WO2008032799A1 - Nouveau polymère d'acide polycarboxylique - Google Patents

Nouveau polymère d'acide polycarboxylique Download PDF

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Publication number
WO2008032799A1
WO2008032799A1 PCT/JP2007/067876 JP2007067876W WO2008032799A1 WO 2008032799 A1 WO2008032799 A1 WO 2008032799A1 JP 2007067876 W JP2007067876 W JP 2007067876W WO 2008032799 A1 WO2008032799 A1 WO 2008032799A1
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Prior art keywords
polycarboxylic acid
acid
alkylene oxide
polymer
based polymer
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PCT/JP2007/067876
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English (en)
Japanese (ja)
Inventor
Haruyoshi Miyauchi
Katsutoshi Satou
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Toho Chemical Industry Co., Ltd.
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Priority to JP2008534393A priority Critical patent/JP5424084B2/ja
Publication of WO2008032799A1 publication Critical patent/WO2008032799A1/fr

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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
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • 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
    • C04B28/14—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 calcium sulfate cements
    • 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
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • 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
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials

Definitions

  • the present invention relates to a novel polycarboxylic acid-based polymer. More specifically, the polycarboxylic acid system is characterized by comprising a constituent unit derived from an unsaturated alcohol alkylene oxide adduct having a hydrophobic group at the end and a constituent unit derived from an unsaturated carboxylic acid carboxylic acid. It relates to a polymer.
  • a polymer composed of an unsaturated alcohol alkylene oxide adduct monomer and an unsaturated carboxylic acid monomer collects various particles and has an excellent dispersibility in water. It is widely used as a surfactant and dispersant for various solid powder systems.
  • Patent Document 1 discloses an aqueous slurry dispersant of a water-soluble copolymer obtained from the unsaturated carboxylic acid-based component unit (I) and the unsaturated alcohol-based component unit (II), a cement admixture, a scale inhibitor, It has been proposed for use in detergent builders, waste paper recycling deinking agents, cotton scouring cleaners, coal dispersants, etc.
  • Patent Document 2 a copolymer of an ⁇ , ⁇ -unsaturated carboxylic acid or an anhydride thereof and an alkenyl ether having an C 2 to C 18 oxyalkylene group is suitable as a dispersant for gypsum. It is shown that the results of fluidization and water reduction are shown.
  • Patent Documents 1 to 4 unsaturated alcohol alkylene oxide adducts Although a mixed addition of two or more alkylene oxides (eg, ethylene oxide and propylene oxide) has been proposed in Japan, the actual test examples were limited to the results using alcohols of a single addition of ethylene oxide, If the above alkylene oxide is used, the order or site to be added is / is studied! //! Patent document 1: JP-A-62-68806
  • Patent Document 2 Japanese Patent Application Laid-Open No. 11 314953
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2003-192722
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2005 46781
  • the present invention has been made to further improve the performance as a dispersant under such conventional technical background.
  • the curing retardancy is often influenced by the type of acid group contained in the polymer, or depending on the amount of dispersing agent added, ie, the water loss of the dispersing agent.
  • mechanical formability is also regarded as important, and it is desirable that the releasability from the formwork and the pressing surface be excellent and that there is no corner chipping of the molded body.
  • the amount of air in the above composition can be adjusted, or that the appearance of the molded product (for example, plaster products (reinforced board, plaster for porcelain etc., etc.) is not impaired by coloring etc. depending on the application. It is considered as a sex store.
  • a polycarboxylic acid-based polymer composed of a reactive alcohol derivative having a polymerizable binding site and a dibasic acid-based derivative! Part of the terminal part of the polyalkylene oxide chain of Or 4 polyalkylene oxide addition, that is, containing at a terminal portion an alkylene oxide having 3 or 4 carbon atoms at a ratio of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. It has been found that the polycarboxylic acid-based polymer exhibits excellent dispersion performance in an aqueous dispersion of solid powder, and also exhibits water reduction performance and low curing delay when added to a hydraulic composition.
  • the present invention relates to a polycarboxylic acid-based polymer including a constituent unit derived from an unsaturated alcohol alkylene oxide compound and a constituent unit derived from an unsaturated carboxylic acid compound.
  • the graft chain bonded to the main chain skeleton of the polymer contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal part of the polyalkylene oxide chain is the total molar amount of the alkylene oxide of the graft chain.
  • the present invention relates to a polycarboxylic acid-based polymer characterized in that it has an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol%.
  • the present invention is also directed to a polycarboxylic acid-based polymer, characterized in that it is a structural unit derived from a part or all of a structural unit derived from the unsaturated carboxylic acid-based compound and a nucleic acid and / or a derivative thereof. Regarding coalescence.
  • the polycarboxylic acid-based polymer is constituted by including a constituent unit (I) represented by the following formula (I) and a constituent unit (II) represented by the formula (II):
  • the terminal part of the polyalkylene oxide chain in the constituent unit (I) has an alkylene oxide having 3 or 4 carbon atoms in an amount of 0.1 to 30 mol% based on the total molar amount of the alkylene oxide chain.
  • the present invention relates to a polycarboxylic acid-based polymer characterized in having a proportion.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms
  • X represents one (CH 2) bO—
  • AO represents Represents an alkylene oxide group having 2 to 4 carbon atoms
  • a represents an average addition mole number of alkylene oxide
  • b represents an integer of 1 to 20.
  • R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, —COOH, —COOM, —COOY, or R 5 And R 6 or R 7 and R 8 together form an acid anhydride
  • M represents an alkali metal, an alkaline earth metal, an amine, an alkanolamine
  • Y represents a C 1-22 carbon atom.
  • AO represents an alkylene oxide group having 2 to 4 carbon atoms
  • c is a number from 1 to 200 in average molar number of addition of alkylene oxide
  • R 9 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.
  • the polycarboxylic acid-based polymer comprises the structural unit (I) and the structural unit
  • the present invention relates to a polycarboxylic acid-based polymer characterized in that it is constituted by further comprising a constituent unit (III) represented by the following formula (III) in addition to (II).
  • Z is a polyamidepolyamine obtained by condensing a dibasic acid with a polyalkylenepolyamine and / or an active imino group, an amino group or an amide residue of the polyamidepolyamine, an alkylene oxide having 2 to 4 carbon atoms per equivalent
  • the modified polyamide polyamine obtained by adding 0.1 to 10 mol of represents a group bonded to a carbon atom of the main chain via an amide bond.
  • the present invention provides a polyamidepolyamine obtained by condensing a dibasic acid and a polyalkylenepolyamine and / or an active imino group, an amino group, and an amide residue of the polyamidepolyamine.
  • the present invention relates to a polycarboxylic acid-based polymer composition comprising a polyamidepolyamine modified product obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms per equivalent.
  • the above-mentioned polycarboxylic acid polymer or polycarboxylic acid polymer composition relates to a dispersant for hydraulic composition, an additive for gypsum, an additive for concrete exterior plate, and a water-reducing agent for lightweight concrete. Effect of the invention
  • the resin composition has excellent dispersion performance with respect to aqueous dispersions of various solid powders, further improves the curing delaying property and the moldability, is excellent in the air amount adjusting ability, and has the obtained curing. It is possible to provide a polycarboxylic acid-based polymer that can make the appearance of the body excellent.
  • a dispersant for hydraulic composition an additive for gypsum, an additive for concrete exterior plate, and a water reducing agent for lightweight concrete can be provided.
  • the present invention is directed to a polymer based on a polybasic acid comprising a structural unit derived from an unsaturated alcohol alkylene oxide compound and a structural unit derived from an unsaturated carboxylic acid compound,
  • the graft chain bonded to the main chain skeleton of the polymer contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal part of the poly (alkylene oxide) chain is the total molar amount of the alkylene oxide of the graft chain.
  • the present invention relates to a polycarboxylic acid-based polymer having an alkylene oxide of 3 to 4 carbon atoms in a ratio of 0.1 to 30 mol%.
  • the polycarboxylic acid-based polymer is composed of the structural unit (I) and the structural unit (II) shown above, and the polycarboxylic acid-based polymer further comprises the structural unit (I) and (C) And the above-mentioned structural unit (III) derived from a modified polyamidepolyamine and / or polyamidepolyamine.
  • the polycarboxylic acid-based polymer thus configured has a comb polymer structure in which a graft chain such as a polyalkylene oxide chain or a polyamide polyamine chain is bonded to a main chain skeleton.
  • the polycarboxylic acid polymer of the present invention may further contain a polyamidepolyamine and / or a modified polyamidepolyamine and may be in the form of a composition.
  • Structural unit (I) which comprises the polycarboxylic acid type polymer of this invention is represented by a following formula. [4]
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms
  • X represents one (CH 2) bO 2
  • AO represents carbon
  • an alkylene oxide group having 2 to 4 atoms wherein a represents an average addition mole number of alkylene oxide and represents a number of 1 to 200, and b represents an integer of 1 to 20.
  • the above polyalkylene oxide chain one (AO) a is preferably mainly ethylene oxide, and the average addition mole number is preferably 30 or more, more preferably 50 or more to improve the dispersion performance. Desirable in terms of
  • the terminal part of the polyalkylene oxide chain (the bonding position with R 4 ) is a propylene oxide having 3 carbon atoms or a butylene oxide having 4 carbon atoms in the total number of moles of the alkylene oxide chain.
  • the content is in the range of 0.1 to 30 mol%. More preferably, it is in the range of 0.1 to 20 mol%, more preferably in the range of 0.1 to 10 mol% or 12 to 20 mol%, and most preferably in the range of 0.5 to 5 mol% or 15 to 20 mol% It is preferable in that the dispersibility is significantly improved.
  • R 4 be selected from a hydrogen atom, a methyl group, an ethyl group, a butyl group, an isobutyl group, a propyl group or an isopropyl group.
  • the above structural unit (I) is a structural unit derived from, for example, the following compounds: polyalkylene glycol monochloro nore no tene, poly anolechi lene gluco nor mono mono norole kin norere tenole
  • alkenyl ethers formed from (alkoxy) polyalkylene glycols such as methoxypolyanolexylene glyconololemono alino lea tenore and methoxy poly anolexylene glyco-nole mono alkenyl ether and alkenyl ether having 3 to 8 carbon atoms And unsaturated aliphatic ethers which are unsaturated aliphatic alcohol alkylene oxide adducts.
  • specific examples of the most preferable compounds are: 3-methyl-3-butene-1-ol, 3-methyl-ol-2-butene, 2-methyl-1-butene, 2-methyl-3-butene 2-nonole, aryl alcohol, oleyl alcohol, etc. It is an alkylene oxide adduct of alcohol Yes
  • the constituent unit (I) is derived from one or more of these compounds.
  • Structural unit (II) constituting the polycarboxylic acid polymer of the present invention is represented by the following formula.
  • R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, COOH, —COOM, or —COOY, or R 5 R 6 or R 7 and R 8 together form an acid anhydride
  • M represents an alkali metal, an alkaline earth metal, an ammonium, an alkanolamine
  • Y represents a carbon number of 1 to 22 carbon atoms or hydrogen group - represents the (AO) c- R 9
  • AO represents an alkylene oxide group having 2 to 4 carbon atoms
  • c is a number from 1 to 200 in average molar number of addition of alkylene oxide
  • R 9 Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.
  • the above structural unit (II) is a structural unit derived from acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid and the like, and exhibits the best performance.
  • fumaric acid is contained in a considerable proportion, for example, 10% by mass or more based on the total mass of the polymer.
  • Y is specifically a partial ester or a whole ester having 1 to 22 carbon atoms, or a part of a polyalkylene oxide adduct. Esters or whole esters, partial esters or whole esters of (alkoxy) polyalkylene glycols and the like can be mentioned.
  • (alkoxy) polyalkylene glycol mono (meth) atalylates such as methoxypoly ethylene glycol mono (meth) atalylate, polyethylene glycol mono (meth) atalylate, etc .
  • (Anolekoxy) polyanolequile glycol malates such as N-glyco monole monomaleate, methoxy polyethylene glycolo di-state maleate, polyethylene glycolone mono-maleate, polyethylene glycolo mono-lemenalate, methoxypolyethylene glycol monofumarate, methoxypolyethylene monoglycolate
  • Examples include (alkoxy) polyalkylene glycol fumarates such as fumarate, polyethylene glycol monolemono fumarate, polyethylene glycol difumarate and the like.
  • the alkylene oxide can be added singly or in combination, and when two or more alkylene oxides are used, the block addition power P or random addition may be used.
  • the fumaric acid derivative methoxypolyethylene glycol difumarate can be mentioned.
  • the above structural unit (II) contains a fumaric acid and / or a structural unit derived from a fumaric acid derivative, it is preferably 10 to 100% by mass, more preferably 10% to 100% by mass in the total mass of all the structural units (II). It is desirable to include 20 to 100% by mass, particularly preferably 30 to 100% by mass, and most preferably 50 to 100% by mass.
  • the polycarboxylic acid-based polymer of the present invention is most preferably a polyalkylene oxide chain obtained by bonding propylene oxide or butylene oxide to the end of an ethylene oxide chain having an average addition mole number of 50 or more.
  • Component units (I) derived from an unsaturated alcohol alkylene oxide compound having a propylene oxide or butylene oxide ratio of 0.1 to 20 mol% with respect to the total number of moles of the alkylene oxide chain and fumar Structural unit (II) force containing an acid-derived structural unit in a substantial proportion (10% by mass or more with respect to the total mass of the polymer), force that is desirable S, desired.
  • the polycarboxylic acid-based polymer of the present invention comprises structural units (III) derived from polyamide polyamines and / or polyamide polyamine modified products in addition to the above structural units (I) and (II).
  • Structural unit (III) is represented by the following formula.
  • z is a polyamidepolyamine obtained by condensing a dibasic acid with a polyalkylenepolyamine and / or an active imino group, an amino group or an amide residue of the polyamidepolyamine, an alkylene oxide having 2 to 4 carbon atoms per equivalent
  • the above dibasic acid constituting Z has a total of 2 to 2 carbon atoms.
  • aliphatic saturated dibasic acids such as oxalic acid, malonic acid, succinic acid, daltalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like
  • polyalkylene polyamines include ethylene diamine, diethylene acid Triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a mixture of high molecular weight polyethylenepolyamine which is a mixture containing a large number of ethylene units and nitrogen atoms, and the like can be mentioned. .
  • the above structural unit (III) is a polyamide which is a condensation product of the dibasic acid and a polyalkylenepolyamine, a polyamine and / or (or, the active polyamide, an active amino group of an polyamine, an amino group, an amide, 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms is added per 1 equivalent of the remaining group with respect to the polyamidepolyamine modified product force Maleic anhydride, maleic acid, fumanoleic acid and the like via an amide bond Component unit.
  • polyamidepolyamines or polyalkyleneoxide-modified polyamidepolyamines have the property of exhibiting basicity in aqueous solution, they sometimes act as neutralizing agents for polycarboxylic acid polymers.
  • the constituent unit (IV) can be contained S in addition to the constituent units (I) to (III).
  • Examples of the compound from which the above-mentioned constituent unit (IV) can be derived include (meth) acrylic acid (salt), (meth) acrylic acid polyalkylene glycol monoalkyl ether, (meth) aryl sulfonic acid (salt), styrene It is a compound such as sulfonic acid (salt), alkyl (meth) acrylate, styrene, (meth) acrylamide and the like if it is a compound capable of forming a polymer with the above structural units (I) to (III). It is not particularly limited.
  • structural unit (IV) 100 to 70% by mass (structural units (I) to (III)) (provided that a sum total 100 mass 0/0) is preferably in the range of.
  • the polycarboxylic acid polymer composition of the present invention is a polyamidepolyamine obtained by condensing a dibasic acid and a polyalkylenepolyamine in addition to the above polycarboxylic acid polymer, and / or an active imino group of the polyamidepolyamine, amino
  • a polyamide polyamide modified product obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms to 1 equivalent of an amide residue can be contained.
  • the polyalkylene polyamines constituting the above polyamide polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a large number of ethylene units and nitrogen atoms.
  • Polymers of high-molecular-weight polyethylene polyamines which are mixtures including, etc., polymers of cyclic amines such as polyethyleneimine, polypropyleneimine, poly (3-methylpropylimine), poly (2-ethylpropylimine), unsaturated amines such as polyureamin and polyallylamine
  • polymers and the like include polymers and the like.
  • polyalkylene polyamines include cyclic amines such as ethyleneimine, propyleneimine, 3-methylpropylimine, 2-acetylpropylimine, unsaturated amides such as N-butylacetamide, N-butylformamide, and N-butylphthalimide, and unsaturated imides And a copolymer of an unsaturated compound copolymerizable with Examples of unsaturated compounds copolymerizable with cyclic imides, unsaturated amides, unsaturated imides and the like include, for example, dimethyleacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid and the like These salts, cyclic sulfide compounds such as ethylene sulfide and propylene sulfide, oxetanes, mono or bis alkyl oxetanes, mono or bis alkyl
  • dibasic acid constituting the above polyamidepolyamine examples include a oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like having a total of 2 to 2 carbon atoms. There are 10 aliphatic saturated dibasic acids.
  • Derivatives thereof may also be used as dibasic acids, such as dibasic acid anhydrides (eg, anhydrides of the above dibasic acids), dibasic acid esters (eg, monomethyl esters of the above dibasic acids, monoethinole ester).
  • dibasic acid anhydrides eg, anhydrides of the above dibasic acids
  • dibasic acid esters eg, monomethyl esters of the above dibasic acids, monoethinole ester.
  • dibasic acid dihalide diichloride of the above dibasic acid, dibrominated compound, Iodide etc.
  • the above-mentioned modified polyamidepolyamine means an alkylene oxide having 2 to 4 carbon atoms per 0.1 equivalent of the active imino group, amino group and amide residue of the above polyamidepolyamine. It shows a compound to which 10 moles have been added. That is, as this alkylene oxide,
  • ethylene oxide, propylene oxide, butylene oxide, etc. which may be used alone or in combination, and when two or more alkylene oxides are used, they may be polymerized in block form to give random or random Polymerize on!
  • the method for producing the unsaturated alcohol alkylene oxide adduct from which the structural unit (I) is derived and the polymerization method for obtaining the polycarboxylic acid polymer are not particularly limited.
  • the polymerization active group (unsaturated group) does not lose its polymerization activity, does not transfer the position of the polymerization active group, and is by-produced. It needs to be manufactured paying attention to reducing the diol content.
  • the polyalkylene oxide adduct of alcohol having a polymerization active group can be used as a raw material for polymerization after production regardless of the purification process.
  • the same polymer can be obtained by any of solvent polymerization, aqueous solution polymerization, continuous type and notch type. Many things to be done ,.
  • the dibasic acid and the polyamidepolyamine are condensed according to a conventional amidation method, and further, an amide group with maleic acid, fumaric acid and maleic anhydride is formed, which is necessary.
  • an alkylene oxide is added, a condensation product of a dibasic acid and a polyamide polyamine, or an alkylene oxide-modified polyamide polyamide to which an alkylene oxide is added is formed to be grafted on a polycarboxylic acid polymer.
  • Examples thereof include a method of adding alkylene oxide to an aqueous polymer solution grafted with a polycarboxylic acid polymer after formation.
  • the polycarboxylic acid-based polymer of the present invention finally obtained has a weight-average molecular weight of 10,000-2000 by gel permeation chromatography (hereinafter referred to as “GPC method”, polyethylene glycol conversion).
  • GPC method gel permeation chromatography
  • the range of 500,000 is appropriate, and more preferably, the weight-average molecular weight is in the range of 000 to 100,000. Power is desirable in order to exhibit excellent dispersion performance. Yes.
  • it is also possible to control molecular weight distribution by using in combination a force chain transfer agent or the like whose molecular weight can be controlled by adjusting the type and / or amount of radical polymerization initiator etc. in aqueous solution polymerization. It is.
  • the "polycarboxylic acid polymer” may be a polymer only, but in general, unreacted components and by-products generated in each polymerization step, alkylene oxide addition step, etc.
  • the ingredients included are also included.
  • the polycarboxylic acid-based polymer and polymer composition of the present invention are aqueous dispersions of various solid powders by adjusting the neutralization ratio of the acid group, adjusting the content of the polyamide polyamine, etc. according to various uses. Its performance can be widely exhibited as a dispersant in
  • the polycarboxylic acid-based polymer of the present invention can be used as the above-mentioned dispersant as it is (without adding anything), and, according to various applications, publicly known and commonly used additives are appropriately adopted. It can also be used in the form of combined admixtures.
  • polycarboxylic acid-based polymer of the present invention examples include inorganic dispersants, pigment dispersants, hair setting agents, cosmetic base materials * additives, and paints, using dispersion techniques of inorganic compounds.
  • a pitch dispersant a paper strength additive, a binder for pigment coating, a papermaking dispersant, a deinking agent, a detergent additive, a powder detergent builder, a liquid detergent builder, and others of the present invention
  • It can also be used as a cell regulator, scale inhibitor, etc., and can be suitably used in a wide range of applications.
  • additives for hydraulic composition for example, various additives for concrete products, additives for grout, additives for concrete repair material, additives for gypsum board, water Additive for hard self-felling, additive for cement gypsum composite material It can be used for
  • a known additive can be added to form a gypsum dispersant composition.
  • the additive include foams such as alkyl sulfates, alkyl ether sulfates and alkyl sulfonates, foam stabilizers, antifoams, water repellents, adhesives and the like. These may be used alone or in combination of two or more.
  • the above-mentioned gypsum board additive may be used by adding 0.1 to 5% by mass (additive solid content mass ratio) to the raw material gypsum.
  • Additive solid content mass ratio additive solid content mass ratio
  • Gypsum includes anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum and the like.
  • additives used with the above-mentioned gypsum board additives include general-purpose water reducing agents, foam agents, antifoaming agents, foam stabilizers, hardening regulators, etc. Further, glass fibers, carbon fibers, waste paper as reinforcing fibers, etc. It is also practiced to add virgin pulp or the like, or to make a gypsum board together with a lightweight aggregate such as perlite and foamed steel.
  • the polycarboxylic acid-based polymer and polymer composition of the present invention are a dispersant for hydraulic composition, an additive for gypsum, an additive for concrete exterior plate, which is particularly preferable among the above-mentioned applications, and a lightweight It can be used as a water reducing agent for concrete.
  • the change of the arrangement state of the acid group in the polymer occurs, and the dispersion performance of the aqueous dispersion of various solid powders is improved.
  • the use of a fumaric acid compound reduces the unreacted monomers due to an increase in the polymerization rate of the polycarboxylic acid polymer, and controls the molecular weight of the polymer. In addition to the fact that it has become easier, it is considered that the synergetic effect of these will lead to the improvement of the dispersion performance.
  • the present invention will be described in more detail based on the following examples.
  • the present invention is obtained by the above production method, and is not limited to this example.
  • % and part described below represent mass% and a mass part.
  • reaction solution is cooled to 50 ° C. and neutralized with 48% caustic soda until pH 7 to obtain 837 g of an aqueous solution of polycarboxylic acid polymer C2 (solids concentration: 40%, weight average molecular weight: 26,000) I got
  • Necessary amounts of polycarboxylic acid polymers B1 to B7 and C1 and C2 of the above Production Example and melamine sodium sulfonate formalin condensate (MSFF) as Comparative Example 3 are weighed based on the solid content, water is added, and the total amount is 65 g. Adjust the mixing water to become To this, add 100 g of Sakura Indoku Gypsum Grade A (manufactured by Yoshino Gypsum Co., Ltd.) (65% water / gypsum ratio), The mixing was done for a second.
  • MSFF melamine sodium sulfonate formalin condensate
  • a ⁇ 50 mm ⁇ H50 mm cylindrical hollow cylinder was prepared in advance at the center of a urethane board (35 cm ⁇ 35 cm), and the mixed gypsum slurry was poured until the container was full. After that, the hollow cylinder was pulled up in the direction perpendicular to the urethane board, and the spread of the gypsum slurry was measured. The maximum diameter of the spread and the diameter perpendicular to it were measured, and the average value was used as an indicator of dispersibility.
  • polyboric acid polymers B1 to B7, C1 and C2, and melamine sulfonic acid soda formalin condensate are positively weighed on the basis of solid content, and mixing water is added to total. Adjusted to 162 g. To this was added 250 g of Sakura Indoku Gypsum Grade A (manufactured by Yoshino Shikoshi Co., Ltd.) (65% water / gypsum ratio), and mixed for 10 seconds with a small juicer mixer.
  • Comparative Example 1 in which no PO group is added to the end of the alkylene oxide chain is inferior to both the examples in the dispersion property and the curing delay property, and the conventional polycarboxylic acid polymer Although Comparative Example 2 corresponding to Comparative Example 2 showed relatively excellent results in dispersibility, results were obtained that curing delay was caused.
  • Comparative Example 3 corresponding to the conventional dispersant containing formaldehyde, although the curing was fast, the result that the dispersibility was inferior was obtained.
  • the finished gypsum slurry was poured into an aluminum cup (diameter 54 mm, depth 23 mm) and allowed to stand at 80 ° C. for 24 hours.
  • the color of the solidified gypsum block surface after 24 hours was visually confirmed to evaluate the colorability.
  • the polycarboxylic acid-based polymer of the present invention can be used to prevent the decline in product value due to coloring when used in the preparation of gypsum products (strengthened board, plaster for pottery, etc.) in which gypsum skin is exposed. It also has an accompanying effect.
  • a molded plate (width 100 mm, thickness 15 mm) was produced by extrusion, and the extrusion moldability as an extruded plate was evaluated from the extrusion speed at this time.
  • Waste paper pulp 2. 8 parts
  • NSF Naphthalene sulfonic acid soda
  • the polycarboxylic acid-based polymers Bl, B3 and B5 of the above-mentioned production example, and (meth) acrylic acid-methoPEG (meth) atalylate polymer (PC) and sodium naphthalenesulfonate (NSF) were used to obtain the following Table 6
  • the hardenability and air bubble entrapment property of the mortar slurry were evaluated by the composition shown in the above.
  • NSF Naphthalene sulfonic acid soda
  • the polycarboxylic acid-based polymer of the present invention is useful as a water reducing agent for ALC because it satisfies both the curability and the bubble entrapment property.
  • Comparative Example 7 in which a general-purpose polycarboxylic acid-based polymer is blended, demolding can not be performed within a predetermined time due to curing delay, and in Comparative Example 8 in which sodium naphthalenesulfonate is blended. Although it is excellent in the curability, it has a low water removability, so that the force viscosity becomes large, and the result is that coarse bubbles are not removed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyethers (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à proposer un polymère d'acide polycarboxylique doté d'une aptitude élevée à la dispersion dans divers systèmes solide-poudre. La solution proposée consiste à former le polymère d'acide polycarboxylique à partir d'un dérivé alcool réactif comportant un site de liaison polymérisable et d'un dérivé acide dibasique, ledit procédé de formation étant caractérisé en ce que le dérivé alcool réactif comporte une chaîne poly(oxyde d'alkylène) dont une extrémité est formée par addition de poly(oxyde d'alkylène) en C3 ou C4, la teneur en oxyde d'alkylène en C3 ou C4 dans les parties terminales allant de 0,1 à 30 % en mole, par rapport à la totalité des chaînes d'oxyde d'alkylène.
PCT/JP2007/067876 2006-09-13 2007-09-13 Nouveau polymère d'acide polycarboxylique WO2008032799A1 (fr)

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JP2009242611A (ja) * 2008-03-31 2009-10-22 Nof Corp 共重合体の製造方法
JP2010528976A (ja) * 2007-06-11 2010-08-26 シーカ・テクノロジー・アーゲー 石膏組成物のための分散剤
WO2012012923A1 (fr) * 2010-07-27 2012-02-02 上海台界化工有限公司 Procédé de synthèse d'un agent de réduction de l'eau de type acide polycarboxylique
CN102372458A (zh) * 2010-08-24 2012-03-14 上海台界化工有限公司 固体聚羧酸减水剂
WO2013137400A1 (fr) * 2012-03-14 2013-09-19 東邦化学工業株式会社 Dispersant à base de gypse
JP2013227170A (ja) * 2012-04-26 2013-11-07 Sanyo Chem Ind Ltd 押出成型セメント組成物用添加剤
WO2014203953A1 (fr) * 2013-06-19 2014-12-24 花王株式会社 Composition de dispersant liquide pour gypse
JP2017052843A (ja) * 2015-09-08 2017-03-16 株式会社日本触媒 結合剤

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WO2020196574A1 (fr) * 2019-03-25 2020-10-01 株式会社日本触媒 Composition contenant un polymère
CN111995327B (zh) * 2020-09-01 2022-02-11 中国建材检验认证集团北京天誉有限公司 一种超高性能混凝土及其制备方法

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Publication number Priority date Publication date Assignee Title
JP2010528976A (ja) * 2007-06-11 2010-08-26 シーカ・テクノロジー・アーゲー 石膏組成物のための分散剤
JP2009242611A (ja) * 2008-03-31 2009-10-22 Nof Corp 共重合体の製造方法
WO2012012923A1 (fr) * 2010-07-27 2012-02-02 上海台界化工有限公司 Procédé de synthèse d'un agent de réduction de l'eau de type acide polycarboxylique
US8933184B2 (en) 2010-07-27 2015-01-13 Shanghai Taijie Chemical Co., Ltd. Synthesis method of polycarboxylic acid water-reducing agent
CN102372458A (zh) * 2010-08-24 2012-03-14 上海台界化工有限公司 固体聚羧酸减水剂
KR20150004341A (ko) * 2012-03-14 2015-01-12 도호 가가꾸 고오교 가부시키가이샤 석고용 분산제
CN104271531A (zh) * 2012-03-14 2015-01-07 东邦化学工业株式会社 石膏用分散剂
WO2013137400A1 (fr) * 2012-03-14 2013-09-19 東邦化学工業株式会社 Dispersant à base de gypse
JPWO2013137400A1 (ja) * 2012-03-14 2015-08-03 東邦化学工業株式会社 石膏用分散剤
AU2013233152B2 (en) * 2012-03-14 2016-12-08 Yoshino Gypsum Co.,Ltd. Gypsum dispersant
RU2648781C2 (ru) * 2012-03-14 2018-03-28 Йосино Джипсум Ко., Лтд. Диспергирующая добавка для гипса
KR102006667B1 (ko) * 2012-03-14 2019-08-02 요시노 셋고 가부시키가이샤 석고용 분산제
JP2013227170A (ja) * 2012-04-26 2013-11-07 Sanyo Chem Ind Ltd 押出成型セメント組成物用添加剤
WO2014203953A1 (fr) * 2013-06-19 2014-12-24 花王株式会社 Composition de dispersant liquide pour gypse
JP2015024949A (ja) * 2013-06-19 2015-02-05 花王株式会社 石膏用液体分散剤組成物
CN105308001A (zh) * 2013-06-19 2016-02-03 吉野石膏株式会社 石膏用液体分散剂组合物
RU2656053C2 (ru) * 2013-06-19 2018-05-30 Йосино Джипсум Ко., Лтд. Жидкая диспергирующая композиция для гипса
JP2017052843A (ja) * 2015-09-08 2017-03-16 株式会社日本触媒 結合剤

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