value obtained by dividing the UV chromatogram area by the RI chromatogram area) for the peak ⁇ and the peak ⁇ detected by GPC is larger. It is suggested from becoming.
  • the ratio of the high molecular weight corresponding to the peak ⁇ increases in the entire copolymer, not only the separation occurs in the copolymer solution, but also the hydrophobicity of the copolymer having an Mw corresponding to the peak ⁇ of 200,000 or less. Since the content of the structural unit derived from the polymerizable monomer (B) (and optionally the unsaturated carboxylic acid monomer (C)) is decreased, the desired performance may not be sufficiently exhibited. On the other hand, since the copolymer of the present invention has a small proportion of such a high molecular weight, it is presumed that the composition ratio of the constituent units in the copolymer is relatively uniform regardless of Mw. . Thus, the copolymer of this invention will be excellent also in the performance at the time of using for a cement composition etc. because the composition of a copolymer is uniform.
  • the measurement conditions of GPC of the copolymer are as follows. ⁇ GPC analysis conditions> Device: Waters Alliance (2695) Analysis software: Waters, Empor2 Professional + GPC option column: Tosoh Co., Ltd., TSKguardcolumns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL Detector: differential refractive index (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996) Eluent: A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and adjusting the pH to 6.0 with acetic acid.
  • RI differential refractive index
  • PDA multi-wavelength visible ultraviolet
  • Standard substance for preparing calibration curve polyethylene glycol (peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
  • Calibration curve Prepared by a cubic equation based on the Mp value and elution time of the standard. Flow rate: 1 mL / min Column temperature: 40 ° C Measurement time: 45 minutes
  • Standard substance sample solution injection amount 100 ⁇ L (eluent solution with polymer concentration of 0.1% by mass)
  • Polymer sample solution injection amount 100 ⁇ L (eluent solution having a polymer concentration of 0.5% by mass)
  • ⁇ GPC analysis conditions analysis of polymer>
  • the peaks ⁇ and ⁇ are defined as follows.
  • the weight average molecular weight (Mw) of each peak obtained was determined, and the peak with Mw greater than 200,000 was defined as ⁇ , and Mw was 20 A peak of 10,000 or less is defined as ⁇ .
  • the peak ⁇ is a peak whose Mw is 200,000 or less among peaks that can be analyzed in the chromatogram. There may be a plurality of peaks ⁇ and ⁇ , but the molecular weight and area are calculated together.
  • the peaks ⁇ and ⁇ are detected without overlapping completely, the peaks ⁇ and ⁇ are separated by vertical division at the most concave portion (lowest point) between the peaks. When the lowest point continues in the most concave portion, the peak is vertically divided at the intermediate point.
  • the flat and stable portions are connected with a straight line to form a baseline.
  • the peak areas of the peaks ⁇ and ⁇ are defined as follows.
  • the area of ⁇ is an area surrounded by a peak curve belonging to the peak ⁇ , a base line, and a perpendicular line extending from the concave portion to the base line.
  • the area of the peak ⁇ is an area surrounded by a peak curve belonging to the peak ⁇ , a base line, and a perpendicular line extending from the most concave portion to the base line.
  • a peak is isolate
  • the copolymer of the present invention comprises a structural unit (a) derived from the (poly) alkylene glycol-containing monomer (A) represented by the above formula (1) and a structural unit derived from the hydrophobic monomer (B) ( b), each of which may be one type or two or more types.
  • the proportion of the structural unit (a) in the copolymer of the present invention is sufficient to exhibit performances such as hydrophilicity, compatibility, and dispersion force derived from the structural unit (a). It is preferable that it is 50 mass% or more. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more, Most preferably, it is 80 mass% or more.
  • the proportion of the structural unit (b) in the copolymer of the present invention is sufficient to exhibit performances such as hydrophobicity, compatibility, and surface activity derived from the structural unit (b). And preferably 1% by mass or more. More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more, Still more preferably, it is 7.5 mass% or more, Most preferably, it is 10 mass% or more. Further, in order to reduce the proportion of the high molecular weight substance, more sufficiently suppress the separation in the copolymer solution, and sufficiently exhibit the performance derived from other structural units, 30% with respect to 100% by mass of all structural units It is preferable that it is below mass%. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less, Most preferably, it is 12.5 mass% or less.
  • the proportion of the structural unit (c) in the copolymer of the present invention may be 0% by mass or more with respect to 100% by mass of all the structural units.
  • the content is preferably 1% by mass or more with respect to 100% by mass of all structural units. More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more, Still more preferably, it is 7.5 mass% or more, Most preferably, it is 10 mass% or more.
  • the mass of the structural unit (c) is calculated as the corresponding sodium salt type structural unit. For example, if the structure is derived from (meth) acrylic acid, the mass ratio is calculated as a structure derived from sodium (meth) acrylate, and if the structure is derived from maleic acid, the structure is derived from disodium maleate.
  • the copolymer of the present invention comprises other monomers (other than the above (poly) alkylene glycol-containing monomer (A), hydrophobic monomer (B) and unsaturated carboxylic acid monomer (C)). You may have the structural unit (e) derived from E).
  • the proportion of the structural unit (e) in the copolymer of the present invention may be 0% by mass or more with respect to 100% by mass of all the structural units, but sufficiently exhibits the performance derived from the structural unit (e). It is preferable that it is 1 mass% or more. More preferably, it is 2.5 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 7.5 mass% or more, Most preferably, it is 10 mass% or more.
  • the copolymer of the present invention preferably has a weight average molecular weight of 5,000 to 200,000. In order to sufficiently exhibit the performance of the copolymer, it is more preferably 7,000 or more, still more preferably 10,000 or more, still more preferably 15,000 or more, and particularly preferably 20,000 or more. It is. In order to more sufficiently suppress the separation in the copolymer solution, it is more preferably 150,000 or less, still more preferably 100,000 or less, even more preferably 70,000 or less, and particularly preferably 50. , 000 or less.
  • the weight average molecular weight of a copolymer can be measured by the method as described in an Example.
  • R 1 to R 3 are the same or different and each represents a hydrogen atom or a methyl group.
  • R 1 and R 2 are hydrogen atoms
  • R 3 is a hydrogen atom or a methyl group. More preferably, R 1 and R 2 are hydrogen atoms and R 3 is a methyl group.
  • AO represents “the same or different,” and represents an oxyalkylene group having 2 to 18 carbon atoms, which is the same for all oxyalkylene groups of AO present in n in polyalkylene glycol. Means that it may be different.
  • the oxyalkylene group represented by AO is an alkylene oxide adduct, and examples of such alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2- Examples thereof include alkylene oxides having 2 to 8 carbon atoms such as butene oxide, styrene oxide, glycidol and epichlorohydrin.
  • alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and still more preferred are ethylene oxide and propylene oxide.
  • the polyalkylene glycol is any two or more alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., any of random addition, block addition, alternating addition, etc. Form may be sufficient.
  • the oxyalkylene group represented by AO is preferably selected as appropriate according to the use required for the copolymer of the present invention, but in order to ensure a balance between hydrophilicity and hydrophobicity.
  • the oxyalkylene group in the polyalkylene glycol preferably has an oxyethylene group as an essential component, more preferably 50 mol% or more is an oxyethylene group, and 90 mol% or more is an oxyethylene group. Further preferred.
  • n represents an average addition mole number of the oxyalkylene group and is 1 to 300. From the viewpoint of sufficiently exerting the performance derived from the oxyalkylene group, it is preferably 2 or more, more preferably 10 or more, still more preferably 25 or more, particularly preferably 30 or more, and still more preferably 50. That's it. On the other hand, if it exceeds 300, the viscosity becomes too high during production and use, and workability may not be sufficient. Preferably it is 200 or less, More preferably, it is 150 or less, More preferably, it is 100 or less, Most preferably, it is 75 or less.
  • R 4 in the above formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • Preferred is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferred is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and still more preferred is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
  • Particularly preferred is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and most preferred is a methyl group or a hydrogen atom.
  • hydrocarbon group examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl (amyl), n-hexyl, n-heptyl, n-octyl, and n-nonyl.
  • n-decyl group n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl
  • y represents a number from 0 to 2, and z represents 0 or 1.
  • y is preferably 1 or 2.
  • z is preferably 0.
  • y is preferably 1 or 2, and more preferably y is 2.
  • the monomer (A) include (poly) alkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate, and alkoxy-modified alkoxy groups having 1 to 30 carbon atoms at the ends thereof ( Poly) alkylene glycol (meth) acrylate; vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-butene Compounds obtained by adding 1 to 300 moles of alkylene oxide to unsaturated alcohols having 2 to 8 carbon atoms such as -1-ol, 2-methyl-2-buten-1-ol, and 3-allyloxy-1,2-propanediol And compounds in which these ends are hydrophobically modified with a hydrocarbon group having 1 to 30 carbon atoms.
  • poly alkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate, and alkoxy-modified alkoxy groups having 1 to 30
  • a compound obtained by adding 1 to 300 moles of alkylene oxide to an unsaturated alcohol having 2 to 8 carbon atoms and a compound obtained by hydrophobically modifying these terminals with a hydrocarbon group having 1 to 30 carbon atoms are preferable. More preferred is a compound obtained by adding 1 to 300 moles of an alkylene oxide to an unsaturated alcohol having 2 to 8 carbon atoms, and further preferred is adding an alkylene oxide to methallyl alcohol or 3-methyl-3-buten-1-ol. It has been made.
  • the hydrophobic monomer (B) has an ethylenically unsaturated group and has an octanol / water partition coefficient value (Log P value) of 1.0 to 8.0. Since the copolymer of the present invention has such a structural unit (b) derived from the hydrophobic monomer (B), it is compatible with a hydrophobic substance by a hydrophobic interaction, and is inorganic by a surface active action. Various excellent performances such as reducing the viscosity of the powder slurry will be exhibited.
  • the Log P value is described in, for example, ChemBioDraw Ultra ver. It can be calculated using the software of No. 14 (Kabumoto Cambridge Software).
  • the Log P value is more preferably 1.3 or more, still more preferably 1.5 or more, still more preferably 1.85 or more, particularly preferably from the viewpoint of sufficiently exhibiting hydrophobicity. 2 or more.
  • separation in a copolymer solution cannot fully be suppressed at the time of manufacture and a storage. More preferably, it is 6 or less, More preferably, it is 4 or less, Even more preferably, it is 3 or less, Most preferably, it is 2.5 or less.
  • the hydrophobic monomer (B) is not particularly limited as long as the Log P value is 1.0 to 8.0, but examples thereof include esters of unsaturated carboxylic acids and alcohols, aromatic vinyl monomers, olefins. And amides of unsaturated carboxylic acids and amines, maleimide monomers and esters of unsaturated alcohols and carboxylic acids.
  • an ester of an unsaturated carboxylic acid monomer (C) described later and an alcohol having 2 to 18 carbon atoms is preferable.
  • the alcohol having 2 to 18 carbon atoms include ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, lauryl alcohol, stearyl alcohol and other alkyl alcohols; Alcohol; unsaturated alcohols such as allyl alcohol, methallyl alcohol, propargyl alcohol, crotyl alcohol, pentenol, hexenol, heptenol, octenol, nonenol, decenol, dodecenol, octadecenol and the like.
  • the alcohol preferably has 3 to 16 carbon atoms, more preferably 4
  • unsaturated carboxylic acid As said unsaturated carboxylic acid, the thing similar to the specific example of the unsaturated carboxylic acid-type monomer (C) mentioned later is mentioned.
  • unsaturated carboxylic acid (meth) acrylic acid and maleic acid are preferable.
  • esters of unsaturated carboxylic acid and alcohol include (meth) acrylic acid alkyl ester (alkyl (meth) acrylate) having an alkyl group having 2 to 18 carbon atoms, maleic having an alkyl group having 4 to 20 carbon atoms. Acid monoalkyl esters (monoalkyl malates) and maleic acid dialkyl esters (dialkyl malates) having two alkyl groups with a total carbon number of 4 to 20 are preferred.
  • alkyl group examples include the above-mentioned aliphatic alkyl groups and alicyclic alkyl groups.
  • the number of carbon atoms of the alkyl group of the alkyl (meth) acrylate is more preferably 3 to 16, further preferably 4 to 12, still more preferably 4 to 8, and particularly preferably 4 to 6.
  • the number of carbon atoms of the alkyl group of the monoalkyl malate and the total number of carbon atoms of the two alkyl groups of the dialkyl malate are more preferably 5 to 16, and further preferably 6 to 12. More preferably, it is 6 to 10, particularly preferably 6 to 8.
  • alkyl (meth) acrylate examples include ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth).
  • (mono, di) alkyl malate examples include dipropyl malate, (mono, di) n-butyl malate, (mono, di) isobutyl malate, (mono, di) tert-butyl malate, (mono, Examples thereof include di) sec-butyl malate, (mono, di) 2-ethylhexyl malate, (mono, di) octyl malate, (mono, di) decyl malate, monolauryl malate, monostearyl malate and the like.
  • aromatic vinyl monomer examples include styrene, vinyl toluene, ⁇ -methyl styrene, methoxy styrene, 2,4-dimethyl styrene, 4-ethyl styrene, 4-isopropyl styrene, 4-butyl styrene, 4- Examples include phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, 4-crotylbenzene, 2-vinylnaphthalene. Styrene, vinyltoluene and ⁇ -methylstyrene are preferred.
  • olefin monomers include ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene and other alkenes having 2 to 16 carbon atoms; butadiene, isoprene, 1,4- Examples thereof include alkadienes having 4 to 19 carbon atoms such as pentadiene, 1,6-heptadiene, and 1,7-octadiene.
  • an amide of an unsaturated carboxylic acid monomer (C) described later and an amine having 4 to 20 carbon atoms is preferable.
  • the amine include methylamine, ethylamine, (iso) propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octyl Examples thereof include amines having 1 to 20 carbon atoms such as amine, dioctylamine and dodecylamine.
  • the unsaturated carboxylic acid (meth) acrylic acid is preferable. That is, as the amide of unsaturated carboxylic acid and amine, a (meth) acrylamide monomer is preferable.
  • the (meth) acrylamide monomer examples include N-monosubstituted (meth) acrylamides in which the hydrogen atom of the amino group of (meth) acrylamide is substituted with a hydrocarbon group having 4 to 20 carbon atoms, N, N-disubstituted (meth) acrylamide is mentioned.
  • a hydrocarbon group the above-mentioned alkyl group; alkenyl group; aryl group etc. are mentioned.
  • N-alkyl (meth) acrylamide and N, N-dialkyl (meth) acrylamide are preferable.
  • Specific examples of the alkyl group that the (meth) acrylamide monomer has are as described above.
  • the number of carbon atoms of the alkyl group of the N-alkyl substituent of (meth) acrylamide is more preferably 5 to 16, more preferably 6 to 6 as the total number of carbon atoms of two alkyl groups. 12, more preferably 6 to 10, and particularly preferably 6 to 8.
  • maleimide monomer examples include N-substituted maleimide in which the hydrogen atom of the amino group of maleimide is substituted with a hydrocarbon group having 1 to 16 carbon atoms.
  • hydrocarbon group examples include an alkyl group; an alkenyl group; an aryl group, and specific examples thereof are as described above.
  • maleimide monomer examples include N-heptylmaleimide, N-octylmaleimide, N-dodecylmaleimide (N-laurylmaleimide), N-hexadecylmaleimide, N-octadecylmaleimide (N-stearylmaleimide) and the like
  • N- Preferred are alkyl-substituted maleimides; N-aryl-maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-ethylphenylmaleimide, N-butylphenylmaleimide, and N-dimethylphenylmaleimide.
  • the number of carbon atoms of the hydrocarbon group in the N-alkyl-substituted maleimide is more preferably 5 to 16, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6 to 8.
  • ester of the unsaturated alcohol and the carboxylic acid for example, the ester of the unsaturated alcohol having 2 to 8 carbon atoms and the carboxylic acid having 2 to 16 carbon atoms described in the monomer (A) is preferable.
  • carboxylic acid having 2 to 16 carbon atoms include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, and palmitic acid.
  • esters of unsaturated alcohols and carboxylic acids include vinyl propionate, vinyl butyrate, vinyl caprylate, vinyl palmitate; 2-methylallyl propionate, 2-methylallyl butyrate, 2-methylallyl caprylate, palmitate 2-methylallyl acid; 3-methyl-3-buten-1-yl acetate, 3-methyl-3-buten-1-yl propionate, 3-methyl-3-buten-1-yl butyrate, 3-methyl caprylate -3-buten-1-yl, 3-methyl-3-buten-1-yl palmitate and the like.
  • the number of carbon atoms of the carboxylic acid is more preferably 3 to 14, still more preferably 4 to 12, still more preferably 5 to 10, and particularly preferably 6 to 8.
  • the hydrophobic monomer (B) is preferably an ester of an unsaturated carboxylic acid and an alcohol, an aromatic vinyl monomer, an olefin monomer, a (meth) acrylamide monomer, or a maleimide monomer.
  • esters of unsaturated alcohols and carboxylic acids more preferably esters of unsaturated carboxylic acids and alcohols, aromatic vinyl monomers, and olefin monomers, and more preferably Esters of saturated carboxylic acids and alcohols and aromatic vinyl monomers are preferred, and esters of unsaturated carboxylic acids and alcohols are particularly preferred.
  • the copolymer of the present invention preferably has a structural unit (c) derived from an unsaturated carboxylic acid monomer (C).
  • an unsaturated monocarboxylic acid monomer or an unsaturated dicarboxylic acid monomer is suitable, and as the unsaturated monocarboxylic acid monomer, Any monomer may be used as long as it has one unsaturated group and one group capable of forming a carbanion in the molecule.
  • the unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule. Maleic acid, itaconic acid, mesaconic acid, Citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides or half esters are preferred.
  • unsaturated carboxylic acid monomer (C) (meth) acrylic acid, maleic acid and salts thereof are preferable. More preferred is (meth) acrylic acid, and even more preferred is acrylic acid.
  • the copolymer of the present invention comprises other monomers (other than the above (poly) alkylene glycol-containing monomer (A), hydrophobic monomer (B) and unsaturated carboxylic acid monomer (C)). You may have the structural unit (e) derived from E). Specific examples of the other monomer (E) will be given below. These are all those having the Log P value of less than 1 or greater than 8.
  • Esters of unsaturated (mono, di) carboxylic acids and alcohols such as methyl (meth) acrylate, methoxyethyl (meth) acrylate, monopropyl malate, diethyl malate; hydroxyethyl (meth) acrylate, hydroxyprotyl ( Esters of unsaturated (mono, di) carboxylic acids such as meth) acrylates and diols; amides of unsaturated carboxylic acids such as methyl (meth) acrylamide and diethylacrylamide and amines; N-methylmaleimide; Maleimide monomers such as N-ethylmaleimide; vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl- Such as 3-buten-1-ol and 2-methyl-2-buten-1-ol Japanese alcohols; Diesters of alkyl (poly) alkylene glycols and unsaturated di
  • the method for producing the (poly) alkylene glycol-containing copolymer of the present invention is not particularly limited, but it can be produced by polymerizing the monomer component. Specific examples and preferred examples of the monomer component are described above. It is as follows. Moreover, the content rate of each monomer component with respect to 100 mass% of all monomer components is the same as the ratio of each structural unit with respect to 100 mass% of the above-mentioned all structural units.
  • a chain transfer agent can be used for adjusting the molecular weight of the obtained polymer.
  • the chain transfer agent include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid; isopropyl alcohol ( Secondary alcohols such as 2-propanol); phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, dithionic acid and salts thereof (sodium sulfite, sulfurous acid, etc.)
  • hydrophilic chain transfer agents such as lower oxides such as sodium dithionate and the like, hydrogen sulfites (such as sodium hydrogen sulfite) and metabisulfites (such as sodium metabisulfite) and salts thereof.
  • hydrophilic chain transfer agents such as lower
  • a hydrophobic chain transfer agent can also be used as the chain transfer agent.
  • the hydrophobic chain transfer agent include 3 carbon atoms such as butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 3-mercaptopropionate, etc.
  • a thiol chain transfer agent having the above hydrocarbon group is preferably used.
  • a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) as the monomer (E).
  • the amount of the chain transfer agent used may be appropriately set, but is 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.5 mol or more, based on 100 mol of the total amount of monomer components. In particular, it is 1.0 mol or more, preferably 20 mol or less, still more preferably 10 mol or less, particularly preferably 5 mol or less, and most preferably 3 mol or less.
  • the polymerization reaction can be performed by a method such as solution polymerization or bulk polymerization using a radical polymerization initiator as necessary.
  • the polymerization can also be carried out batchwise, semi-batchwise, continuous, or combinations thereof.
  • semi-batch solution polymerization is preferable from the viewpoint of increasing the yield of the copolymer.
  • a solvent for the solution polymerization water, an organic solvent, or a mixed solvent thereof can be used.
  • organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; acetone, methyl ethyl ketone, and the like Ketone compounds; and cyclic ether compounds such as tetrahydrofuran and dioxane.
  • organic solvents hydrophilic solvents such as alcohol are preferable. More preferred is isopropyl alcohol.
  • water or a mixed solvent of water and an organic solvent is preferable.
  • the ratio of the organic solvent to 100% by mass of the mixed solvent is preferably 20 to 80% by mass, more preferably 40 to 60% by mass.
  • the concentration of the monomer may be set as appropriate, but the amount of all raw materials used such as the monomer and solvent used from the start to the end of the polymerization reaction Is 100% by mass, the mass concentration of all monomers is preferably 50% by mass or more and 90% by mass or less.
  • variation of a monomer concentration shall be 30 mass% or less from the start to the completion
  • a water-soluble polymerization initiator for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2,2′-azobis- Azoamidine compounds such as 2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, and azonitriles such as 2-carbamoylazoisobutyronitrile Water-soluble azo initiators such as compounds are used.
  • a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate
  • hydrogen peroxide 2,2′-azobis- Azoamidine compounds
  • 2,2′-azobis- Azoamidine compounds such as 2-methylpropionamidine hydrochloride
  • cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin
  • alkali metal sulfites such as sodium hydrogen sulfite, metabisulphite, sodium hypophosphite, Fe (II) salts such as Mole salt, hydroxymethanesulfine Acid sodium dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), erythorbium It can also be used in combination accelerator acid (salt) and the like.
  • a combination of persulfate or hydrogen peroxide and an accelerator such as L-ascorbic acid (salt) or Fe (II) salt is preferable.
  • These radical polymerization initiators and accelerators may be used alone or in combination of two or more.
  • the amount of the radical polymerization initiator used is preferably 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.5 mol or more, particularly preferably with respect to 100 mol of the total amount of monomer components. 1.0 mole or more, preferably 20 moles or less, even more preferably 10 moles or less, particularly preferably 5 moles or less, and most preferably 3 moles or less.
  • the polymerization conditions such as the polymerization temperature are appropriately determined depending on the polymerization method used, the solvent, the polymerization initiator, and the chain transfer agent. Moreover, it is preferable that it is 150 degrees C or less. More preferably, it is 40 degreeC or more, More preferably, it is 50 degreeC or more. More preferably, it is 120 degrees C or less, More preferably, it is 100 degrees C or less. Furthermore, from the viewpoint of proceeding the copolymerization reaction more uniformly, it is preferable to set the fluctuation range of the polymerization temperature to 15 ° C. or less from the start to the end of the polymerization reaction.
  • the method of charging each monomer component into the reaction vessel is not particularly limited, a method in which the entire amount is initially charged into the reaction vessel; a method in which the entire amount is divided or continuously charged into the reaction vessel; a part is initially in the reaction vessel
  • a method may be used in which the remainder is charged and the remainder is divided or continuously charged into the reaction vessel.
  • the charging rate of each monomer into the reaction vessel in the middle of the reaction continuously or stepwise, and changing the weight ratio of each monomer per unit time continuously or stepwise the monomer ratio
  • Two or more types of copolymers having different values may be synthesized simultaneously during the polymerization reaction.
  • the radical polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined according to the purpose.
  • Each polymer obtained as described above can be used as it is as a dispersant, but if necessary, it may be further neutralized with an alkaline substance.
  • alkaline substance inorganic salts such as hydroxides or carbonates of monovalent metals or divalent metals; ammonia; organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.
  • the (poly) alkylene glycol-containing copolymer of the present invention exhibits good performance as a water-insoluble inorganic or organic dispersant.
  • good performance can be exhibited as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating; a dispersant for water slurry such as cement and coal;
  • water treatment agents for scale prevention in cooling water systems, boiler water systems, seawater desalination equipment, pulp digesters, and black liquor concentration tanks scale treatment agents; textile treatments such as dyeing aids and textile antistatic aids Agent; Adhesive; Sealing agent; Flexibility-imparting component for various polymers; Detergent builder and the like.
  • the method of using the (poly) alkylene glycol-containing copolymer of the present invention as a cement admixture is also one aspect of the present invention. It is particularly useful as a cement admixture for ready-mixed concrete and shotcrete.
  • the form in which the copolymer is a copolymer for cement admixture is a preferred form of the present invention, and the cement admixture containing the copolymer, the copolymer and cement are combined.
  • a cement composition that includes the cement admixture and cement.
  • the manufacturing method of the cement composition including the process of adding the said (poly) alkylene glycol containing copolymer to a hydraulic material is also one of this invention.
  • a cement admixture will be described as a typical dispersant.
  • the cement admixture of the present invention essentially comprises the copolymer of the present invention, but may contain two or more kinds of the above-mentioned copolymers, and one or more kinds of copolymers different from the above-mentioned copolymers. May be included.
  • the content of the copolymer in the cement admixture (the total content in the case where two or more types of copolymers are included) is not particularly limited, but in order to sufficiently exhibit the performance derived from the copolymer.
  • the solid content (that is, the non-volatile content) in the cement admixture is preferably 30% by mass or more in 100% by mass.
  • cement admixture refers to a cement additive added to a cement composition such as cement paste, mortar, and concrete, and may be an agent composed only of the above copolymer. Moreover, it may be an agent containing not only the above copolymer but also other components and additives as required.
  • the cement admixture may further contain other commonly used cement dispersants and water reducing agents, and can be used in combination.
  • Other cement dispersants water reducing agents
  • Other cement dispersants are not particularly limited.
  • various sulfonic acid-based dispersants having a sulfonic acid group in the molecule, polyoxyalkylene chains and carboxyl groups in the molecule.
  • examples thereof include various polycarboxylic acid-based dispersants (water reducing agents) and various phosphoric acid-based dispersants (water reducing agents) having a phosphate group in the molecule.
  • the content of the copolymer of the present invention is contained in the cement admixture in order to sufficiently exhibit the performance derived from the copolymer. It is preferable that it is 30 mass% or more in total solid content (namely, non-volatile content) of 100 mass%. More preferably, it is 50 mass% or more, More preferably, it is 60 mass% or more, Most preferably, it is 70 mass% or more.
  • the cement admixture includes, for example, water-soluble polymer substances, polymer emulsions, retarders, early strengthening agents / accelerators, mineral oil-based antifoaming agents, fat-based antifoaming agents, fatty acid-based antifoaming agents, and fatty acid esters.
  • Antifoaming agent oxyalkylene antifoaming agent, alcohol antifoaming agent, amide antifoaming agent, phosphate ester antifoaming agent, metal soap antifoaming agent, silicone antifoaming agent, AE agent, surfactant Agent, waterproof agent, rust preventive agent, crack reducing agent, expansion agent, cement wetting agent, thickener, separation reducing agent, flocculant, drying shrinkage reducing agent, strength enhancer, self-leveling agent, rust preventive agent, colorant ,
  • cement additives materials such as fungicides, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and gypsum may be included.
  • the cement admixture can be used for various hydraulic materials, that is, cement compositions such as cement and gypsum, and other hydraulic materials.
  • cement compositions such as cement and gypsum
  • other hydraulic materials As a specific example of a hydraulic composition containing such a hydraulic material, water and the above cement admixture, and further containing fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.) as necessary, Cement paste, mortar, concrete, plaster, etc. are mentioned.
  • a cement composition using cement as the hydraulic material is most preferable, and a cement composition containing the cement admixture and cement is also one aspect of the present invention.
  • cement composition In the cement composition of the present invention, as the cement, Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate resistance and low alkali type thereof); 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 heat cement (low heat blast furnace cement, fly Ash mixed low heat generation type blast furnace cement, cement with high belite content); ultra high strength cement; cement-based solidified material; eco-cement (cement manufactured using one or more of municipal waste incineration ash and sewage sludge incineration ash) Besides these, blast furnace slag, fly ash, shi Dar ash, clinker ash, husk ash, silica fume, silica powder, and a film obtained by adding a fine powder and gypsum limestone powder.
  • the cement contained in the cement composition of the present invention may be only one type or two or more types.
  • As the above aggregate in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia, etc. Refractory aggregate and the like.
  • the unit water amount per 1 m 3 , the amount of cement used, and the water / cement ratio are not particularly limited.
  • the unit water amount is 100 to 200 kg / m 3
  • the cement amount used is 200 to 800 kg / m 3
  • the cement composition of the present invention can be widely used from poor blends to rich blends, and is effective for both high-strength concrete with a large amount of unit cement and poor blend concrete with a unit cement amount of 300 kg / m 3 or less. It is.
  • the resulting cement composition has excellent workability for a long time in a wide range of blending, and therefore it can be effectively applied particularly to ready-mixed concrete, shotcrete and the like.
  • it can be applied to concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, and the like.
  • precast concrete precast concrete
  • concrete for centrifugal molding concrete for centrifugal molding
  • concrete for vibration compaction concrete for vibration compaction
  • steam-cured concrete and the like.
  • high fluidity such as medium fluidity concrete (concrete with slump flow value in the range of 350 to 500 mm), high fluidity concrete (concrete with slump flow value in the range of 500 to 700 mm), self-filling concrete, self-leveling material, etc.
  • the cement admixture of the present invention is also effective for required mortar and concrete.
  • the blending ratio of the cement admixture of the present invention is, for example, the copolymer (the total amount when there are a plurality of components) as an essential component of the present invention, the total amount of cement mass in terms of solid content. It is preferably set to be 0.01 to 5% by mass with respect to 100% by mass. If the amount is less than 0.01% by mass, the performance may not be sufficient. On the other hand, if the amount exceeds 5% by mass, the effect will be practically peaked and disadvantageous in terms of economy, or the cement composition may be separated from the material. And may cause abnormal condensation. More preferably, the content is 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass.
  • the solid content can be measured as follows. ⁇ Method for measuring solid content> 1. Weigh the aluminum dish. The solid content to be measured is precisely weighed on the aluminum dish precisely weighed in 2.1. 3. A solid content measurement product precisely weighed in 2 is placed in a dryer adjusted to 130 ° C. in a nitrogen atmosphere for 1 hour. 4. After 1 hour, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes. 5. After 15 minutes, remove from the desiccator and precisely weigh the aluminum dish and the measurement object. The solid content is measured by subtracting the mass of the aluminum pan obtained in 1 from the mass obtained in 6.5 and dividing by the mass of the solid content measurement product obtained in 2.
  • “monomer composition (preparation)” and “monomer composition (finish)” have the following meanings.
  • “Monomer composition (preparation)” A composition calculated from the amount of monomers charged in a reaction vessel to produce a copolymer.
  • “Monomer composition (finished)” Analyzes the consumption rate in the polymerization reaction of the monomer charged in the reaction vessel to produce the copolymer, and all the consumed monomer is copolymerized by the polymerization reaction. A composition calculated to convert to coalescence.
  • ⁇ Storage stability test> An aqueous solution having a copolymer concentration of 30% by mass was prepared, placed in a 20 mL test tube with a lid, and allowed to stand in a thermostat at 50 ° C., and the presence or absence of turbidity or separation of the solution was visually determined.
  • storage stability it is preferable that the solution is uniform and stable for a long time. It is preferred that no separation occurs in the solution, and more preferred that neither turbidity nor separation occur.
  • Example 1 A solution (1a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 68.0 parts of water and 29.2 parts of 2-propanol.
  • a solution of 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) (Log P value: 1.88) dissolved in 2.8 parts of water and 1.2 parts of 2-propanol (1b ) was prepared.
  • Ethylene oxide is added to 65.4 parts of water, 28.0 parts of 2-propanol, and 3-methyl-3-buten-1-ol in a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser.
  • Example 2 An aqueous solution (2a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 77.8 parts of water and 19.4 parts of 2-propanol.
  • a solution (2b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.3 parts of water and 0.8 part of 2-propanol.
  • AA acrylic acid
  • BA butyl acrylate
  • Example 3 A solution (3a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 82.6 parts of water and 14.6 parts of 2-propanol.
  • a solution (3b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.5 parts of water and 0.6 part of 2-propanol.
  • AA acrylic acid
  • BA butyl acrylate
  • 2-propanol 2-propanol
  • Example 4 A solution (4a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 87.5 parts of water and 9.7 parts of 2-propanol.
  • a solution (4b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.7 parts of water and 0.4 part of 2-propanol.
  • AA acrylic acid
  • BA butyl acrylate
  • 2-propanol 2-propanol
  • Example 5 A solution (5a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 90.4 parts of water and 6.8 parts of 2-propanol.
  • a solution (5b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.8 parts of water and 0.3 part of 2-propanol.
  • AA acrylic acid
  • BA butyl acrylate
  • a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser 86.8 parts of water, 6.5 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol.
  • Example 6 A solution (6a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 94.3 parts of water and 2.9 parts of 2-propanol.
  • a solution (6b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.9 parts of water and 0.1 part of 2-propanol.
  • AA acrylic acid
  • BA butyl acrylate
  • a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser 90.6 parts of water, 2.8 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol.
  • Example 7 A solution (7a) in which 2.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 105.7 parts of 2-propanol was prepared.
  • a solution (7b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA) (Log P value: 3.53) in 4.1 parts of 2-propanol.
  • EHA 2-ethylhexyl acrylate
  • a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser 41.5 parts of water, 94.2 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol.
  • Example 8 A solution (8a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 45.1 parts of water and 57.3 parts of 2-propanol.
  • a solution (8b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
  • AA acrylic acid
  • EHA 2-ethylhexyl acrylate
  • ethylene oxide is added to 41.1 parts of water, 52.3 parts of 2-propanol, and 3-methyl-3-buten-1-ol.
  • Example 9 A solution (9a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 41.0 parts of water and 61.4 parts of 2-propanol.
  • Ethylene oxide was added to 37.3 parts of water, 56.0 parts of 2-propanol, and 3-methyl-3-buten-1-ol in a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser.
  • Example 10 A solution (10a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 43.0 parts of water and 59.4 parts of 2-propanol.
  • a solution (10b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
  • AA acrylic acid
  • EHA 2-ethylhexyl acrylate
  • 39.2 parts of water, 54.1 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol.
  • Example 11 A solution (11a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 47.1 parts of water and 55.3 parts of 2-propanol.
  • a solution (11b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
  • EHA 2-ethylhexyl acrylate
  • a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser 42.9 parts of water, 50.4 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol.
  • Example 12 A solution (12a) was prepared by dissolving 0.4 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 44.3 parts of water. A solution (12b) in which 24.7 parts of acrylic acid (AA) and 22.6 parts of butyl acrylate (BA) were mixed was prepared.
  • a reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser, 2.8 parts of water, and an unsaturated polysiloxane having an average of 50 moles of ethylene oxide added to 3-methyl-3-buten-1-ol Charge 334.6 parts of an 80% aqueous solution of an alkylene glycol ether monomer (IPN-50) and 1.4 parts of a 70% aqueous solution of paratoluenesulfonic acid monohydrate, and then stir in the reaction vessel. After replacing with nitrogen and raising the temperature to 60 ° C. in a nitrogen atmosphere, 13.0 parts of a 2% aqueous hydrogen peroxide solution was added.
  • the above mixed solution (12a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (12b) over 3 hours.
  • the temperature during this period was constant at 60 ° C.
  • the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction.
  • ⁇ ⁇ 100 / ( ⁇ + ⁇ ) of the obtained copolymer (12) was 0.
  • Table 1 The obtained copolymer (12) was subjected to a storage stability test. The results are shown in Table 2.
  • Example 13 A solution (13a) was prepared by dissolving 0.2 part of L-ascorbic acid and 0.6 part of 3-mercaptopropionic acid in 68.2 parts of water and 68.2 parts of 2-propanol. Ethylene oxide is added to 43.6 parts of water, 43.6 parts of 2-propanol, and 2-methyl-2-propen-1-ol in a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser.
  • Example 14 A solution (14a) in which 3.3 parts of ammonium persulfate was dissolved in 107.3 parts of water was prepared. A solution (14b) in which 16.5 parts of butyl acrylate (BA) and 19.7 parts of methacrylic acid (MAA) were mixed was prepared. A solution (14c) was prepared by dissolving 123.8 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23) (PGM-23) and 1.2 parts of 3-mercaptopropionic acid in 53.6 parts of water. .
  • a reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser is 79.5 parts of water, and an unsaturated polysiloxane having an average of 50 mol of ethylene oxide added to 3-methyl-3-buten-1-ol. Then, 267.4 parts of an alkylene glycol ether monomer (IPN-50) and 3.0 parts of acrylic acid were charged. Subsequently, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere.
  • IPN-50 alkylene glycol ether monomer
  • a solution (c-2a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 51.2 parts of water and 51.2 parts of 2-propanol.
  • a solution (c-2b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
  • EHA 2-ethylhexyl acrylate
  • a reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser 46.7 parts of water, 46.7 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol.
  • a solution (c-4a) in which 3.2 parts of ammonium persulfate was dissolved in 77.4 parts of water was prepared.
  • 41.8 parts of methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 23) (PGM-23), 1.9 parts of 3-mercaptopropionic acid, 11.1 parts of methacrylic acid were dissolved in 23.5 parts of water.
  • a solution (c-4b) was prepared.
  • a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser was charged with 253.9 parts of water, and the inside of the reaction vessel was purged with nitrogen under stirring.
  • Mw ( ⁇ ) represents a high molecular weight-derived peak ⁇
  • Mw ( ⁇ 1) represents a copolymer-derived peak ⁇ 1
  • Mw ( ⁇ 2) represents a weight-average molecular weight of a monomer-derived peak ⁇ 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le but de la présente invention concerne un copolymère contenant du (poly)alkylèneglycol présentant une séparation suffisamment supprimée dans une solution de copolymère et possédant une excellente stabilité au stockage. La présente invention concerne un copolymère contenant une chaîne (poly)alkylèneglycol possédant un motif structural (a) dérivé d'un monomère contenant du (poly)alkylèneglycol (A) représenté par la formule (1) ci-dessous et un motif structural (b) dérivé d'un monomère hydrophobe (B), le monomère hydrophobe (B) possédant un groupe éthyléniquement insaturé et possédant un coefficient de partage octanol/eau (valeur Log P) de 1,0-8,0. Dans un chromatogramme du copolymère tel que mesuré par un détecteur d'indice de réfraction différentiel pour chromatographie par perméation de gel (CPG), les surfaces de pic α et de pic ß définies ci-dessous satisfont à l'équation (2) ci-dessous. (2): α×100/(α+β)≤3,0 <Pics α et β> Pic α : un pic correspondant à un poids moléculaire moyen en poids (Mw) supérieur à 200000. Pic ß : un pic correspondant à un Mw de 200.000 ou moins.
PCT/JP2019/018551 2018-05-16 2019-05-09 Copolymère contenant du (poly)alkylèneglycol WO2019221002A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020519594A JPWO2019221002A1 (ja) 2018-05-16 2019-05-09 （ポリ）アルキレングリコール含有共重合体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018094599 2018-05-16
JP2018-094599 2018-05-16

Publications (1)

Publication Number Publication Date
WO2019221002A1 true WO2019221002A1 (fr) 2019-11-21

Family

ID=68539931

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/018551 WO2019221002A1 (fr) 2018-05-16 2019-05-09 Copolymère contenant du (poly)alkylèneglycol

Country Status (2)

Country Link
JP (1) JPWO2019221002A1 (fr)
WO (1) WO2019221002A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845326B (zh) * 2021-10-22 2022-05-20 株洲宏信科技发展有限公司 一种混凝土抗泥剂

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004519406A (ja) * 2001-05-28 2004-07-02 株式会社日本触媒 セメント混和剤及びセメント組成物
JP2010209134A (ja) * 2009-03-06 2010-09-24 Nippon Shokubai Co Ltd ポリオキシアルキレン系重合体およびその製造方法
JP2012171818A (ja) * 2011-02-18 2012-09-10 Nippon Shokubai Co Ltd セメント混和剤およびセメント組成物
WO2014010572A1 (fr) * 2012-07-13 2014-01-16 株式会社日本触媒 Copolymère polycarboxylique, agent de dispersion de ciment, mélange de ciment et composition de ciment
WO2018088529A1 (fr) * 2016-11-11 2018-05-17 株式会社日本触媒 Copolymère à base d'acide polycarboxylique, adjuvant du béton, et composition de béton
JP2018154712A (ja) * 2017-03-16 2018-10-04 株式会社日本触媒 ポリカルボン酸系共重合体、セメント分散剤、コンクリート混和剤、およびコンクリート組成物
JP2019085434A (ja) * 2017-11-01 2019-06-06 株式会社日本触媒 ポリカルボン酸系共重合体、コンクリート混和剤、およびコンクリート組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004519406A (ja) * 2001-05-28 2004-07-02 株式会社日本触媒 セメント混和剤及びセメント組成物
JP2010209134A (ja) * 2009-03-06 2010-09-24 Nippon Shokubai Co Ltd ポリオキシアルキレン系重合体およびその製造方法
JP2012171818A (ja) * 2011-02-18 2012-09-10 Nippon Shokubai Co Ltd セメント混和剤およびセメント組成物
WO2014010572A1 (fr) * 2012-07-13 2014-01-16 株式会社日本触媒 Copolymère polycarboxylique, agent de dispersion de ciment, mélange de ciment et composition de ciment
WO2018088529A1 (fr) * 2016-11-11 2018-05-17 株式会社日本触媒 Copolymère à base d'acide polycarboxylique, adjuvant du béton, et composition de béton
JP2018154712A (ja) * 2017-03-16 2018-10-04 株式会社日本触媒 ポリカルボン酸系共重合体、セメント分散剤、コンクリート混和剤、およびコンクリート組成物
JP2019085434A (ja) * 2017-11-01 2019-06-06 株式会社日本触媒 ポリカルボン酸系共重合体、コンクリート混和剤、およびコンクリート組成物

Also Published As

Publication number Publication date
JPWO2019221002A1 (ja) 2021-05-20

Similar Documents

Publication Publication Date Title
JP5769930B2 (ja) 分散剤
JP4874255B2 (ja) クラフトリグニンを利用した分散剤および新規なリグニン誘導体
JP5955386B2 (ja) ポリカルボン酸系共重合体、セメント分散剤、セメント混和剤及びセメント組成物
EP0995727B1 (fr) Additif pour ciment sur la base de polymères acryliques
JP2007076969A (ja) 水硬性材料用混和剤組成物
JP6012139B2 (ja) セメント混和剤及びセメント組成物
JP5584638B2 (ja) セメント混和剤およびセメント組成物
JP6145381B2 (ja) （ポリ）アルキレングリコール系ブロック共重合体及びその用途
JP2007112703A (ja) セメント混和剤用ポリカルボン酸系重合体およびセメント混和剤
JP5707165B2 (ja) セメント混和剤及びこれを含むセメント組成物
WO2019221002A1 (fr) Copolymère contenant du (poly)alkylèneglycol
JP2020023422A (ja) 再生骨材含有セメント組成物用添加剤
JP5806558B2 (ja) 分散剤
JP2004043280A (ja) セメント混和剤及びその製造方法
JP4274838B2 (ja) セメント混和剤及びその製造方法
JP4883901B2 (ja) セメント混和剤
JP4497830B2 (ja) セメント混和剤及びその製造方法
JP6109240B2 (ja) セメント混和剤及びセメント組成物
JP7160632B2 (ja) ポリカルボン酸系共重合体
JP5581461B1 (ja) セメント混和剤用共重合体（塩）およびその製造方法、並びにこれを用いたセメント組成物
JP2005118684A (ja) 分散剤
JP2014031296A (ja) セメント混和剤用ポリカルボン酸系共重合体
JP2006069859A (ja) セメント混和剤組成物
JP2024079062A (ja) 貧配合コンクリート組成物用添加剤
WO2024101285A1 (fr) Dispersant pour composition de ciment contenant du carbonate de calcium et composition de ciment contenant du carbonate de calcium

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19803219

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2020519594

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19803219

Country of ref document: EP

Kind code of ref document: A1