CA2125521A1 - Fluidity control of cementitious compositions - Google Patents
Fluidity control of cementitious compositionsInfo
- Publication number
- CA2125521A1 CA2125521A1 CA002125521A CA2125521A CA2125521A1 CA 2125521 A1 CA2125521 A1 CA 2125521A1 CA 002125521 A CA002125521 A CA 002125521A CA 2125521 A CA2125521 A CA 2125521A CA 2125521 A1 CA2125521 A1 CA 2125521A1
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- CA
- Canada
- Prior art keywords
- monomer
- weight
- meth
- polymer
- glycol
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
- 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
- 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
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
-
- 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
- C04B2103/50—Defoamers, air detrainers
Abstract
ABSTRACT
An admixture for modifying the fluidity of a cementitious mixture comprises a cement-dispersing agent which is an aqueous solution of polymer, in which solution an oxyalkylene-based defoaming agent is dissolved or dispersed in particles of no greater that 20µM diameter. The polymer is preferably a polymer which comprises units derived from unsaturated carboxylic acid monomer and the polymer is preferably prepared in the presence of the defoaming agent. Particular addition copolymers give particularly good results. The admixture permits good control of the fluidity of cementitious compositions and has extended shelf life.
An admixture for modifying the fluidity of a cementitious mixture comprises a cement-dispersing agent which is an aqueous solution of polymer, in which solution an oxyalkylene-based defoaming agent is dissolved or dispersed in particles of no greater that 20µM diameter. The polymer is preferably a polymer which comprises units derived from unsaturated carboxylic acid monomer and the polymer is preferably prepared in the presence of the defoaming agent. Particular addition copolymers give particularly good results. The admixture permits good control of the fluidity of cementitious compositions and has extended shelf life.
Description
-154-0244 212~21 FLIJIDll Y CONTROL OF CEMENmlOUS COMPOSITIONS
This invention relates to fluidit,v control of cementitious compositions, to admixtures ~or achieving such control and to cementitious compositions comprising such admixtures.
Water-reducing compositions are widely used in cementitious compositions such as5 concrete to reduce the water content (and thereby increase strength) while maintaining fluidity or "slump" (so that the compositions can flow easily, for example, around complicated formwork). Typical water-reducing agents are the so-called "superplasticisers", for example, ,B-naphthalene sulphonate-formaldehyde ("BNS")condensates and various polycarboxylate-based materials. One of the problems which 10 water-reducing agents, especially the aforementioned polycarboxylates, can introduce is the entrainment into the cementitious composition of excessive volumes of air.
While the presence of some air is harmless and even beneficial, excessive air entrainment leads to reduced strength. Air entrainment can of course be reduced by reducing the concentration of water-reducing agent used, but the desired slump 15 control is then diminished. It has been proposed to use known defoaming agents to counteract excessive aeration, but this has also often proved unsatisfactory, one reason being that a mixture of water-reducing agent and defoaming agent, a commercially desirable package, is usually unstable.
It has now been found that it is possible to make an admixture which confers high 20 slump on cementitious compositions, but without excessive aeration. There is therefore provided, according to the present invention, a fluidity-controlling admixture for cementitious compositions, comprising at least one cement-dispersing agent and at least one defoaming agent, characterised in that (a) the cement-dispersing agent is an aqueous solution of polymer; and ~- ~ 2~2S~l (b) the defoaming agent is oxyalkylene-based and is either dissolved in the polymer solution or is stably dispersed therein in particles of no more than 20,uM diameter.
When the defoaming agent is soluble in the aqueous polymer solution, the admixture according to the invention is prepared simply by dissolving the defoaming agent in 5 the solution. When the defoam;ng agent is not soluble in the solution, it is dispersed such that the disperse particles are no greater than 20,uM m diameter. It is to be understood here that the use of the word "particle" encompasses not only solid particulate matter (in which case the diameter referred to is the largest dimension of the particle) but also droplets of dispersed liquid, whether of inherently liquid matter 10 or of dissolved solid material.
The particles are stably dispersed in the solution. By "stably dispersed" is meant that.
when prepared and allowed to stand, a dispersion will remain a dispersion for atleast 24 hours. The reason for this is not fully understood, but it is noticeable that a dispersion which does not comply with this requirement does not give such good 15 results in a cementitious composition, even when it is used when it is still a dispersion, for example, immediately upon preparation or shortly thereafter.
Dispersion of an insoluble defoaming agent is achievable in two ways. The first way is simple dispersion of the defoaming agent in the solution so that a dispersion of the appropriate particle size is given. The second way is the dispersion of the defoaming 20 agent in the presence of polymerisable monomer and polymerisation of the monomer to give the polymer. It has been found that dispersions prepared in this second manner give especially good results and are preferred. A further practical advantage is that the achievement of the desired small particle size is more easily achievable.
Details of pxeferred monomer compositions are given hereinunder.
25 The polymer for use in this invention may be any polymer which is water-soluble and which is a water-reducing agent or a cement-dispersing agent. However, it has been found that certain polymers give especially good results. Thus, in a preferred admixture, the polymer comprises a main component which is selected from at least - . ., ,- , - ~ . ~ ~ .
... .. . ~ ,, ~ :.. . . . .
; ~ . , ~ ,. .....
-1540244 3 2125~2 1 one of (A) a copolymer obtained by polymerising a monomer mixture which comprises an unsaturated carboxylic acid monomer;
(B) the neutralised salt of (A); and (C) the polymer obtained by crosslinking (A) and/or (B) by means of a a~g agent.
In a preferred embodiment, the monomer mixture comprises from 5-98% by weight of an alkylene glycol mono(meth)acrylic acid ester monomer (a) of the formula I
R2 ~ .
Rl-CH=C-Coo(R3O)m-R4 (I) wherein Rl and R2 are independently hydrogen or methyl, R3 is an alkylene group of from 2-4 carbon atoms, R4 is hydrogen or an alkyl group of 1 to 22 carbon atoms, and m represents an integer of 1 to 100, and 2 to 95% by weight of a (meth)acrylic acid 15 base monomer (b) of the formula (II) Rl-CH=C-COOMI (II) wherein Rl and R2 have the abovementioned significances, and Ml is hydrogen, 2n monovalent metal, divalent metal, ammoniurn group or an organic amine group, and 0 to 50% by weight of a monomer (c) capable of being copolymerized with these monomers provided that the sum of (a), (b) and (c) shall be 100% by weight.
In a further embodiment of the invention, said monomer mixture comprises from 5-98% by weight of an alkoxypolyalkylene glycol mono(meth)allyl ether base monomer25 (d) of the formula (m);
212~21 Rl-CH-C-((::H2)n-o-(R30)m-R4 (III) wherein Rl, R2, R3, R4 and m are as hereinabove defined and n is O or 1, and 2 to 95%
5 by weight of a (meth)acrylic acid base monomer (b) of the formula (IV) Y Z
X-C=C-COOM2 (IV) wherein X and Y are independently selected from hydrogen, methyl and -COOM3, 10 or X or Y together with -COOM2 form an anhydride ring, Z is selected from -CH2COoM3, hydrogen or methyl and M2 and M3 are independently selected from the significances of Ml given hereinabove, an alkyl group of 1-20 carbon atoms, an alkylene glycol of 2-4 carbon atoms and a polyalkylene glycol of from 2-100 mols of a glycol adduct, provided that at least one of M2, M3 is selected from hydrogen,15 monovalent metal, divalent metal, ammonium group and an organic amine group;
and from 0-50% by weight of monomer (f) capable of copolymerisation with (d) and(e), (d)+(e)+(f) being 100% by weight.
In a further preferred embodiment, said monomer mixture comprises from 5-98% by weight of at least one a-olefinic monomer (g) having from 2-12 carbon atoms, from 20 2-95% by weight of an ethylenically unsaturated dicarboxylic acid anhydride base monomer (h~ and from 0-50% by weight of monomer (i) copolymerisable with (g) and(h), (g)+(h)+(i) being 100% by weight.
Polycarboxylic acid base is a general name of a cement-dispersing agent which contains as a main component a copolymer (A) obtained by polymerising a monomer 25 mixture containing an unsaturated carboxylic acid base monomer as an essential component and/or a copolymer (B) obtained by further neutralizing the copolymer (A) with an alkaline substance and/or a cross-linked copolymer (C) obtained by post cross-linking the copolymer (A~ by using a cross-linking agent. The unsaturated :^ :
l54-0244 5 2~25~2~
carboxylic acid monomer may include unsaturated monocarboxylic acid such as (meth)acrylic acid and monovalent metal salt, divalent metal salt, ammonium salt and an organic amine salt thereof; an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, itaconic acid, etc. and monovalent metal salt, divalent 5 metal salt, ammonium salt, an organic amine salt, anhydride thereof or a monoester of these acids with an aliphatic alcohol having 1 to 20 carbon atoms or a glycolhaving 2 to 4 carbon atoms or a polyalkylene glycol having 2 to 100 addition molnumber. One or rnore of these can be used.
Further preferable monomer rnixtures comprise a mixture containing 5 to 98%, preferably 50 to 97%, by weight of an alkylene glycol mono(meth)acrylate (a) designated by the abovementioned general formula (I), 2 to 95% by weight, preferably 3 to 50% by weight of a (meth)acrylate base monomer (b) designated by the abovementioned formula (II) and 0 to 50% by weight, preferably 0 to 30% by weight of monomer (c) capable of being copolymerized with these monomers, provided thatthe sum of (a), (b) and (c) is 100% by weight; a mixture containing 5 to 98% by weight, preferably 50 to 97% by weight of an (alkoxy)polyalkylene glycol mono(meth)allyl ether base monomer (d) designated by the abovementioned general formula (III), 2 to 95% by weight, preferably 3 to 50% by weight of an unsaturated carboxylic acid base monomer (e) designated by the above mentioned general formula (IV), and 0 to 50% by weight, preferably 0 to 30% by weight of monomer (f) capable of being copolymerized with these monomers, provided that the sum of (d), (e), and (f) is 100% by weight; and a mixture of 5 to 98% by weight, preferably 10 to 70% by weight of an a-olefinic monomer (g) having 2 to 12 carbon atoms, 2 to 95% by weight, preferably 30 to 90% by weight of an ethylenically unsaturated dicarboxylic acidanhydride base monomer (h), and 0 to 50% by weight, preferably 0 to 30% by weight of monomer (i) capable of being copolymerized with these monomers, provided thatthe sum of ~g), (h) and (i) is 100% by weight.
Examples of monomer (a) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol 212S~l polypropylene glycol mono(meth)acrylate, polyethylene glycol polybutylene glycolmono(meth)acrylate, polypropylene glycol polybutylene glycol mono(meth)acrylate,polyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate,methoxy polyethylene glycol mono(meth)acrylate, methoxy polypropylene glycol 5 mono(meth)acrylate, methoxy polybutylene glycol mono(meth)acrylate, methoxy polybutylene glycol mono(meth)-acrylate, me~oxy polyethylene glycol polypropylene glycol mono(meth)acrylate, methoxy polyethylene glycol polybutylene glycol mono(meth)acrylate, methoxy polypropylene glycol polybutylene glycol mono(meth)acrylate, methoxy propyethylene glycol polypropylene glycol 10 polybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol mono(meth)acrylate, ethoxypolypropylene glycol mono-(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolypropylene glycol polybutylene glycol 15 mono(meth)acrylate and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate. More ~an one such monomer may be used.
Suitable examples of monomer (b) include acrylic and methacrylic acids and theirmonovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
More than one such monomer may be used.
20 The monomer (c) is a monomer capable of copolymerization with the monomers (a) and (b). Examples of monomer (c) include esters of aliphatic alcohols of 1 to 20carbons with (meth)acrylic acid unsaturated dicarboxylic acids of maleic acid, fumaric acid, citraconic acid, etc., or monoesters or diesters of these acids with aliphatic alcohols of 1 to 20 carbons or glycols of 2 to 4 carbons, or polyalkylene glycols of 25 added mol number 2 to 100 of these glycols, unsaturated amides such as (meth)acrylamide and (meth)acryl alkylamide, vinyl esters such as vinyl acetate and vinyl propionate, aromatic vinyls such as styrene, unsaturated sulfonates such as vinyl sulfonates, (meth)allylsulfonic acid, sulfoethyl(meth)acrylate, 2-(meth)-acrylamido-2-methylpropane sulfonic acid and styrene sulfonate, and their 30 monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
.
This invention relates to fluidit,v control of cementitious compositions, to admixtures ~or achieving such control and to cementitious compositions comprising such admixtures.
Water-reducing compositions are widely used in cementitious compositions such as5 concrete to reduce the water content (and thereby increase strength) while maintaining fluidity or "slump" (so that the compositions can flow easily, for example, around complicated formwork). Typical water-reducing agents are the so-called "superplasticisers", for example, ,B-naphthalene sulphonate-formaldehyde ("BNS")condensates and various polycarboxylate-based materials. One of the problems which 10 water-reducing agents, especially the aforementioned polycarboxylates, can introduce is the entrainment into the cementitious composition of excessive volumes of air.
While the presence of some air is harmless and even beneficial, excessive air entrainment leads to reduced strength. Air entrainment can of course be reduced by reducing the concentration of water-reducing agent used, but the desired slump 15 control is then diminished. It has been proposed to use known defoaming agents to counteract excessive aeration, but this has also often proved unsatisfactory, one reason being that a mixture of water-reducing agent and defoaming agent, a commercially desirable package, is usually unstable.
It has now been found that it is possible to make an admixture which confers high 20 slump on cementitious compositions, but without excessive aeration. There is therefore provided, according to the present invention, a fluidity-controlling admixture for cementitious compositions, comprising at least one cement-dispersing agent and at least one defoaming agent, characterised in that (a) the cement-dispersing agent is an aqueous solution of polymer; and ~- ~ 2~2S~l (b) the defoaming agent is oxyalkylene-based and is either dissolved in the polymer solution or is stably dispersed therein in particles of no more than 20,uM diameter.
When the defoaming agent is soluble in the aqueous polymer solution, the admixture according to the invention is prepared simply by dissolving the defoaming agent in 5 the solution. When the defoam;ng agent is not soluble in the solution, it is dispersed such that the disperse particles are no greater than 20,uM m diameter. It is to be understood here that the use of the word "particle" encompasses not only solid particulate matter (in which case the diameter referred to is the largest dimension of the particle) but also droplets of dispersed liquid, whether of inherently liquid matter 10 or of dissolved solid material.
The particles are stably dispersed in the solution. By "stably dispersed" is meant that.
when prepared and allowed to stand, a dispersion will remain a dispersion for atleast 24 hours. The reason for this is not fully understood, but it is noticeable that a dispersion which does not comply with this requirement does not give such good 15 results in a cementitious composition, even when it is used when it is still a dispersion, for example, immediately upon preparation or shortly thereafter.
Dispersion of an insoluble defoaming agent is achievable in two ways. The first way is simple dispersion of the defoaming agent in the solution so that a dispersion of the appropriate particle size is given. The second way is the dispersion of the defoaming 20 agent in the presence of polymerisable monomer and polymerisation of the monomer to give the polymer. It has been found that dispersions prepared in this second manner give especially good results and are preferred. A further practical advantage is that the achievement of the desired small particle size is more easily achievable.
Details of pxeferred monomer compositions are given hereinunder.
25 The polymer for use in this invention may be any polymer which is water-soluble and which is a water-reducing agent or a cement-dispersing agent. However, it has been found that certain polymers give especially good results. Thus, in a preferred admixture, the polymer comprises a main component which is selected from at least - . ., ,- , - ~ . ~ ~ .
... .. . ~ ,, ~ :.. . . . .
; ~ . , ~ ,. .....
-1540244 3 2125~2 1 one of (A) a copolymer obtained by polymerising a monomer mixture which comprises an unsaturated carboxylic acid monomer;
(B) the neutralised salt of (A); and (C) the polymer obtained by crosslinking (A) and/or (B) by means of a a~g agent.
In a preferred embodiment, the monomer mixture comprises from 5-98% by weight of an alkylene glycol mono(meth)acrylic acid ester monomer (a) of the formula I
R2 ~ .
Rl-CH=C-Coo(R3O)m-R4 (I) wherein Rl and R2 are independently hydrogen or methyl, R3 is an alkylene group of from 2-4 carbon atoms, R4 is hydrogen or an alkyl group of 1 to 22 carbon atoms, and m represents an integer of 1 to 100, and 2 to 95% by weight of a (meth)acrylic acid 15 base monomer (b) of the formula (II) Rl-CH=C-COOMI (II) wherein Rl and R2 have the abovementioned significances, and Ml is hydrogen, 2n monovalent metal, divalent metal, ammoniurn group or an organic amine group, and 0 to 50% by weight of a monomer (c) capable of being copolymerized with these monomers provided that the sum of (a), (b) and (c) shall be 100% by weight.
In a further embodiment of the invention, said monomer mixture comprises from 5-98% by weight of an alkoxypolyalkylene glycol mono(meth)allyl ether base monomer25 (d) of the formula (m);
212~21 Rl-CH-C-((::H2)n-o-(R30)m-R4 (III) wherein Rl, R2, R3, R4 and m are as hereinabove defined and n is O or 1, and 2 to 95%
5 by weight of a (meth)acrylic acid base monomer (b) of the formula (IV) Y Z
X-C=C-COOM2 (IV) wherein X and Y are independently selected from hydrogen, methyl and -COOM3, 10 or X or Y together with -COOM2 form an anhydride ring, Z is selected from -CH2COoM3, hydrogen or methyl and M2 and M3 are independently selected from the significances of Ml given hereinabove, an alkyl group of 1-20 carbon atoms, an alkylene glycol of 2-4 carbon atoms and a polyalkylene glycol of from 2-100 mols of a glycol adduct, provided that at least one of M2, M3 is selected from hydrogen,15 monovalent metal, divalent metal, ammonium group and an organic amine group;
and from 0-50% by weight of monomer (f) capable of copolymerisation with (d) and(e), (d)+(e)+(f) being 100% by weight.
In a further preferred embodiment, said monomer mixture comprises from 5-98% by weight of at least one a-olefinic monomer (g) having from 2-12 carbon atoms, from 20 2-95% by weight of an ethylenically unsaturated dicarboxylic acid anhydride base monomer (h~ and from 0-50% by weight of monomer (i) copolymerisable with (g) and(h), (g)+(h)+(i) being 100% by weight.
Polycarboxylic acid base is a general name of a cement-dispersing agent which contains as a main component a copolymer (A) obtained by polymerising a monomer 25 mixture containing an unsaturated carboxylic acid base monomer as an essential component and/or a copolymer (B) obtained by further neutralizing the copolymer (A) with an alkaline substance and/or a cross-linked copolymer (C) obtained by post cross-linking the copolymer (A~ by using a cross-linking agent. The unsaturated :^ :
l54-0244 5 2~25~2~
carboxylic acid monomer may include unsaturated monocarboxylic acid such as (meth)acrylic acid and monovalent metal salt, divalent metal salt, ammonium salt and an organic amine salt thereof; an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, itaconic acid, etc. and monovalent metal salt, divalent 5 metal salt, ammonium salt, an organic amine salt, anhydride thereof or a monoester of these acids with an aliphatic alcohol having 1 to 20 carbon atoms or a glycolhaving 2 to 4 carbon atoms or a polyalkylene glycol having 2 to 100 addition molnumber. One or rnore of these can be used.
Further preferable monomer rnixtures comprise a mixture containing 5 to 98%, preferably 50 to 97%, by weight of an alkylene glycol mono(meth)acrylate (a) designated by the abovementioned general formula (I), 2 to 95% by weight, preferably 3 to 50% by weight of a (meth)acrylate base monomer (b) designated by the abovementioned formula (II) and 0 to 50% by weight, preferably 0 to 30% by weight of monomer (c) capable of being copolymerized with these monomers, provided thatthe sum of (a), (b) and (c) is 100% by weight; a mixture containing 5 to 98% by weight, preferably 50 to 97% by weight of an (alkoxy)polyalkylene glycol mono(meth)allyl ether base monomer (d) designated by the abovementioned general formula (III), 2 to 95% by weight, preferably 3 to 50% by weight of an unsaturated carboxylic acid base monomer (e) designated by the above mentioned general formula (IV), and 0 to 50% by weight, preferably 0 to 30% by weight of monomer (f) capable of being copolymerized with these monomers, provided that the sum of (d), (e), and (f) is 100% by weight; and a mixture of 5 to 98% by weight, preferably 10 to 70% by weight of an a-olefinic monomer (g) having 2 to 12 carbon atoms, 2 to 95% by weight, preferably 30 to 90% by weight of an ethylenically unsaturated dicarboxylic acidanhydride base monomer (h), and 0 to 50% by weight, preferably 0 to 30% by weight of monomer (i) capable of being copolymerized with these monomers, provided thatthe sum of ~g), (h) and (i) is 100% by weight.
Examples of monomer (a) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol 212S~l polypropylene glycol mono(meth)acrylate, polyethylene glycol polybutylene glycolmono(meth)acrylate, polypropylene glycol polybutylene glycol mono(meth)acrylate,polyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate,methoxy polyethylene glycol mono(meth)acrylate, methoxy polypropylene glycol 5 mono(meth)acrylate, methoxy polybutylene glycol mono(meth)acrylate, methoxy polybutylene glycol mono(meth)-acrylate, me~oxy polyethylene glycol polypropylene glycol mono(meth)acrylate, methoxy polyethylene glycol polybutylene glycol mono(meth)acrylate, methoxy polypropylene glycol polybutylene glycol mono(meth)acrylate, methoxy propyethylene glycol polypropylene glycol 10 polybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol mono(meth)acrylate, ethoxypolypropylene glycol mono-(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolypropylene glycol polybutylene glycol 15 mono(meth)acrylate and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate. More ~an one such monomer may be used.
Suitable examples of monomer (b) include acrylic and methacrylic acids and theirmonovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
More than one such monomer may be used.
20 The monomer (c) is a monomer capable of copolymerization with the monomers (a) and (b). Examples of monomer (c) include esters of aliphatic alcohols of 1 to 20carbons with (meth)acrylic acid unsaturated dicarboxylic acids of maleic acid, fumaric acid, citraconic acid, etc., or monoesters or diesters of these acids with aliphatic alcohols of 1 to 20 carbons or glycols of 2 to 4 carbons, or polyalkylene glycols of 25 added mol number 2 to 100 of these glycols, unsaturated amides such as (meth)acrylamide and (meth)acryl alkylamide, vinyl esters such as vinyl acetate and vinyl propionate, aromatic vinyls such as styrene, unsaturated sulfonates such as vinyl sulfonates, (meth)allylsulfonic acid, sulfoethyl(meth)acrylate, 2-(meth)-acrylamido-2-methylpropane sulfonic acid and styrene sulfonate, and their 30 monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
.
2~2~2~
More than one such monomer may be used.
Examples of the monomer (d) ~nclude alkoxypolylkylene glycol mono(meth)allyl ether, e.g., polyethylene glycol mono(meth)allyl ether, polypropylene glycol mono(meth)allyl ether, polyethylene glycol polypropylene glycol mono(meth)allyl 5 ether, polyethylene glycol polybutylene glycol mono(meth)allyl ether, polypropylene glycol polybuthylene glycol mono(meth)allyl ether, polyethylene glycol polypropylene glycol polybutylene glycol mono(meth)allyl ether, methoxypolyethylene glycol mono(meth)allyl ether, methoxypolypropylene glycol mono(meth)allyl ether, methoxypolybutylene glycol mono(meth)allyl ether, methoxypolyethylene glycol 10 polypropylene glycol mono(meth)allyl ether, methoxypolyethylene glycol polybutylene glycol mono(meth)allyl ether, methoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)allyl ether, ethoxypolyethylene glycol mono(meth)allyl ether, ethoxypolypropylene glycol mono(meth)allyl ether, ethoxypolybutylene glycol mono(meth)allyl ether, ethoxypolybutylene glycol 15 mono(meth)allyl ether, ethoxypolyethylene glycol polypropylene glycol mono(meth)allyl ether, ethoxypolyethylene glycol polybutylene glycol mono(meth)ally ether, ethoxypolypropylene glycol polybutylene glycol mono(meth)allyl ether, andethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)allyl ether, and an alkoxypolyalkylene glycol monocrotyl ether, polyethylene glycol 20 monocrotyl ether, polyethylene glycol monocrotyl ether, polypropylene glycol monocrotyl ether, polybutylene glycol monocrotyl ether, polyethylene glycol polypropylene glycol monocrotyl ether, polyethylene glycol polybutylene glycol monocrotyl ether, polypropalene glycol polybutylene glycol monocrotyl ether, polyethylene glycol polypropylene glycol polybutylene glycol monocrotyl ether, 25 methoxypolyethylene glycol monocrotyl ether, methoxypolypropylene glycol monocrotyl ether, methoxybutylene glycol monocrotyl ether, methoxypolyethylene glycol polypropylene glycol monocrotyl ether, methoxpolyethylene glycol polybutylene glycol monocrotyl ether, methoxypolypropylene glycol polybutylene glycol monocrotyl ether, methoxypolyethylene glycol polypropylene glycol 30 polybutylene glycol monocrotyl ether, ethoxypolyethylene glycol monocrotyl ether, ethoxypolypropylene glycol monocrotyl ether, ethoxypolypropylene glycol monocrotyl - ~25~2 ether, ethoxypolybutylene glycol monocrotyl ether, et~oxypolybutylene glycol monocrotyl ether, ethoxypolyethylene glycol polypropylene glycol monocrotyl ether, ethoxypolye~ylene glycol polybutylene glycol monocrotyl ether, ethoxypolypropylene glycol polybutylene glycol monocrotyl ether, ethoxypolypropylene glycol polybutylene glycol monocrotyl ether, and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol monocrotyl ether. More than one of these monomers maybe used.
Examples of the monomer (e) include an unsaturated monocarboxylic acid and monovalent metal salt, divalent metal salt, ammonium salt and an organic amine salt thereof, e.g. acrylic acid and methacylic acid; an unsaturated dicarboxylic acid and monovalent metal salt, divalent metal salt, ammonium salt, an organic amine salt and anhydride thereof, e.g., maleic acid, fumaric acid, citraconic acid and itaconic acid; or a monoester of these acids with an aliphatic alcohol having 1 to 20 carbon atoms or glycol having 2 to 4 carbon atoms or a polyalkylene glycol having 2 to 100 mols of these glycols. More than one of these monomers may be used.
Examples of the monomer (f) include ester of an aliphatic alcohol having 1 to 20carbon atoms and acrylic acid, and a diester of an unsaturated dicarboxylic acid such as maleic acid, fumaric acid and citraconic acid acids with an aliphatic alcohol having 1 to 20 carbon atoms or glycol having 2 to 4 carbon atoms or a polylkylene glycol having 2 to 4 carbon atoms or a polyalkylene glycol having 1 to 10~ mols of these glycols; an unsaturated amide such as (meth)acrylamide and (meth)acryl alkylamide, a vinyl ester such as vinyl acetate and vinyl propionate; an aromatic vinyl such as styrene; an unsaturated sulfonic acid such as vinyl sulfonic acid, (meth)allyl sulfonic acid, sulfoethyl (meth)acrylate, 2-~meth)acrylamide-2-methylpropane sulfonic acid and styrene sulfonic acid and monovalent metal salt, divalent metal salt, ammonium salt and an organic amine salt thereof. More than one of these monomers may be used.
The monomer (g) may be an unsaturated hydrocarbon having 2 to 12 carbon atoms, and examples of the monomer (g) include ethylene, propylene, 1-butene, 2-butene,isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexane, 2-methyl-1-pentene, . . . - . . . ~ . .. . . . .
212~21 3-methyl-1-pentene, ~methyl-1-pentene, 2~thyl-1-butene, diisobutylene, 1,~
butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 2-me~yl-~dimethyl-1-pentene, 2-methyl-4-dimethyl-2-pentene. Isobutylene also means spent BB containing isobutylene. Preferably a-olefin having 2 to 8 carbon atoms, especially a-olefin having 5 4 to 5 carbon atoms is used. More than one kind of these monomers may be used.
Examples of the monomer (h) include maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride,. Maleic anhydride is the preferred monomer bècause of its reactivity, quality and lower cost. More than one such monomer may be used.
10 Examples of the monomer (i) include (meth)acrylic acid and monovalent metal salt, divalent metal salt, ammonium salt, and an organic amine salt thereof; an ester of an aliphatic alcohol having 1 to 20 carbon atoms with (meth)acrylic acid; an unsaturated dicarboxylic acid such as maleic acid, fumaric acid and citraconic acid, and mono- or diester of these acids with an aliphatic alcohol having 1 to 20 carbon atoms or glycol having 2 to 4 carbon atoms or a polyalkylene glycol having 2 to 100 mols of these glycols; unsaturated amide such as (meth)acrylamide and (meth)acryl alkylamide; a vinyl ester such as vinyl acetate and vinyl propionate; an aromatic vinyl such as styrene; an unsaturated sulfonic acid such as vinyl sulfonic acid, (meth)allyl sulfonic acid, sulfoethyl (meth)acIylate, 2-(meth)acrylamide-2-methylpropane sulfonic acid and 20 styrene sulfonic acid and monovalent metal salt, divalent metal salt, ammonium salt, and an organic amine salt thereof. More than one such monomer may be used.
Examples of suitable defoaming agents include polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene (poly)oxyalkylene alkyl ethers such as diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl 25 ether, polyoxyethylene polyoxypropylene-2-ethyl hexyl ether, and oxyethylene oxypropylene adducts of high alcohols of 12 to 14 carbons; polyoxyalkylene (alkyl)aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether; acetylene ethers of alkylene oxide additional polymerized with acetylene alcohols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 2,5-d~methyl-3-hexyn-154^0244 10 212~21 acetylene alcohols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 2,5-dimethyl-3-hexyn-2,5-diol, 3-methyl-1-butyn-3-ol; (poly)oxyalkylene aliphatic acid esters such asdiethylene glycol oleic acid ester and ethylene glycol distearic acid ester;
(poly)oxyalkylene sorbitan aliphatic acid esters such as polyoxyethylene sorbitan 5 monolauric acid ester, and polyoxyethylene sorbitan trioleic acid ester;
(poly)oxyalkylene alkyl (aryl)ether sulfuric acid esters such as polyoxypropylene methyl ester sodium sulfate and polyoxyethylene dodecyl phenol ether sodium sulfate; (poly)oxyalkylene alkyl phosphates such as (poly)oxye~ylene stearyl phosphates; and (poly)oxyalkylene alkylamines such as polyoxyethylene laurylamine.
10 More than one kind of these may be used.
The copolymer (A) is obtained by polymerization of a monomer mixture containing an unsaturated carboxylic acid base monomer as hereinabove described. As previously mentioned, this is preferably carried out in the presence of the defoaming agent. The proportion of the unsaturated carboxylic acid base monomer in the 15 mixture is from 2 to 95% by weight; it is essential that this range be adhered to, otherwise the advantages of the present invention are not given. The proportion is preferably from 2 to 95% by weight, and more preferably from 3-50% in the cases of (a),(b),(c) and (c),~d),(e), and from 30-90% in the case of (g),(h),(i).
To manufacture the copolymer (A), the abovementioned monomer mixture is 20 copolymerized in, when required, the presence of the abovementioned defoamingagent using a polymerization initiator. The quantity of defoaming agent to be used is in the range of 0.01 to 10 weight percent of the monomer mixture, preferably 0.05 to 5 weight percent. When less than 0.01 weight percent of defoaming agent is used, adjustment of entrained air content of the cement mixture is difficult and a cement 25 mixture of stable strength cannot be obtained. When the quantity of defoaming agent used exceeds 10 weight percent, the performance of the admixture obtained is reduced and a cement mixture of good fluidity cannot be obtained.
The copolymer (A) may be synthesised by known methods such as solution polymerization or bulk polymerization.
~ 12~ '32 i54-0244 1 1 polymerization or bulk polymerization.
Solution polymerization may be done by a batch or a continuous process. Solventswhich may be used include water, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic or aliphatic hydrocarbons such as benzene, toluene, 5 xylene, cyclohexane, and n-hexane and ketone compounds such as acetone and methyl ethyl ketone. For solubility of both the monomers and the resultant copolymer (A), it is desirable to use at least 1 solvent selected from the groupconsisting of water and lower alcohols of 1 to 4 carbon atoms. Methyl, ethyl andisopropyl alcohols are especially effective alcohols.
10 When the polymerization is carried out in an aqueous liquid, water-soluble polymerization initiators such as ammonium persulfate, sodium persulfate, hydrogen peroxide and azoamidine compounds such as azobis-2-methyl propionamide hydrochloric acid salt may be used. Accelerators such as sodium hydrogen sulfitemay be used in combination with these initiators. Further, in polymerization with 15 a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester compound or a ketone compound as the solvent, peroxides such as benzoyl peroxideand lauroy] peroxide; hydroperoxides such as cumene hydroperoxide; and azo compounds such as 2,2'-azo-bis-isobutyronitrile may be used as polymerization initiators. In this case, it is possible to use accelerators such as amine compounds in 20 combination. Further, in the event of using a water-lower alcohol solvent mixture, one of the various polymerization initiators or combinations of polymerization initiator and accelerator may be selected as suited and used. The polymerizationtemperature may be selected as required according to the solvent and polymerization initiator, but normally, the polymerization is carried out in the range of 0 to 120C.
25 Bulk polymerization is carried out using peroxides such as benzoyl peroxide and lauroyl peroxide, hydroperoxides such as cumene hydroperoxide and aliphatic azo compounds such as 2,2'-azo-bis-isobutyronitrile as polymerization initiators and in a temperatures range of 50 to 200C.
;
~2~21 The copolymer (A) obtained in this manner can be used as prepared as the main ingredient of a fluidity-controlling admixture according to the invention. The copolymer (B) obtained by further neutralizing copolymer (A) with an alkaline substance as necessary may also be thus used, as may a crosslinked copolymer (C).
5 Alkaline substances particularly suitable for neutralisation include hydroxides of monovalent metals and divalent metals, inorganic salts of sulfates and carbonates ammonia and organic amines.
Further, although the cross-linking agent may be selected from any suitable crosslinked agent capable of reactions with a functional group such as carboxyl 10 group, hydroxyl group, amino group, sulfonic acid group, etc. contained in the copolymer (A), a cross-linking agent which has at least one divalent group designated by the following general formula (V) tRS-¢-O-R6~
wherein Rs and R6 are independently selected from the group consisting of -CH2-, -CH-, ~ , -C- and -CH2CH-, wherein R6 is OH
I
-CH2CH-~
,.. ,.. ,.. ,,.. ,; .. ,.,. ,, j . . ~ .
2 ~ 2 ~ ;3 2 1 Rs may be unnecessary, and R7 and R8 are independently alkyl group of 1 to 5 carbon atoms, as a structural unit and/or can be formed is preferable. Examples of these cross-linking agents include polyvalent glycidyl compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, 5 diglycerol diglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcin diglycidyl ether, 1,~hexanediol diglycidyl ether, adipic acid diglycidyl ester, s-phtalic acid diglycidyl ester, etc. :
It is desirable that the weight average molecular weight (hereinafter ''Mw'') of10 copolymer (A) (either as such or as the raw material of copolymer (C)) and copolymer (B) lie in the range of 500 to 500,000. When the monomer mixture comprises monomers (a), (b) and (c), M~, lies preferably in the range of 5,000-500,000, when the mixture comprises monomers (d), (e) and (f) or monomers (g), (h) and (i), it lies preferably in the range 500-100,000. If M,~ is less than 500, the water-reducing15 capability and slump loss prevention capability of the cement dispersing agent are reduced. When M,~ exceeds 500,000, the water-reducing capability of the cement dispersing agent is reduced.
The copolymer (A) and/or the copolymer (B) and/or the crosslinked copolymer (C) may be used as a cement dispersing agent in an admixture according to the invention 20 in the form of an aqueous solution or an aqueous emulsion and the air-entraining property in a cementitious mixture such as concrete may be adjusted arbitrarily by suitably adjusting the variety and/or dosage of the defoaming agent used. Further, with (A) and/or (B) and/or (C) as main ingredient, it is permissible to use the admixture according to the invention in combination with another known admixtures.
25 Examples of such cement admixtures include conventional cement dispersing agents, air-entraining agents, cement wetting agents, expansion agents, waterproofing agents, retarding agents, quick-setting agents, water-soluble polymeric substances, thickeners, coagulants, drying shrinkage reducing agents, strength increasing agents and hardening accelerators.
21 2 ~
The admixture of the invention may be used with hydraulic cements such as portland cement, high alumina cement and various blended cements or hydraulic materials other than cement, such as gypsum.
The admixture of this invention gives excellent performance even when relatively5 small quantities compared with conventional dispersing agents are used For example, when used in mortars or concretes containing hydraulic cement, quantities used are typically from 0.01 to 1.0%, preferably from 0.02 to 0.5% by weight of cement.
Various desirable effects such as increase in slump, reduction in unit water content, increase in strength and improvement in durability are brought about by such 10 addition. With less than 0.01% addition, the performance is inadequate, whereas, when a large quantity in excess of 1.0% is used, the results are no better and costs more. It has the additional advantage of long shelf stability.
The invention therefore also provides a process of modifying the fluidity of a cementitious composition, comprising the incorporation into the composition of an 15 admixture as hereinabove described. The use of an admixture as hereinabove described to modify the fluidity of a cementitious composition is also provided.
The invention is further described with reference to the following examples. In the examples, unless otherwise stated, "percent" and "part" shall indicate "weight percent"
and "part by weight" respectively.
20 Example 1 for manufacturing Admixture No. 1 1695 parts of water is introduced in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen whilestirring and heating to 95C is carried out under a nitrogen atmosphere. An aqueous 25 solution of monomer comprising 750 parts of methoxy polyethylene glycol monomethacrylate (average mol addition number of ethylene oxide, 10), 250 parts of 212~
methacrylic acid, 7 parts of "Pluronic" (trade mark) L-64 (polyoxyethylene-polyoxypropylene adduct manufactured by Asahi Denka Kogyo KK) as oxyalkylene base defoaming agent, and 1500 parts of water, and 672 parts of a 5% ammonium persulfate aqueous solution is then drip-fed for 4 hours, and after completion of 5 dropping, 168 parts of 5% ammonium persulfate is further drip-fed for 1 hour. The temperature is then maintained at 95C for 1 hour to complete the polymerizationreaction. An admixture of the present ~nvention comprising an aqueous solution of a copolymer of Mw 35,000 is obtained.
Examples 2 to 5 for Manufacturing AdmLxtures Nos. (2) to (5).
10 Admixtures (2) to (5) of the present invention comprising ~e copolymer (A) manufactured by operations similar to those in Example 1 are summarized in Tables 1 and 2.
Example 6 for manufacturing Admixture No. 6.
349.6 parts of water, 1648 parts of polyethylene glycol monoallyl ether (average mol 15 addition number of ethylene oxide, 5) and 23.2 parts of oxyethylene oxypropylene adduct to C,2-CI4 alcohols as oxyalkylene base defoaming agent in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen while stirring, and heating was carried out to 95C under a20 nitrogen atmosphere. A monomer/polymerization initiator mixture aqueous solution comprising 687 parts of maleic acid, 1030 parts of water and 57.2 parts of 5%
amrnonium persulfate aqueous solution is then drip-fed for 2 hours, and after completion of dropping, 527 parts of 5% ammonium persulfate aqueous solution is dropped for 1 hour. The temperature is then maintained at 95C to complete the 25 polymerization reaction. The result is an admixture (6) of the present invention comprising an aqueous solution of a copolymer of average molecular weight of 6,000.
Example 7 for manufacturing Admixture (7) :
-~ 212~a21 Admixture (7) of the present invention is obtained by drip-feeding 185 parts of 50%
NaOH aqueous solution into the admixture (1) obtained in Example 1, this bringing it to pH 8.
Examples 8 to 21 for manufacturing Admixtures Nos. (8)-(21). -Admixhlres (8) to (21) comprising the copolymer (B) of the present invention obtained in a similar method to Example 7 are summarized in Tables 3 and 4.
Examples 22 for manufacturing Admixture No. (22) 5000 parts of 20% admixture aqueous solution (solids content: 1000 parts) obtained in Example 1 is introduced into a glass Teaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, and heating to 95C is carried out.35 parts of ~phthalic acid diglycidyl ester is then added. The temperature is maintained at 95C for 3 hours to complete the cross-linking reaction and the result is admixture (22) comprising a cross-linked copolymer aqueous solution.
Examples 23 to 25 for manufacturing Admixtures No. (23) to (25).
Admixtures Nos. (23) to (25) of the present invention comprising the cross-linked copolymer (C) of the present invention manufactured by a similar method to Example 22 are summarized in Table 5.
Example 26 for manufacturing Admixture No. (26) 420 Parts of l-hexane, 490 parts of maleic anhydride, 9.1 parts of oxyethylene oxypropylene adduct of C12-C14 alcohols, 27 parts of azobisisobutylonitrile and 2730 parts of toluene are introduced in a glass reaction vessel equipped with a ~:
thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, and ~e interior is purged with nitrogen under stirring. After reacting at 80C for 7 hours under nitrogen atmoThere, and precipitated while polymer was .; ~ . . , - , i ., . ;. . . . :, -.
2~2~21 collected and dried. 2500 Parts of 10% aqueous sodium hydroxide solution is added into 6~4 parts of the copolymer thus obtained and heated at 90C under stirring to obtain an admixture (26) of the present invention comprising a copolymer of average molecular weight of 6100.
Examples 27 to 28 for manufacturing Admixtures Nos. (27) to (28) Admixtures (27) to (28) of the present invention comprising the copolymer (B) of the present invention manufactured by a similar method to Example 26 are summarized in Table 6.
2~2~
18 Case 154-0244 Table 1 _ =~
_. _ _ Admixture ~nsaturated E~ample No. charged carbo~ylic other monomer other mo~omer solvent aGid ba~e mono~er 1 ~ t~r ~ ~ __ _ ¦
2 j (2) ¦water [1695.0~ ¦AA t200.0]PEGMA (n_~5) 1 3 ~ ¦Water [1315.0] jMAA ~250.0] ¦ [740.0] =cthaorylate _ , . _ _ _ _ _ r 4 (4) uatar [1S95.0~ MA~ 1300.0] [I00.0]
More than one such monomer may be used.
Examples of the monomer (d) ~nclude alkoxypolylkylene glycol mono(meth)allyl ether, e.g., polyethylene glycol mono(meth)allyl ether, polypropylene glycol mono(meth)allyl ether, polyethylene glycol polypropylene glycol mono(meth)allyl 5 ether, polyethylene glycol polybutylene glycol mono(meth)allyl ether, polypropylene glycol polybuthylene glycol mono(meth)allyl ether, polyethylene glycol polypropylene glycol polybutylene glycol mono(meth)allyl ether, methoxypolyethylene glycol mono(meth)allyl ether, methoxypolypropylene glycol mono(meth)allyl ether, methoxypolybutylene glycol mono(meth)allyl ether, methoxypolyethylene glycol 10 polypropylene glycol mono(meth)allyl ether, methoxypolyethylene glycol polybutylene glycol mono(meth)allyl ether, methoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)allyl ether, ethoxypolyethylene glycol mono(meth)allyl ether, ethoxypolypropylene glycol mono(meth)allyl ether, ethoxypolybutylene glycol mono(meth)allyl ether, ethoxypolybutylene glycol 15 mono(meth)allyl ether, ethoxypolyethylene glycol polypropylene glycol mono(meth)allyl ether, ethoxypolyethylene glycol polybutylene glycol mono(meth)ally ether, ethoxypolypropylene glycol polybutylene glycol mono(meth)allyl ether, andethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)allyl ether, and an alkoxypolyalkylene glycol monocrotyl ether, polyethylene glycol 20 monocrotyl ether, polyethylene glycol monocrotyl ether, polypropylene glycol monocrotyl ether, polybutylene glycol monocrotyl ether, polyethylene glycol polypropylene glycol monocrotyl ether, polyethylene glycol polybutylene glycol monocrotyl ether, polypropalene glycol polybutylene glycol monocrotyl ether, polyethylene glycol polypropylene glycol polybutylene glycol monocrotyl ether, 25 methoxypolyethylene glycol monocrotyl ether, methoxypolypropylene glycol monocrotyl ether, methoxybutylene glycol monocrotyl ether, methoxypolyethylene glycol polypropylene glycol monocrotyl ether, methoxpolyethylene glycol polybutylene glycol monocrotyl ether, methoxypolypropylene glycol polybutylene glycol monocrotyl ether, methoxypolyethylene glycol polypropylene glycol 30 polybutylene glycol monocrotyl ether, ethoxypolyethylene glycol monocrotyl ether, ethoxypolypropylene glycol monocrotyl ether, ethoxypolypropylene glycol monocrotyl - ~25~2 ether, ethoxypolybutylene glycol monocrotyl ether, et~oxypolybutylene glycol monocrotyl ether, ethoxypolyethylene glycol polypropylene glycol monocrotyl ether, ethoxypolye~ylene glycol polybutylene glycol monocrotyl ether, ethoxypolypropylene glycol polybutylene glycol monocrotyl ether, ethoxypolypropylene glycol polybutylene glycol monocrotyl ether, and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol monocrotyl ether. More than one of these monomers maybe used.
Examples of the monomer (e) include an unsaturated monocarboxylic acid and monovalent metal salt, divalent metal salt, ammonium salt and an organic amine salt thereof, e.g. acrylic acid and methacylic acid; an unsaturated dicarboxylic acid and monovalent metal salt, divalent metal salt, ammonium salt, an organic amine salt and anhydride thereof, e.g., maleic acid, fumaric acid, citraconic acid and itaconic acid; or a monoester of these acids with an aliphatic alcohol having 1 to 20 carbon atoms or glycol having 2 to 4 carbon atoms or a polyalkylene glycol having 2 to 100 mols of these glycols. More than one of these monomers may be used.
Examples of the monomer (f) include ester of an aliphatic alcohol having 1 to 20carbon atoms and acrylic acid, and a diester of an unsaturated dicarboxylic acid such as maleic acid, fumaric acid and citraconic acid acids with an aliphatic alcohol having 1 to 20 carbon atoms or glycol having 2 to 4 carbon atoms or a polylkylene glycol having 2 to 4 carbon atoms or a polyalkylene glycol having 1 to 10~ mols of these glycols; an unsaturated amide such as (meth)acrylamide and (meth)acryl alkylamide, a vinyl ester such as vinyl acetate and vinyl propionate; an aromatic vinyl such as styrene; an unsaturated sulfonic acid such as vinyl sulfonic acid, (meth)allyl sulfonic acid, sulfoethyl (meth)acrylate, 2-~meth)acrylamide-2-methylpropane sulfonic acid and styrene sulfonic acid and monovalent metal salt, divalent metal salt, ammonium salt and an organic amine salt thereof. More than one of these monomers may be used.
The monomer (g) may be an unsaturated hydrocarbon having 2 to 12 carbon atoms, and examples of the monomer (g) include ethylene, propylene, 1-butene, 2-butene,isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexane, 2-methyl-1-pentene, . . . - . . . ~ . .. . . . .
212~21 3-methyl-1-pentene, ~methyl-1-pentene, 2~thyl-1-butene, diisobutylene, 1,~
butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 2-me~yl-~dimethyl-1-pentene, 2-methyl-4-dimethyl-2-pentene. Isobutylene also means spent BB containing isobutylene. Preferably a-olefin having 2 to 8 carbon atoms, especially a-olefin having 5 4 to 5 carbon atoms is used. More than one kind of these monomers may be used.
Examples of the monomer (h) include maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride,. Maleic anhydride is the preferred monomer bècause of its reactivity, quality and lower cost. More than one such monomer may be used.
10 Examples of the monomer (i) include (meth)acrylic acid and monovalent metal salt, divalent metal salt, ammonium salt, and an organic amine salt thereof; an ester of an aliphatic alcohol having 1 to 20 carbon atoms with (meth)acrylic acid; an unsaturated dicarboxylic acid such as maleic acid, fumaric acid and citraconic acid, and mono- or diester of these acids with an aliphatic alcohol having 1 to 20 carbon atoms or glycol having 2 to 4 carbon atoms or a polyalkylene glycol having 2 to 100 mols of these glycols; unsaturated amide such as (meth)acrylamide and (meth)acryl alkylamide; a vinyl ester such as vinyl acetate and vinyl propionate; an aromatic vinyl such as styrene; an unsaturated sulfonic acid such as vinyl sulfonic acid, (meth)allyl sulfonic acid, sulfoethyl (meth)acIylate, 2-(meth)acrylamide-2-methylpropane sulfonic acid and 20 styrene sulfonic acid and monovalent metal salt, divalent metal salt, ammonium salt, and an organic amine salt thereof. More than one such monomer may be used.
Examples of suitable defoaming agents include polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene (poly)oxyalkylene alkyl ethers such as diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl 25 ether, polyoxyethylene polyoxypropylene-2-ethyl hexyl ether, and oxyethylene oxypropylene adducts of high alcohols of 12 to 14 carbons; polyoxyalkylene (alkyl)aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether; acetylene ethers of alkylene oxide additional polymerized with acetylene alcohols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 2,5-d~methyl-3-hexyn-154^0244 10 212~21 acetylene alcohols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 2,5-dimethyl-3-hexyn-2,5-diol, 3-methyl-1-butyn-3-ol; (poly)oxyalkylene aliphatic acid esters such asdiethylene glycol oleic acid ester and ethylene glycol distearic acid ester;
(poly)oxyalkylene sorbitan aliphatic acid esters such as polyoxyethylene sorbitan 5 monolauric acid ester, and polyoxyethylene sorbitan trioleic acid ester;
(poly)oxyalkylene alkyl (aryl)ether sulfuric acid esters such as polyoxypropylene methyl ester sodium sulfate and polyoxyethylene dodecyl phenol ether sodium sulfate; (poly)oxyalkylene alkyl phosphates such as (poly)oxye~ylene stearyl phosphates; and (poly)oxyalkylene alkylamines such as polyoxyethylene laurylamine.
10 More than one kind of these may be used.
The copolymer (A) is obtained by polymerization of a monomer mixture containing an unsaturated carboxylic acid base monomer as hereinabove described. As previously mentioned, this is preferably carried out in the presence of the defoaming agent. The proportion of the unsaturated carboxylic acid base monomer in the 15 mixture is from 2 to 95% by weight; it is essential that this range be adhered to, otherwise the advantages of the present invention are not given. The proportion is preferably from 2 to 95% by weight, and more preferably from 3-50% in the cases of (a),(b),(c) and (c),~d),(e), and from 30-90% in the case of (g),(h),(i).
To manufacture the copolymer (A), the abovementioned monomer mixture is 20 copolymerized in, when required, the presence of the abovementioned defoamingagent using a polymerization initiator. The quantity of defoaming agent to be used is in the range of 0.01 to 10 weight percent of the monomer mixture, preferably 0.05 to 5 weight percent. When less than 0.01 weight percent of defoaming agent is used, adjustment of entrained air content of the cement mixture is difficult and a cement 25 mixture of stable strength cannot be obtained. When the quantity of defoaming agent used exceeds 10 weight percent, the performance of the admixture obtained is reduced and a cement mixture of good fluidity cannot be obtained.
The copolymer (A) may be synthesised by known methods such as solution polymerization or bulk polymerization.
~ 12~ '32 i54-0244 1 1 polymerization or bulk polymerization.
Solution polymerization may be done by a batch or a continuous process. Solventswhich may be used include water, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic or aliphatic hydrocarbons such as benzene, toluene, 5 xylene, cyclohexane, and n-hexane and ketone compounds such as acetone and methyl ethyl ketone. For solubility of both the monomers and the resultant copolymer (A), it is desirable to use at least 1 solvent selected from the groupconsisting of water and lower alcohols of 1 to 4 carbon atoms. Methyl, ethyl andisopropyl alcohols are especially effective alcohols.
10 When the polymerization is carried out in an aqueous liquid, water-soluble polymerization initiators such as ammonium persulfate, sodium persulfate, hydrogen peroxide and azoamidine compounds such as azobis-2-methyl propionamide hydrochloric acid salt may be used. Accelerators such as sodium hydrogen sulfitemay be used in combination with these initiators. Further, in polymerization with 15 a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester compound or a ketone compound as the solvent, peroxides such as benzoyl peroxideand lauroy] peroxide; hydroperoxides such as cumene hydroperoxide; and azo compounds such as 2,2'-azo-bis-isobutyronitrile may be used as polymerization initiators. In this case, it is possible to use accelerators such as amine compounds in 20 combination. Further, in the event of using a water-lower alcohol solvent mixture, one of the various polymerization initiators or combinations of polymerization initiator and accelerator may be selected as suited and used. The polymerizationtemperature may be selected as required according to the solvent and polymerization initiator, but normally, the polymerization is carried out in the range of 0 to 120C.
25 Bulk polymerization is carried out using peroxides such as benzoyl peroxide and lauroyl peroxide, hydroperoxides such as cumene hydroperoxide and aliphatic azo compounds such as 2,2'-azo-bis-isobutyronitrile as polymerization initiators and in a temperatures range of 50 to 200C.
;
~2~21 The copolymer (A) obtained in this manner can be used as prepared as the main ingredient of a fluidity-controlling admixture according to the invention. The copolymer (B) obtained by further neutralizing copolymer (A) with an alkaline substance as necessary may also be thus used, as may a crosslinked copolymer (C).
5 Alkaline substances particularly suitable for neutralisation include hydroxides of monovalent metals and divalent metals, inorganic salts of sulfates and carbonates ammonia and organic amines.
Further, although the cross-linking agent may be selected from any suitable crosslinked agent capable of reactions with a functional group such as carboxyl 10 group, hydroxyl group, amino group, sulfonic acid group, etc. contained in the copolymer (A), a cross-linking agent which has at least one divalent group designated by the following general formula (V) tRS-¢-O-R6~
wherein Rs and R6 are independently selected from the group consisting of -CH2-, -CH-, ~ , -C- and -CH2CH-, wherein R6 is OH
I
-CH2CH-~
,.. ,.. ,.. ,,.. ,; .. ,.,. ,, j . . ~ .
2 ~ 2 ~ ;3 2 1 Rs may be unnecessary, and R7 and R8 are independently alkyl group of 1 to 5 carbon atoms, as a structural unit and/or can be formed is preferable. Examples of these cross-linking agents include polyvalent glycidyl compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, 5 diglycerol diglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcin diglycidyl ether, 1,~hexanediol diglycidyl ether, adipic acid diglycidyl ester, s-phtalic acid diglycidyl ester, etc. :
It is desirable that the weight average molecular weight (hereinafter ''Mw'') of10 copolymer (A) (either as such or as the raw material of copolymer (C)) and copolymer (B) lie in the range of 500 to 500,000. When the monomer mixture comprises monomers (a), (b) and (c), M~, lies preferably in the range of 5,000-500,000, when the mixture comprises monomers (d), (e) and (f) or monomers (g), (h) and (i), it lies preferably in the range 500-100,000. If M,~ is less than 500, the water-reducing15 capability and slump loss prevention capability of the cement dispersing agent are reduced. When M,~ exceeds 500,000, the water-reducing capability of the cement dispersing agent is reduced.
The copolymer (A) and/or the copolymer (B) and/or the crosslinked copolymer (C) may be used as a cement dispersing agent in an admixture according to the invention 20 in the form of an aqueous solution or an aqueous emulsion and the air-entraining property in a cementitious mixture such as concrete may be adjusted arbitrarily by suitably adjusting the variety and/or dosage of the defoaming agent used. Further, with (A) and/or (B) and/or (C) as main ingredient, it is permissible to use the admixture according to the invention in combination with another known admixtures.
25 Examples of such cement admixtures include conventional cement dispersing agents, air-entraining agents, cement wetting agents, expansion agents, waterproofing agents, retarding agents, quick-setting agents, water-soluble polymeric substances, thickeners, coagulants, drying shrinkage reducing agents, strength increasing agents and hardening accelerators.
21 2 ~
The admixture of the invention may be used with hydraulic cements such as portland cement, high alumina cement and various blended cements or hydraulic materials other than cement, such as gypsum.
The admixture of this invention gives excellent performance even when relatively5 small quantities compared with conventional dispersing agents are used For example, when used in mortars or concretes containing hydraulic cement, quantities used are typically from 0.01 to 1.0%, preferably from 0.02 to 0.5% by weight of cement.
Various desirable effects such as increase in slump, reduction in unit water content, increase in strength and improvement in durability are brought about by such 10 addition. With less than 0.01% addition, the performance is inadequate, whereas, when a large quantity in excess of 1.0% is used, the results are no better and costs more. It has the additional advantage of long shelf stability.
The invention therefore also provides a process of modifying the fluidity of a cementitious composition, comprising the incorporation into the composition of an 15 admixture as hereinabove described. The use of an admixture as hereinabove described to modify the fluidity of a cementitious composition is also provided.
The invention is further described with reference to the following examples. In the examples, unless otherwise stated, "percent" and "part" shall indicate "weight percent"
and "part by weight" respectively.
20 Example 1 for manufacturing Admixture No. 1 1695 parts of water is introduced in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen whilestirring and heating to 95C is carried out under a nitrogen atmosphere. An aqueous 25 solution of monomer comprising 750 parts of methoxy polyethylene glycol monomethacrylate (average mol addition number of ethylene oxide, 10), 250 parts of 212~
methacrylic acid, 7 parts of "Pluronic" (trade mark) L-64 (polyoxyethylene-polyoxypropylene adduct manufactured by Asahi Denka Kogyo KK) as oxyalkylene base defoaming agent, and 1500 parts of water, and 672 parts of a 5% ammonium persulfate aqueous solution is then drip-fed for 4 hours, and after completion of 5 dropping, 168 parts of 5% ammonium persulfate is further drip-fed for 1 hour. The temperature is then maintained at 95C for 1 hour to complete the polymerizationreaction. An admixture of the present ~nvention comprising an aqueous solution of a copolymer of Mw 35,000 is obtained.
Examples 2 to 5 for Manufacturing AdmLxtures Nos. (2) to (5).
10 Admixtures (2) to (5) of the present invention comprising ~e copolymer (A) manufactured by operations similar to those in Example 1 are summarized in Tables 1 and 2.
Example 6 for manufacturing Admixture No. 6.
349.6 parts of water, 1648 parts of polyethylene glycol monoallyl ether (average mol 15 addition number of ethylene oxide, 5) and 23.2 parts of oxyethylene oxypropylene adduct to C,2-CI4 alcohols as oxyalkylene base defoaming agent in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen while stirring, and heating was carried out to 95C under a20 nitrogen atmosphere. A monomer/polymerization initiator mixture aqueous solution comprising 687 parts of maleic acid, 1030 parts of water and 57.2 parts of 5%
amrnonium persulfate aqueous solution is then drip-fed for 2 hours, and after completion of dropping, 527 parts of 5% ammonium persulfate aqueous solution is dropped for 1 hour. The temperature is then maintained at 95C to complete the 25 polymerization reaction. The result is an admixture (6) of the present invention comprising an aqueous solution of a copolymer of average molecular weight of 6,000.
Example 7 for manufacturing Admixture (7) :
-~ 212~a21 Admixture (7) of the present invention is obtained by drip-feeding 185 parts of 50%
NaOH aqueous solution into the admixture (1) obtained in Example 1, this bringing it to pH 8.
Examples 8 to 21 for manufacturing Admixtures Nos. (8)-(21). -Admixhlres (8) to (21) comprising the copolymer (B) of the present invention obtained in a similar method to Example 7 are summarized in Tables 3 and 4.
Examples 22 for manufacturing Admixture No. (22) 5000 parts of 20% admixture aqueous solution (solids content: 1000 parts) obtained in Example 1 is introduced into a glass Teaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, and heating to 95C is carried out.35 parts of ~phthalic acid diglycidyl ester is then added. The temperature is maintained at 95C for 3 hours to complete the cross-linking reaction and the result is admixture (22) comprising a cross-linked copolymer aqueous solution.
Examples 23 to 25 for manufacturing Admixtures No. (23) to (25).
Admixtures Nos. (23) to (25) of the present invention comprising the cross-linked copolymer (C) of the present invention manufactured by a similar method to Example 22 are summarized in Table 5.
Example 26 for manufacturing Admixture No. (26) 420 Parts of l-hexane, 490 parts of maleic anhydride, 9.1 parts of oxyethylene oxypropylene adduct of C12-C14 alcohols, 27 parts of azobisisobutylonitrile and 2730 parts of toluene are introduced in a glass reaction vessel equipped with a ~:
thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, and ~e interior is purged with nitrogen under stirring. After reacting at 80C for 7 hours under nitrogen atmoThere, and precipitated while polymer was .; ~ . . , - , i ., . ;. . . . :, -.
2~2~21 collected and dried. 2500 Parts of 10% aqueous sodium hydroxide solution is added into 6~4 parts of the copolymer thus obtained and heated at 90C under stirring to obtain an admixture (26) of the present invention comprising a copolymer of average molecular weight of 6100.
Examples 27 to 28 for manufacturing Admixtures Nos. (27) to (28) Admixtures (27) to (28) of the present invention comprising the copolymer (B) of the present invention manufactured by a similar method to Example 26 are summarized in Table 6.
2~2~
18 Case 154-0244 Table 1 _ =~
_. _ _ Admixture ~nsaturated E~ample No. charged carbo~ylic other monomer other mo~omer solvent aGid ba~e mono~er 1 ~ t~r ~ ~ __ _ ¦
2 j (2) ¦water [1695.0~ ¦AA t200.0]PEGMA (n_~5) 1 3 ~ ¦Water [1315.0] jMAA ~250.0] ¦ [740.0] =cthaorylate _ , . _ _ _ _ _ r 4 (4) uatar [1S95.0~ MA~ 1300.0] [I00.0]
5 I ~5) ¦water [1800.~] ITEGMM 1369.6~ ,__ 6 (6) water 1349.6~ MA ~687.0~ ~1648.0]
AA msthaor ~lic acld AA : aorylio acld TE~MM : tetraethylene gly~ol monomaleate MA : ~alelc aold MPEGMMA ~ metho~y polyethylene glycol monometbacryiate PEGMA : polyethylene glycol monoaorylate PEGMME : polyethylene glycol monomethallyl ether PEGMAE : polyethyleno glycol monoallyl ether :
" '':
~ ,:
2~2~
19 Case l54-0244 .
Table 2 c~otlon composltion : numerals in brackets are . _ _ part~ by we~h~ reaetlo~ molecular E~ample ~ - temperature weight poly~eri~ation defoaming agent (II)initiator I ~ __ _ 1 Pluronic L-64 a) ammonium persul~ate 9535000 _ l7 ~l l2~ ~1 _ _ .
poly~thylene glyeol a20bls-2-methyl 2 polypropylene glycol propiomidine 8038000 _nonyl phenyl ether I 1 _ ~ . l 3 oxypropylene adduct o~ ammonlum persulrate 9523000 C12 - C14 al¢ohols l40.0]
~ [1.0] , ~__ 4 Surrynol 440 b) ammonium per~uli~aSe 9~ 30000 t7.0~ t20.0]
_ 5 polypropylene glycol ammonlum persulfate 95 10000 L nonyl phenyl ether t15.0~ l _ 6 oryethylene f am~onlum persul~ate 95 6000 :
I C12 - C1~ alcohol~ 1 ~85.8~ l a pDlyo~yethylene poly xypropylsne ~dduct (Asahi Denka K.K.) b) acetylene alcohol polyoxyethylene adduct (Nisshln Xagaku X~gyo K.X.) o) Monomer mlxture i9 added ln 40 % aq~eous solution and polymerlzation ln~t~ator is added in 5 ~ aqueou~ solution.
' ~ `"
.
---` 212~
Case 154-0244 Table 3 . . _ Reaction co~poslt~on: numeralq in bracket~ are parts by ~elght . ~ ~ . _ __ E le Admixture unsaturated xamp No. cbar8ed carbo2ylicother monomer other monomer ~olvent acad base ~onomer __ _ . _ ~ . .
AA msthaor ~lic acld AA : aorylio acld TE~MM : tetraethylene gly~ol monomaleate MA : ~alelc aold MPEGMMA ~ metho~y polyethylene glycol monometbacryiate PEGMA : polyethylene glycol monoaorylate PEGMME : polyethylene glycol monomethallyl ether PEGMAE : polyethyleno glycol monoallyl ether :
" '':
~ ,:
2~2~
19 Case l54-0244 .
Table 2 c~otlon composltion : numerals in brackets are . _ _ part~ by we~h~ reaetlo~ molecular E~ample ~ - temperature weight poly~eri~ation defoaming agent (II)initiator I ~ __ _ 1 Pluronic L-64 a) ammonium persul~ate 9535000 _ l7 ~l l2~ ~1 _ _ .
poly~thylene glyeol a20bls-2-methyl 2 polypropylene glycol propiomidine 8038000 _nonyl phenyl ether I 1 _ ~ . l 3 oxypropylene adduct o~ ammonlum persulrate 9523000 C12 - C14 al¢ohols l40.0]
~ [1.0] , ~__ 4 Surrynol 440 b) ammonium per~uli~aSe 9~ 30000 t7.0~ t20.0]
_ 5 polypropylene glycol ammonlum persulfate 95 10000 L nonyl phenyl ether t15.0~ l _ 6 oryethylene f am~onlum persul~ate 95 6000 :
I C12 - C1~ alcohol~ 1 ~85.8~ l a pDlyo~yethylene poly xypropylsne ~dduct (Asahi Denka K.K.) b) acetylene alcohol polyoxyethylene adduct (Nisshln Xagaku X~gyo K.X.) o) Monomer mlxture i9 added ln 40 % aq~eous solution and polymerlzation ln~t~ator is added in 5 ~ aqueou~ solution.
' ~ `"
.
---` 212~
Case 154-0244 Table 3 . . _ Reaction co~poslt~on: numeralq in bracket~ are parts by ~elght . ~ ~ . _ __ E le Admixture unsaturated xamp No. cbar8ed carbo2ylicother monomer other monomer ~olvent acad base ~onomer __ _ . _ ~ . .
7 ~7) w~tcr ~1695.0] MA~~50-0~ ~750.0; _ a (8) water [2838.0~ MAA~239.0] ~1200-0;
_ (~) wat~r [2338.0) MAA~239.03 [1200.0l _ _ (lO) water ~2931.0] MAA[239.0] MPEGMMA (n;50) _ _ 11 (ll) water ~3158.0] NAA[239.0] [1200.0i _ _ 12 t12) water t3077.0] HAA[177.0~ t1262.0; . ~
13 (13) water [297~.0~ MAAt239.0] ~1Z00.0] . :.
. ~ .
14 ~14) water ~3334.] SAt2B8.03 MP~GMMA tnj50) :~
, (15) water t2195.0~ MAAC239.0~ ~1200.0 ., 16 (16) water ~28Z3,0] MAA~239,0] [~080,0;ethacrylate ________________ ________________ t120.03 17 ~17)water t2924-0] MAA [215.0] MPEG~A (nj50) [24.0]
_ (18)water tl695.0~ MAA t250.0] [750.0;
19 (19)water tl695.0] MAA ~300.0~ [700.0]
~ .
(20)water [1695.0] MAA ~300.0] ~700.0¦ .
.
21 (21) water ~349.6~ MA ~667.01 PE~AE (n;5) MAA : methaarylic ac~d SA : ~odim acrylate MA : maleic aold MPEGMMA : methoxy polyethylene glyaol monomethacrglate PEGMMA : polyethylene glycol mcnomethacryla~e PECMAE : polyethylene glycol mon~allyl ether ., . ~ . . ! , , 21 212 ~ ~ 21 case 154-0244 ~ L n -- r - ~ ~ c ~ ~ O O ~ ~O N t-- r- r-- h I n ¦ h ¦ h ¦ z ¦ O 0 l I I I ~1 1 I L
1~ rr r ~ l __ l r _ I ~c 3 ~ON~ llo¦l ll Il~N i I ~
2~2~21 22 Case 1.54-0244 . :
A~nixtw ~ I trDol~eta Dre F rts by aelgtt ¦ l~eaotion ¦ aelght Example No. _ - -- (C) cro~s-copolymer tA) ~ h~g age~t I . linlcin~
_ _ A~nixture o-phthal~c asid 9~ 220000 22 (22) No. diglycidyl e~er .
(NW; 35000)_~ _ 23 i (23) A~::~u~ diglyo1dyl ether 95 300000 tNw ;35000~ l(n--9) _ _ _ __ A~nixture ~ ,6-hexanedlol 95 200000 : :
24 (24) CNw;38000~ diglyoidy1 ether A~ re zdlplo acl~ 95 150000 ¦ ~25) l ¦Na;600D] diglycidyl cster '~
. ` '::
~, '; :` ' 2~2~21 23 Case 154^0244 Table 6 . . . ~
Reaction co~po~ition : nu~erals in bra¢kets are parts by weight _ ~ _ __ Exismple dispersingc~argedunsaturated other mon~mer ~ther monomer ool~ent acid base monomer ~ ~ .-- _ toluene ~al~i~ 1-hesene 26 (26)12730] . 1490~ [420]
. I malelo j _ -~7 (27)ketone anhydride ~3643 styrene - I - L [25~1] r~~--~---~~~-~~ .
methoxy-toluene malel¢ polyethylene 28 (28)[27Y5l anbydride gly¢ol allyl . [147] [7h68]r _ _ , . ~
Reaotlon o~poslt~on : numeral~ in brackets are tlon Example jpart~ b~ weight reac molec~lar : :~
defoam1ng agent (I~)polymerization lnit~ator :::
. ~, o~yethylene oxypropylene 26adduot Of Cl2 - C14 AIBN 80 ~200 alcohols [27.01 _ 19.1) _ ~ I l _ polyosyethylene 27lauryla~ine AIBN 80 6000 ~5.5l Elo~o]
. ~ _ . ., _ polyoxyethylene 28polyoxypropylene adduct butyl peroxide 90 9000 [6.4] [lO.0~
_ _ _ _ 2:12~
Control 1 for manufacturing Comparison Admixture (1) 1695 Parts of water is introduced into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen while5 stirring, and the mixture is heated to 95C under a nitrogen atmosphere. A monomer aqueous solution comprising 800 parts of methoxy polyethylene glycol monomethacrylate (average mol addition number of ethylene oxide, 10) 200 parts of methacrylic acid, and 1500 parts of water, and 672 parts of a 5% ammonium persulfate aqueous solution are respectively drip-fed for 4 hours, and after competion of feeding, 168 parts of 5% ammonium persulfate is added over a period of 1 hour.
The temperature is maintained for 1 hour at 95C to complete a polymerization reaction. A comparison admixture (1) comprising an aqueous solution of a copolymer of average molecular weight of 35,000 is obtained.
Control 2 for manufacturing Comparison Admixture No. (2) 1695 parts of water is introduced into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen whilestirring, and the mixture is heated to 95C under a nitrogen atrnosphere. A monomer aqueous solution comprising 800 parts of methoxy polyethylene glycol monomethacrylate (average mol addition number of ethylene oxide, 10), 200 parts of methacrylic acid, 0.005 parts of "Pluronic" L-64 (polyoxyethylene-polyoxypropylene adduct) as oxyalkylene base defoaming agent, and 1500 parts of water, and 672 parts of a 5% ammonium persulfate aqueous solution are respectively dip-fed for 4 hours, and after completion of feeding, 168 parts of 5% ammonium persulfate is added over a period at 1 hour. The temperature is maintained at 95C for 1 hour to complete a polymerization reaction. A comparison admixture (2) comprising an aqueous solution of a copolymer of M~" 35,000 is obtained.
Control 3 for manufacturing Admixture No. (3) . -. ... , . . , . - . ~, ,: , . . .
21~21 To 100 parts of comparison admixture No. (1) obtained in Control 1, 0.1 part of polyoxyethylene polyoxypropylene nonyl phenyl ether as a polyoxyalkylene base defoaming agent is added to obtain a comparison cement dispersing agent (3).
Control 4 for manufacturing Comparison Admixture No. (4) 349.6 parts of water and 1648 parts of polyethylene glycol monoallyl ether (average mol addition number of ethylene oxide, 5) are introduced into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen while stirring, and the mixture is heated to 95C under a nitrogen atmosphere. A monomer/polymerization initiator mixture aqueous solution comprising 687 parts of maleic acid, 1030 parts of water and 57.2 parts of ammonium persulfate is dip-fed for 2 hours. After completion of feeding, 527 parts of 5%
ammonium persulfate aqueous solution is added over a period of 1 hour. The temperature is maintained at 95C for 1 further hour to complete the polymerization reaction. A comparison admixture (4) comprising an aqueous solution of a copolymer of Mw 6,000 if obtained.
Control 5 for manufacturing Admixture No. (5) A comparison admixture (5) is obtained by mixing 0.1 part of oxyethyleneoxypropylene adduct of Cl2-CI4 alcohol as a polyalkylene base of defoaming agent to the comparison admixture No. ~4) obtained in Control 4.
(Test of storage stability) The 28 varieties of cement dispersing agent of the invention shown in Tables 1 to 6 are left standing at 50C and the storage stability is investigated by visually observing degrees of compatibility. Further, for purposes of comparison, tests are also made of the comparison cement dispersing agent (3) obtained in Control 3 and comparison cement dispersing agent (5) obtained in Control 5. The particle size of the defoaming - -`~ 21~2~
agent is determined by using a laser diffraction t,vpe particle distribution meter (microtruck FRA). The results of these tests are given in Tables 7 and 8.
Further, evalution of compativilities are as follows: :
0: Uniformly compatible or stable dispersion ~ ;
~: Not compatible or unstable dispersion X: Separated into two layers --~. 27 2~L2~21case 154-0244 Table 7 I . Nu~ber o~ days elap~ed . _ _ particl slze .-I E~ample Admixture u~ed immedl- 50C, 50C, (~) ately after 1 day after 1 month i (1) O O O 1.3 r (3) ~ ~ O O _ ~ 7 ~: :
. ~ - (4) ~ O O .
O I O 5 ~ _ - (9) O O i 1 2 ¦
. ~ (10) O O O 1 1.5 2) ¦ ¦~
14 (14) O O O l.
~ =~1 I O ~ I 1 4 -20 - - (20) O ~ O_ O - 1.4 I ~:
21 ~ (21) O O O 5.7 22 ~ ~ O O 1.3 _ 23 ~ O O - O 1.3 24 - (24) O O O 1.4 Z5 - (25) I O O O 5,7 26 - (26) O O O ~ _ 27 ~ (27) o- - O - O
-- _ ._ 28 (2 O O O O _ . . _ '-" ln p rticle size determination : particle si2e 1~ not more than 0.1 ~m or cannot be determined because o~ ~olten state 28 212 ~ Case 154-0244 Table 8 ._ '.
Number Or days elapsed . . ~ partiol si~e Control A~nixture used ~mmedi- 50C, ~0C~ (~m) ately a~ter 1 day ~rter 1 month 3 .~ ~ X 2.2 Adrni~cture No. (3) ~ _ co~arative ~ X ~ - 5 .2 ::
AhTIi~ure No. (5) . _ .
.
, 212~2~
The cement used was ordinary portland cement (blend of equal amounts of 3 brands, specific gravity: 3.16), the fine aggregate was a blend of Oi River System pit sand and Kisarazu mountain sand (specific gravity 2.62, FM 2.71) and coarse aggregate wasOhme, Tokyo graywacke crushed stone (specific gravity 2.64, MS 20mm).
5 The 28 varieties of the admixture according to the invention listed in Tables 1-6 and for comparison the comparison admixtures (1) to (5) and naphthalene sulfonate-formalin condensate (BNS) and melamine sulfonate-formalin condensate (MSF) are tested. As the comparative admixtures (1), (2) and (4) possess air-entraining properties, adjustments of entrained air contents using air-entraining agents are not 10 made, while for the other admixtures of the invention (1)-(17) and the comparison admixtures (3) and (5) and for BNS and MSF, a commercial air-entraining agent ("Pozzolith" (trade mark) No. 303A manufactured by NMB Ltd.) is used in the dosages listed in Tables 9 and 10 to make adjustments of entrained air contents as suited 15 The mix proportions for plain concrete without admixture according to the invention are unit cement content 320kg/m3, unit water content 203kg/m3 (water/cement ratio 0.634) and sand-aggregate ratio 49%, while the proportions for concrete using with the admixture are unit cement content 320kg/m3, unit water content 166kg/m3 (water-cement ratio 0.519), and sand-aggregate ratio 47%
20 Concretes are manufactured under the conditions mentioned above, time-dependent changes in slump values and air content are measured and siump losses and air-entraining properties are evaluated. The time of setting and 28 day age compressive strength of concrete are also measured.
Measuring slump, air content, compressive strength and time of setting and the 25 method of collecting compressive strength specimens are all adaptations of Japan Industrial Standards UIS A 1101, 1108, 1128, 1132, 6204) The results are given in Tables 9-14 `
:
212~21 Case 154-0244 The results are given in Tables 9-14 Table ~ :
. . _ = ADraDt Or air Example A~nixture u~ed d1sper~ing aBent entraining aBent (1)- 0 ~ 0.012 ~ :
2 ----= 0.010 3 ~3) 0.15 0.005 4 . -- ~ 4 ~ 0.15 0 . 012 (5) 0.17 0,011 6 (6) 0.17 0 .015 t (7) ~ ~ 0.012 ~ ~:
_ (~) wat~r [2338.0) MAA~239.03 [1200.0l _ _ (lO) water ~2931.0] MAA[239.0] MPEGMMA (n;50) _ _ 11 (ll) water ~3158.0] NAA[239.0] [1200.0i _ _ 12 t12) water t3077.0] HAA[177.0~ t1262.0; . ~
13 (13) water [297~.0~ MAAt239.0] ~1Z00.0] . :.
. ~ .
14 ~14) water ~3334.] SAt2B8.03 MP~GMMA tnj50) :~
, (15) water t2195.0~ MAAC239.0~ ~1200.0 ., 16 (16) water ~28Z3,0] MAA~239,0] [~080,0;ethacrylate ________________ ________________ t120.03 17 ~17)water t2924-0] MAA [215.0] MPEG~A (nj50) [24.0]
_ (18)water tl695.0~ MAA t250.0] [750.0;
19 (19)water tl695.0] MAA ~300.0~ [700.0]
~ .
(20)water [1695.0] MAA ~300.0] ~700.0¦ .
.
21 (21) water ~349.6~ MA ~667.01 PE~AE (n;5) MAA : methaarylic ac~d SA : ~odim acrylate MA : maleic aold MPEGMMA : methoxy polyethylene glyaol monomethacrglate PEGMMA : polyethylene glycol mcnomethacryla~e PECMAE : polyethylene glycol mon~allyl ether ., . ~ . . ! , , 21 212 ~ ~ 21 case 154-0244 ~ L n -- r - ~ ~ c ~ ~ O O ~ ~O N t-- r- r-- h I n ¦ h ¦ h ¦ z ¦ O 0 l I I I ~1 1 I L
1~ rr r ~ l __ l r _ I ~c 3 ~ON~ llo¦l ll Il~N i I ~
2~2~21 22 Case 1.54-0244 . :
A~nixtw ~ I trDol~eta Dre F rts by aelgtt ¦ l~eaotion ¦ aelght Example No. _ - -- (C) cro~s-copolymer tA) ~ h~g age~t I . linlcin~
_ _ A~nixture o-phthal~c asid 9~ 220000 22 (22) No. diglycidyl e~er .
(NW; 35000)_~ _ 23 i (23) A~::~u~ diglyo1dyl ether 95 300000 tNw ;35000~ l(n--9) _ _ _ __ A~nixture ~ ,6-hexanedlol 95 200000 : :
24 (24) CNw;38000~ diglyoidy1 ether A~ re zdlplo acl~ 95 150000 ¦ ~25) l ¦Na;600D] diglycidyl cster '~
. ` '::
~, '; :` ' 2~2~21 23 Case 154^0244 Table 6 . . . ~
Reaction co~po~ition : nu~erals in bra¢kets are parts by weight _ ~ _ __ Exismple dispersingc~argedunsaturated other mon~mer ~ther monomer ool~ent acid base monomer ~ ~ .-- _ toluene ~al~i~ 1-hesene 26 (26)12730] . 1490~ [420]
. I malelo j _ -~7 (27)ketone anhydride ~3643 styrene - I - L [25~1] r~~--~---~~~-~~ .
methoxy-toluene malel¢ polyethylene 28 (28)[27Y5l anbydride gly¢ol allyl . [147] [7h68]r _ _ , . ~
Reaotlon o~poslt~on : numeral~ in brackets are tlon Example jpart~ b~ weight reac molec~lar : :~
defoam1ng agent (I~)polymerization lnit~ator :::
. ~, o~yethylene oxypropylene 26adduot Of Cl2 - C14 AIBN 80 ~200 alcohols [27.01 _ 19.1) _ ~ I l _ polyosyethylene 27lauryla~ine AIBN 80 6000 ~5.5l Elo~o]
. ~ _ . ., _ polyoxyethylene 28polyoxypropylene adduct butyl peroxide 90 9000 [6.4] [lO.0~
_ _ _ _ 2:12~
Control 1 for manufacturing Comparison Admixture (1) 1695 Parts of water is introduced into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen while5 stirring, and the mixture is heated to 95C under a nitrogen atmosphere. A monomer aqueous solution comprising 800 parts of methoxy polyethylene glycol monomethacrylate (average mol addition number of ethylene oxide, 10) 200 parts of methacrylic acid, and 1500 parts of water, and 672 parts of a 5% ammonium persulfate aqueous solution are respectively drip-fed for 4 hours, and after competion of feeding, 168 parts of 5% ammonium persulfate is added over a period of 1 hour.
The temperature is maintained for 1 hour at 95C to complete a polymerization reaction. A comparison admixture (1) comprising an aqueous solution of a copolymer of average molecular weight of 35,000 is obtained.
Control 2 for manufacturing Comparison Admixture No. (2) 1695 parts of water is introduced into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen whilestirring, and the mixture is heated to 95C under a nitrogen atrnosphere. A monomer aqueous solution comprising 800 parts of methoxy polyethylene glycol monomethacrylate (average mol addition number of ethylene oxide, 10), 200 parts of methacrylic acid, 0.005 parts of "Pluronic" L-64 (polyoxyethylene-polyoxypropylene adduct) as oxyalkylene base defoaming agent, and 1500 parts of water, and 672 parts of a 5% ammonium persulfate aqueous solution are respectively dip-fed for 4 hours, and after completion of feeding, 168 parts of 5% ammonium persulfate is added over a period at 1 hour. The temperature is maintained at 95C for 1 hour to complete a polymerization reaction. A comparison admixture (2) comprising an aqueous solution of a copolymer of M~" 35,000 is obtained.
Control 3 for manufacturing Admixture No. (3) . -. ... , . . , . - . ~, ,: , . . .
21~21 To 100 parts of comparison admixture No. (1) obtained in Control 1, 0.1 part of polyoxyethylene polyoxypropylene nonyl phenyl ether as a polyoxyalkylene base defoaming agent is added to obtain a comparison cement dispersing agent (3).
Control 4 for manufacturing Comparison Admixture No. (4) 349.6 parts of water and 1648 parts of polyethylene glycol monoallyl ether (average mol addition number of ethylene oxide, 5) are introduced into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, and the interior of the reaction vessel is purged with nitrogen while stirring, and the mixture is heated to 95C under a nitrogen atmosphere. A monomer/polymerization initiator mixture aqueous solution comprising 687 parts of maleic acid, 1030 parts of water and 57.2 parts of ammonium persulfate is dip-fed for 2 hours. After completion of feeding, 527 parts of 5%
ammonium persulfate aqueous solution is added over a period of 1 hour. The temperature is maintained at 95C for 1 further hour to complete the polymerization reaction. A comparison admixture (4) comprising an aqueous solution of a copolymer of Mw 6,000 if obtained.
Control 5 for manufacturing Admixture No. (5) A comparison admixture (5) is obtained by mixing 0.1 part of oxyethyleneoxypropylene adduct of Cl2-CI4 alcohol as a polyalkylene base of defoaming agent to the comparison admixture No. ~4) obtained in Control 4.
(Test of storage stability) The 28 varieties of cement dispersing agent of the invention shown in Tables 1 to 6 are left standing at 50C and the storage stability is investigated by visually observing degrees of compatibility. Further, for purposes of comparison, tests are also made of the comparison cement dispersing agent (3) obtained in Control 3 and comparison cement dispersing agent (5) obtained in Control 5. The particle size of the defoaming - -`~ 21~2~
agent is determined by using a laser diffraction t,vpe particle distribution meter (microtruck FRA). The results of these tests are given in Tables 7 and 8.
Further, evalution of compativilities are as follows: :
0: Uniformly compatible or stable dispersion ~ ;
~: Not compatible or unstable dispersion X: Separated into two layers --~. 27 2~L2~21case 154-0244 Table 7 I . Nu~ber o~ days elap~ed . _ _ particl slze .-I E~ample Admixture u~ed immedl- 50C, 50C, (~) ately after 1 day after 1 month i (1) O O O 1.3 r (3) ~ ~ O O _ ~ 7 ~: :
. ~ - (4) ~ O O .
O I O 5 ~ _ - (9) O O i 1 2 ¦
. ~ (10) O O O 1 1.5 2) ¦ ¦~
14 (14) O O O l.
~ =~1 I O ~ I 1 4 -20 - - (20) O ~ O_ O - 1.4 I ~:
21 ~ (21) O O O 5.7 22 ~ ~ O O 1.3 _ 23 ~ O O - O 1.3 24 - (24) O O O 1.4 Z5 - (25) I O O O 5,7 26 - (26) O O O ~ _ 27 ~ (27) o- - O - O
-- _ ._ 28 (2 O O O O _ . . _ '-" ln p rticle size determination : particle si2e 1~ not more than 0.1 ~m or cannot be determined because o~ ~olten state 28 212 ~ Case 154-0244 Table 8 ._ '.
Number Or days elapsed . . ~ partiol si~e Control A~nixture used ~mmedi- 50C, ~0C~ (~m) ately a~ter 1 day ~rter 1 month 3 .~ ~ X 2.2 Adrni~cture No. (3) ~ _ co~arative ~ X ~ - 5 .2 ::
AhTIi~ure No. (5) . _ .
.
, 212~2~
The cement used was ordinary portland cement (blend of equal amounts of 3 brands, specific gravity: 3.16), the fine aggregate was a blend of Oi River System pit sand and Kisarazu mountain sand (specific gravity 2.62, FM 2.71) and coarse aggregate wasOhme, Tokyo graywacke crushed stone (specific gravity 2.64, MS 20mm).
5 The 28 varieties of the admixture according to the invention listed in Tables 1-6 and for comparison the comparison admixtures (1) to (5) and naphthalene sulfonate-formalin condensate (BNS) and melamine sulfonate-formalin condensate (MSF) are tested. As the comparative admixtures (1), (2) and (4) possess air-entraining properties, adjustments of entrained air contents using air-entraining agents are not 10 made, while for the other admixtures of the invention (1)-(17) and the comparison admixtures (3) and (5) and for BNS and MSF, a commercial air-entraining agent ("Pozzolith" (trade mark) No. 303A manufactured by NMB Ltd.) is used in the dosages listed in Tables 9 and 10 to make adjustments of entrained air contents as suited 15 The mix proportions for plain concrete without admixture according to the invention are unit cement content 320kg/m3, unit water content 203kg/m3 (water/cement ratio 0.634) and sand-aggregate ratio 49%, while the proportions for concrete using with the admixture are unit cement content 320kg/m3, unit water content 166kg/m3 (water-cement ratio 0.519), and sand-aggregate ratio 47%
20 Concretes are manufactured under the conditions mentioned above, time-dependent changes in slump values and air content are measured and siump losses and air-entraining properties are evaluated. The time of setting and 28 day age compressive strength of concrete are also measured.
Measuring slump, air content, compressive strength and time of setting and the 25 method of collecting compressive strength specimens are all adaptations of Japan Industrial Standards UIS A 1101, 1108, 1128, 1132, 6204) The results are given in Tables 9-14 `
:
212~21 Case 154-0244 The results are given in Tables 9-14 Table ~ :
. . _ = ADraDt Or air Example A~nixture u~ed d1sper~ing aBent entraining aBent (1)- 0 ~ 0.012 ~ :
2 ----= 0.010 3 ~3) 0.15 0.005 4 . -- ~ 4 ~ 0.15 0 . 012 (5) 0.17 0,011 6 (6) 0.17 0 .015 t (7) ~ ~ 0.012 ~ ~:
8 (~) 0. 15 0 .010 ( 9) 0, 15 0 .003 (10) 0.15 0.015 1 1 ( 11 ) 0.15 o, oo8 _ .~
12 ( 12) 0,15 0.010 13 ( 13) 0.15 o.ola 14 -- (14) 0.15 0,020 ( 15) 0.15 0,010 16 ( 16) 0.15 0.008 17 _ ( 11 ) 0 . 1~ 0 . 016 18 ( 18) 0.15 0.012 19 ~ ~19 I ~ 15 0.010 ~20) 0. 15 0.010 21 (21 ) 0,17 0.015 22 ~) 0 l~ 0.012 ~
23 (23) 0 .18 O.OlZ
Z4 (211) 0.18 0.010 _ (25) 0 .18 0 ,015 _ 26 (26~ 0,17 0.016 ~ ___ 27 (27) o. 15 0.~15 .
_ .. .. .
28 (23) 0. 12 0.012 _ . _ Re~arke: a) Percent by weight o~ solid content ~o cement b) Percent by weight to cerDent 2~2~21 31 Case 154-0244 Table 10 _ = Amount of air Control Admixture . used dispersing a8ent entra~n1n~ a8ent a) _ . `''' Aplain concrete ~ _ B BWS 0~50 0,Do8 _ .
C MSF O.60 O.002 . ._ _ lcomparative 0.15 _ A~mixture No. (~) _ .
. 2 co~par~tlve 0.15 _ Admixture No. ~2) . _ _ _ . _ 3 ¢omparative . 0 ,15 0 , 01 1 Admixture No. (3) ~ _ : `
4 comparative 0.15 ~
Admixtllre No. (4) . _ : ::
comparative . 0.15 0,013 ~:
Admdxture No. (5) _ Remarks a) Peroent by weight ~ 301id content to cement `~ `
b) Peraent by weight to cement ~
212~
32 Case 154-0244 Table 1 l 1- ~
E~ampleimmedia~ely A~ter 30 ~ln. ¦ After 60 min. A~ter 90 min a~ter mlxing ~
¦ 1 19.0 / 4.1 ~ 17.5 / 4.0 Z I ~8.5 / 3~9 l7.0 / 3 7 16.5 / 3 3 17.0 / 3.5 3 I 17.5 / 4,0 1 18.5 / 3.1 ~ 17.0 / 3.8 ¦ 4 1 19. / 4.0I t7.0 / 3.81 16.5 / 3.8 1 17.0 / 3.5 ¦ 17,5 / 4,2~ 18.0 / 4~3 L 17.5 / 4~ r-~ 17.0 / 3~
18.~ / 4.2r 7~5 / 4.t 17.5 / 3 9 18.0 / 3.7 7 1 18.5 / 3.7 _ ~ ~ l7.5 / 3.7 8 18.0 / 4.0 18.0 / 4,0 1B.5 / 3,3 17.5 t 4.1 9 , 18,5 / 3.9 18.0 / 4.1 18.~ / 3 B 11.D / 3.a 1 10 1 19.0 / 4.~ 1 18.0 / 4.~ 17.0 / 4.3 18.5 / 4,2 j 11 1 18.5 / 3~8 17.0 / 4.0 18.0 / 3-~ 19.5 / 3.7 12 1 19.0 / 4.0 17.0 / 4,0 18.3 / 4.~ 17.0 / 3.7 1 13 18.0 / 4.5 17.0 / 4.0 17.5 / 4.1 17,5 / 4.4 14 1 19.0 / 4.0 19.0 / 4.0 17.5 ~ 3.8 17,5 / 3.7 1 15 ¦ 18.0 / 4.0 17.0 / 4.3 18.5 / 3.8 17.0 / 3.7 16 1 18.5 / 4,l 19 0 / 4.0 17.5 / 3.8 17.~ / 3~7 17 1 18.0 / 4.0 18.0 / 4.0 17.5 / 3.7 17.5 / 3.8 18 ¦ 18.5 / 3,9 15.5 / 3.6 17.5 / 3.9 17~5 / 3~?
212~21 - 33 Case 15~-024 Table 12 Slump (cm) / air content (vol%) ::
Exampleafter mi~1ngA~ter 30 mln.After 60 miD~After 90 min. :
19 18.5 / 3-9 18.0 / 4.0 18.0 / 4.0 17.5 / 3.8 _ .
20 1~.0 / 4.1 17.0 ~ 3.8 17.0 / 3.9 17.5 / 3.6 21 19.0 / 3.8 17.D / 3.4 t7.0 / 3.7 17.0 / 3.5 ~ . _ ..
Z2 17.0 / 3.4 20.5 / 3.7 19.5 / 3,6 19.0 / 3.~
_ ...
23 17.0 / 3.6 20.0 / 3.5 19.5 J 3.6l~,0 / 3.6 _ .
2~ 17.0 / 3.9 20.0 ~ 3.9 19.0 / 4.018.5 / 3.7 25 17.0 / 4.0 21.0 / 4.1 19.0 / 3.717.5 / 3.9 __ _ _ 26 19.5 / 4.1 l9.0 / 3.7 18.0 / 3.017.5 / 3.3 27 18.0 / 4.3 18.~ / 4.1 ~7.0 / ~.217.~ / 3.9 28 18.5 / 3.7 18.0 / 3.8 18.5 / 3.517.5 / 3.5 ~_ . - .
~ontrol _ A 19.0 / 2,0 17.5 / 2.0 15.5 ~ 1.812.5 / 1.7 18.0 / 4.4 10.5 / 4.1 6.5 / 3.B 4.0 ~ 3.3 _ C 18.5 J 4.2 9.5 J 4.0 6.5 / 3.9 4.0 t 3.1 1 19.0 / 4.4 19.0 / 4.2 la.0 / 4.417.0 / 4.6 - - 18.5 / 4.Z 18.0 / 4.3 15.5 / 4.317.5 / 4.6 3 18.0 / 3.9 18.5 J 3.9 17.D / 4.316.5 / 4.6 _ _ 4 18.5 / 4.6 17.5 / 4.5 17.5 / 4.517.0 / 4.7 5 19.0 / 3.7 17.û / 4.0 1B.6 / 4,518.5 / 5.1 ~12~2~
34 Case 154-0244 -Table 1 3 ~ _ . Settio~ time (Ir-min) 28-Day Comp.
Example ~ Strehsth Init. Fill~l (kg~lcm ) ~-20 a-30 4ao ~ ~ . .
3 `- 6-30 8-30 467 - I 6-20 L~ ~ 461 : : :
- 5 6-30 _ 8-20__ 458 _ 6-10 a-40 477_ 8 6-20 8-30 470 , 9 6-00_ ' 8-40 ~ 488_ ~1 5-50 8-10 453 12 6-oo 8-50 475 13 6-20 g_oo 455 _ ~8 6-~o 9 00 473 _ Z 12 5 5 21 Case lS4-OZ44 Table 1 4 . _ ~ ~ .:
Setting t~me ~hr-min) 28-Day Comp. :
Exa~p~e __ ~ I Str~h~th Ini~, Final (kgf/cm ) , _ _ _ _ ~ :
19 1 6-30 8-10 ~_,_ 6-~o 8~2~ 45~
22 1 6-50 ~ 9_10 l~ll .
23 1 6-40_ --26 6-30 8-30 _ 479 _ 27- 6-tO 8-20 459 _ .. -- ~ ..
Control A 5_40 7-50 C 5-30 _ 410 _ 3 6-30 1~ _ 419-4 6~oo 8-30 417 _ 6-10 8-20 ~25 . ~ __ --` 212~21 ; ~ 154-0244 36 From Tables 9 to 10, it may be seen that the shelf life of an admixture according to the invention is considerably improved over the case of the blend of defoaming agent with a copolymer.
Tables 9 to 14 show that t~e comparison admixtures (1) and (4) obtained by 5 polymerization without using a defoaming agent and the comparison admixture (2) obtained by using 0.005% of the defoaming agent produces an air content of 4.5-5%, so that dosage must be limited. Moreover, 28-day compressive strength is reduced.
With admixtures according to the invention, air-entraining tendencies are reduced and adjustment can be made to any air content with an air-entraining agent. Further, 10 other physical properties are equal to or better than comparison concretes, and it may particularly be noted that 28 day compressive strengths are greatly increased~
Moreover, comparison admixtures (3) and (5) with added defoaming agents added to comparison cement dispersing agent (1) show increases in entrained air content with elapse of time, whereas the air-entraining properties of admixtures according to 15 the invention are stable with elapse of time and slump loss prevention is also superior compared with plain concrete, BNS and MSF.
The admixtures according to the invention ameliorate and even eliminate the problem of the excessive air-entraining properties of conventional polycarboxylic acid base high range air-entraining, water-reducing agents. They exhibit excellent shelf life and 20 are capable of entraining suitable amounts of air. Thus, the use of an admixture according to the invention confers the possibility of preparing cementitious mixtures such as concrete of good fluidity with a high rate of water reduction, whichon hardening, will provide a hardened concrete object of high compressive strength.
12 ( 12) 0,15 0.010 13 ( 13) 0.15 o.ola 14 -- (14) 0.15 0,020 ( 15) 0.15 0,010 16 ( 16) 0.15 0.008 17 _ ( 11 ) 0 . 1~ 0 . 016 18 ( 18) 0.15 0.012 19 ~ ~19 I ~ 15 0.010 ~20) 0. 15 0.010 21 (21 ) 0,17 0.015 22 ~) 0 l~ 0.012 ~
23 (23) 0 .18 O.OlZ
Z4 (211) 0.18 0.010 _ (25) 0 .18 0 ,015 _ 26 (26~ 0,17 0.016 ~ ___ 27 (27) o. 15 0.~15 .
_ .. .. .
28 (23) 0. 12 0.012 _ . _ Re~arke: a) Percent by weight o~ solid content ~o cement b) Percent by weight to cerDent 2~2~21 31 Case 154-0244 Table 10 _ = Amount of air Control Admixture . used dispersing a8ent entra~n1n~ a8ent a) _ . `''' Aplain concrete ~ _ B BWS 0~50 0,Do8 _ .
C MSF O.60 O.002 . ._ _ lcomparative 0.15 _ A~mixture No. (~) _ .
. 2 co~par~tlve 0.15 _ Admixture No. ~2) . _ _ _ . _ 3 ¢omparative . 0 ,15 0 , 01 1 Admixture No. (3) ~ _ : `
4 comparative 0.15 ~
Admixtllre No. (4) . _ : ::
comparative . 0.15 0,013 ~:
Admdxture No. (5) _ Remarks a) Peroent by weight ~ 301id content to cement `~ `
b) Peraent by weight to cement ~
212~
32 Case 154-0244 Table 1 l 1- ~
E~ampleimmedia~ely A~ter 30 ~ln. ¦ After 60 min. A~ter 90 min a~ter mlxing ~
¦ 1 19.0 / 4.1 ~ 17.5 / 4.0 Z I ~8.5 / 3~9 l7.0 / 3 7 16.5 / 3 3 17.0 / 3.5 3 I 17.5 / 4,0 1 18.5 / 3.1 ~ 17.0 / 3.8 ¦ 4 1 19. / 4.0I t7.0 / 3.81 16.5 / 3.8 1 17.0 / 3.5 ¦ 17,5 / 4,2~ 18.0 / 4~3 L 17.5 / 4~ r-~ 17.0 / 3~
18.~ / 4.2r 7~5 / 4.t 17.5 / 3 9 18.0 / 3.7 7 1 18.5 / 3.7 _ ~ ~ l7.5 / 3.7 8 18.0 / 4.0 18.0 / 4,0 1B.5 / 3,3 17.5 t 4.1 9 , 18,5 / 3.9 18.0 / 4.1 18.~ / 3 B 11.D / 3.a 1 10 1 19.0 / 4.~ 1 18.0 / 4.~ 17.0 / 4.3 18.5 / 4,2 j 11 1 18.5 / 3~8 17.0 / 4.0 18.0 / 3-~ 19.5 / 3.7 12 1 19.0 / 4.0 17.0 / 4,0 18.3 / 4.~ 17.0 / 3.7 1 13 18.0 / 4.5 17.0 / 4.0 17.5 / 4.1 17,5 / 4.4 14 1 19.0 / 4.0 19.0 / 4.0 17.5 ~ 3.8 17,5 / 3.7 1 15 ¦ 18.0 / 4.0 17.0 / 4.3 18.5 / 3.8 17.0 / 3.7 16 1 18.5 / 4,l 19 0 / 4.0 17.5 / 3.8 17.~ / 3~7 17 1 18.0 / 4.0 18.0 / 4.0 17.5 / 3.7 17.5 / 3.8 18 ¦ 18.5 / 3,9 15.5 / 3.6 17.5 / 3.9 17~5 / 3~?
212~21 - 33 Case 15~-024 Table 12 Slump (cm) / air content (vol%) ::
Exampleafter mi~1ngA~ter 30 mln.After 60 miD~After 90 min. :
19 18.5 / 3-9 18.0 / 4.0 18.0 / 4.0 17.5 / 3.8 _ .
20 1~.0 / 4.1 17.0 ~ 3.8 17.0 / 3.9 17.5 / 3.6 21 19.0 / 3.8 17.D / 3.4 t7.0 / 3.7 17.0 / 3.5 ~ . _ ..
Z2 17.0 / 3.4 20.5 / 3.7 19.5 / 3,6 19.0 / 3.~
_ ...
23 17.0 / 3.6 20.0 / 3.5 19.5 J 3.6l~,0 / 3.6 _ .
2~ 17.0 / 3.9 20.0 ~ 3.9 19.0 / 4.018.5 / 3.7 25 17.0 / 4.0 21.0 / 4.1 19.0 / 3.717.5 / 3.9 __ _ _ 26 19.5 / 4.1 l9.0 / 3.7 18.0 / 3.017.5 / 3.3 27 18.0 / 4.3 18.~ / 4.1 ~7.0 / ~.217.~ / 3.9 28 18.5 / 3.7 18.0 / 3.8 18.5 / 3.517.5 / 3.5 ~_ . - .
~ontrol _ A 19.0 / 2,0 17.5 / 2.0 15.5 ~ 1.812.5 / 1.7 18.0 / 4.4 10.5 / 4.1 6.5 / 3.B 4.0 ~ 3.3 _ C 18.5 J 4.2 9.5 J 4.0 6.5 / 3.9 4.0 t 3.1 1 19.0 / 4.4 19.0 / 4.2 la.0 / 4.417.0 / 4.6 - - 18.5 / 4.Z 18.0 / 4.3 15.5 / 4.317.5 / 4.6 3 18.0 / 3.9 18.5 J 3.9 17.D / 4.316.5 / 4.6 _ _ 4 18.5 / 4.6 17.5 / 4.5 17.5 / 4.517.0 / 4.7 5 19.0 / 3.7 17.û / 4.0 1B.6 / 4,518.5 / 5.1 ~12~2~
34 Case 154-0244 -Table 1 3 ~ _ . Settio~ time (Ir-min) 28-Day Comp.
Example ~ Strehsth Init. Fill~l (kg~lcm ) ~-20 a-30 4ao ~ ~ . .
3 `- 6-30 8-30 467 - I 6-20 L~ ~ 461 : : :
- 5 6-30 _ 8-20__ 458 _ 6-10 a-40 477_ 8 6-20 8-30 470 , 9 6-00_ ' 8-40 ~ 488_ ~1 5-50 8-10 453 12 6-oo 8-50 475 13 6-20 g_oo 455 _ ~8 6-~o 9 00 473 _ Z 12 5 5 21 Case lS4-OZ44 Table 1 4 . _ ~ ~ .:
Setting t~me ~hr-min) 28-Day Comp. :
Exa~p~e __ ~ I Str~h~th Ini~, Final (kgf/cm ) , _ _ _ _ ~ :
19 1 6-30 8-10 ~_,_ 6-~o 8~2~ 45~
22 1 6-50 ~ 9_10 l~ll .
23 1 6-40_ --26 6-30 8-30 _ 479 _ 27- 6-tO 8-20 459 _ .. -- ~ ..
Control A 5_40 7-50 C 5-30 _ 410 _ 3 6-30 1~ _ 419-4 6~oo 8-30 417 _ 6-10 8-20 ~25 . ~ __ --` 212~21 ; ~ 154-0244 36 From Tables 9 to 10, it may be seen that the shelf life of an admixture according to the invention is considerably improved over the case of the blend of defoaming agent with a copolymer.
Tables 9 to 14 show that t~e comparison admixtures (1) and (4) obtained by 5 polymerization without using a defoaming agent and the comparison admixture (2) obtained by using 0.005% of the defoaming agent produces an air content of 4.5-5%, so that dosage must be limited. Moreover, 28-day compressive strength is reduced.
With admixtures according to the invention, air-entraining tendencies are reduced and adjustment can be made to any air content with an air-entraining agent. Further, 10 other physical properties are equal to or better than comparison concretes, and it may particularly be noted that 28 day compressive strengths are greatly increased~
Moreover, comparison admixtures (3) and (5) with added defoaming agents added to comparison cement dispersing agent (1) show increases in entrained air content with elapse of time, whereas the air-entraining properties of admixtures according to 15 the invention are stable with elapse of time and slump loss prevention is also superior compared with plain concrete, BNS and MSF.
The admixtures according to the invention ameliorate and even eliminate the problem of the excessive air-entraining properties of conventional polycarboxylic acid base high range air-entraining, water-reducing agents. They exhibit excellent shelf life and 20 are capable of entraining suitable amounts of air. Thus, the use of an admixture according to the invention confers the possibility of preparing cementitious mixtures such as concrete of good fluidity with a high rate of water reduction, whichon hardening, will provide a hardened concrete object of high compressive strength.
Claims (12)
1. A fluidity-controlling admixture for cementitious compositions, comprising at least one cement-dispersing agent and at least one defoaming agent, characterised in that (a) the cement-dispersing agent is an aqueous solution of polymer; and (b) the defoaming agent is oxyalkylene-based and is either dissolved in the polymer solution or is stably dispersed therein in particles of no more than 20µM diameter.
2. An admixture according to claim 1, wherein the polymer comprises a main component which is selected from at least one of (A) a copolymer obtained by polymerising a monomer mixture which comprises an unsaturated carboxylic acid monomer;
(B) the neutralised salt of (A); and (C) the polymer obtained by crosslinking (A) and/or (B) by means of a crosslinking agent.
(B) the neutralised salt of (A); and (C) the polymer obtained by crosslinking (A) and/or (B) by means of a crosslinking agent.
3. An admixture according to claim 1 or claim 2, wherein the polymer is formed from a monomer mixture which comprises from 5-98% by weight of an alkylene glycol mono(meth)acrylic acid ester monomer (a) of the formula I
(I) wherein R1 and R2 are independently hydrogen or methyl, R3 is an alkylene group of from 2-4 carbon atoms, R4 is hydrogen or an alkyl group of from 1 to 22 carbon atoms, and m represents an integer of 1 to 100, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (II) (II) wherein R1 and R2 have the abovementioned significances, and M1 is hydrogen, monovalent metal, divalent metal, ammonium group or an organic amine group, and 0 to 50% by weight of a monomer (c) capable of being copolymerized with these monomers, provided that the sum of (a), (b) and (c) shall be 100% by weight.
(I) wherein R1 and R2 are independently hydrogen or methyl, R3 is an alkylene group of from 2-4 carbon atoms, R4 is hydrogen or an alkyl group of from 1 to 22 carbon atoms, and m represents an integer of 1 to 100, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (II) (II) wherein R1 and R2 have the abovementioned significances, and M1 is hydrogen, monovalent metal, divalent metal, ammonium group or an organic amine group, and 0 to 50% by weight of a monomer (c) capable of being copolymerized with these monomers, provided that the sum of (a), (b) and (c) shall be 100% by weight.
4. An admixture according to claim 1 or claim 2, wherein the polymer is prepared from a monomer mixture which comprises from 5-98% by weight of an alkoxypolyalkylene glycol mono(meth)allyl ether base monomer (d) of the formula (III);
(III) wherein R1, R2, R3, R4 and m are as hereinabove defined and n is 0 or 1, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (IV) (IV) wherein X and Y are independently selected from hydrogen, methyl and -COOM3, or X or Y together with -COOM2 form an anhydride ring, Z is selected from -CH2COOM3, hydrogen or methyl and M2 and M3 are independently selected from the significances of M1 given hereinabove, an alkyl group of 1-20 carbon atoms, an alkylene glycol of 2-4 carbon atoms and a polyalkylene glycol of from 2-100 mols of a glycol adduct, provided that at least one of M2, M3 is selected from hydrogen, monovalent metal, divalent metal, ammonium group and an organic amine group;
and from 0-50% by weight of monomer (f) capable of copolymerisation with (d) and (e), (d)+(e)+(f) being 100% by weight.
(III) wherein R1, R2, R3, R4 and m are as hereinabove defined and n is 0 or 1, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (IV) (IV) wherein X and Y are independently selected from hydrogen, methyl and -COOM3, or X or Y together with -COOM2 form an anhydride ring, Z is selected from -CH2COOM3, hydrogen or methyl and M2 and M3 are independently selected from the significances of M1 given hereinabove, an alkyl group of 1-20 carbon atoms, an alkylene glycol of 2-4 carbon atoms and a polyalkylene glycol of from 2-100 mols of a glycol adduct, provided that at least one of M2, M3 is selected from hydrogen, monovalent metal, divalent metal, ammonium group and an organic amine group;
and from 0-50% by weight of monomer (f) capable of copolymerisation with (d) and (e), (d)+(e)+(f) being 100% by weight.
5. An admixture according to claim 1 or claim 2, wherein the polymer is preparedfrom a monomer mixture which comprises from 5-98% by weight of at least one a-olefinic monomer (g) having from 2-12 carbon atoms, from 2-95% by weight of an ethylenically unsaturated dicarboxylic acid anhydride base monomer (h) and from 0-50% by weight of monomer (i) copolymerisable with (g) and (h),(g)+(h)+(i) being 100% by weight.
6. A process of producing an admixture according to claim 1 or claim 2, comprising the polymerisation of a monomer mixture which comprises at least one unsaturatedcarboxylic acid base monomer in the presence of an oxyalkylene-based defoaming agent.
7. A process according to claim 6, wherein the monomer mix comprises an unsaturated carboxylic acid monomer and the polymerisation forms a polymer selected from the group consisting of (A) a copolymer;
(B) the neutralised salt of (A); and (C) the polymer obtained by crosslinking (A) and/or (B) by means of a crosslinking agent.
(B) the neutralised salt of (A); and (C) the polymer obtained by crosslinking (A) and/or (B) by means of a crosslinking agent.
8. A process according to claim 6, wherein the polymer is formed from a monomer mixture which comprises from 5-98% by weight of an alkylene glycol mono(meth)acrylic acid ester monomer (a) of the formula I
(I) wherein R1 and R2 are independently hydrogen or methyl, R3 is an alkylene group of from 2-4 carbon atoms, R4 is hydrogen or an alkyl group of from 1 to 22 carbon atoms, and m represents an integer of 1 to 100, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (II) (II) wherein R1 and R2 have the abovementioned significances, and M1 is hydrogen, monovalent metal, divalent metal, ammonium group or an organic amine group, and 0 to 50% by weight of a monomer (c) capable of being copolymerized with these monomers, provided that the sum of (a), (b) and (c) shall be 100% by weight.
(I) wherein R1 and R2 are independently hydrogen or methyl, R3 is an alkylene group of from 2-4 carbon atoms, R4 is hydrogen or an alkyl group of from 1 to 22 carbon atoms, and m represents an integer of 1 to 100, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (II) (II) wherein R1 and R2 have the abovementioned significances, and M1 is hydrogen, monovalent metal, divalent metal, ammonium group or an organic amine group, and 0 to 50% by weight of a monomer (c) capable of being copolymerized with these monomers, provided that the sum of (a), (b) and (c) shall be 100% by weight.
9. A process according to claim 6, wherein the polymer is prepared from a monomer mixture which comprises from 5-98% by weight of an alkoxypolyalkylene glycol mono(meth)allyl ether base monomer (d) of the formula (III);
(III) wherein R1, R2, R3, R4 and m are as hereinabove defined and n is 0 or 1, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (IV) (IV) wherein X and Y are independently selected from hydrogen, methyl and -COOM3, or X or Y together with -COOM2 form an anhydride ring, Z is selected from -CH2COOM3, hydrogen or methyl and M2 and M3 are independently selected from the significances of M1 given hereinabove, an alkyl group of 1-20 carbon atoms, an alkylene glycol of 2-4 carbon atoms and a polyalkylene glycol of from 2-100 molsof a glycol adduct, provided that at least one of M2, M3 is selected from hydrogen, monovalent metal, divalent metal, ammonium group and an organic amine group;
and from 0-50% by weight of monomer (f) capable of copolymerisation with (d) and (e), (d)+(e)+(f) being 100% by weight.
(III) wherein R1, R2, R3, R4 and m are as hereinabove defined and n is 0 or 1, and 2 to 95% by weight of a (meth)acrylic acid base monomer (b) of the formula (IV) (IV) wherein X and Y are independently selected from hydrogen, methyl and -COOM3, or X or Y together with -COOM2 form an anhydride ring, Z is selected from -CH2COOM3, hydrogen or methyl and M2 and M3 are independently selected from the significances of M1 given hereinabove, an alkyl group of 1-20 carbon atoms, an alkylene glycol of 2-4 carbon atoms and a polyalkylene glycol of from 2-100 molsof a glycol adduct, provided that at least one of M2, M3 is selected from hydrogen, monovalent metal, divalent metal, ammonium group and an organic amine group;
and from 0-50% by weight of monomer (f) capable of copolymerisation with (d) and (e), (d)+(e)+(f) being 100% by weight.
10. A process according to claim 6, wherein the polymer is prepared from a monomer mixture which comprises from 5-98% by weight of at least one a-olefinic monomer (g) having from 2-12 carbon atoms, from 2-95% by weight of an ethylenically unsaturated dicarboxylic acid anhydride base monomer (h) and rom 0-50% by weight of monomer (i) copolymerisable with (g) and (h), (g)+(h)+(i) being 100% by weight.
11. A process of modifying the fluidity of a cementitious composition, comprising the incorporation into the composition of an admixture according to claim 1 or claim 2.
12. Use of an admixture according to claim 1 or claim 2 to modify the fluidity of a cementitious composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14098693 | 1993-06-11 | ||
| JP140986/93 | 1993-06-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2125521A1 true CA2125521A1 (en) | 1994-12-12 |
Family
ID=15281482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002125521A Abandoned CA2125521A1 (en) | 1993-06-11 | 1994-06-09 | Fluidity control of cementitious compositions |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5661206A (en) |
| AU (1) | AU678458B2 (en) |
| CA (1) | CA2125521A1 (en) |
| CH (1) | CH689118A5 (en) |
| DE (1) | DE4420444B4 (en) |
| FR (1) | FR2706447B1 (en) |
| GB (2) | GB9411604D0 (en) |
| IT (1) | IT1277296B1 (en) |
| MY (1) | MY111223A (en) |
| SG (1) | SG52673A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5703174A (en) * | 1995-06-21 | 1997-12-30 | W. R. Grace & Co.-Conn. | Air controlling superplasticizers |
| US6139623A (en) * | 1997-01-21 | 2000-10-31 | W. R. Grace & Co.-Conn. | Emulsified comb polymer and defoaming agent composition and method of making same |
Families Citing this family (121)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY114306A (en) * | 1995-07-13 | 2002-09-30 | Mbt Holding Ag | Cement dispersant method for production thereof and cement composition using dispersant |
| US5556460A (en) * | 1995-09-18 | 1996-09-17 | W.R. Grace & Co.-Conn. | Drying shrinkage cement admixture |
| DE19541720C2 (en) * | 1995-11-09 | 1999-07-08 | Gatz Hans Peter | Process for the preparation of a mixture of inorganic binders with or without addition and water |
| IT1281587B1 (en) * | 1996-01-03 | 1998-02-20 | Italcementi Spa | SUPERFLUIDIFYING COMPOSITION FOR CEMENTITIOUS COMPOSITIONS |
| US5670578A (en) * | 1996-12-10 | 1997-09-23 | Arco Chemical Technology, L.P. | Cement additives |
| CA2250139C (en) * | 1996-03-26 | 2005-09-13 | Arco Chemical Technology, L.P. | Cement additives |
| US5614017A (en) * | 1996-03-26 | 1997-03-25 | Arco Chemical Technology, L.P. | Cement additives |
| KR100247527B1 (en) * | 1996-04-03 | 2000-03-15 | 겐지 아이다 | Cement dispersing method and cement composition |
| US6384111B1 (en) * | 1996-12-20 | 2002-05-07 | Basf Aktiengesellschaft | Polymers containing carboxyl groups and polyalkylene ether side- chains as additives in mineral building materials |
| US5912284A (en) * | 1996-12-26 | 1999-06-15 | Nippon Shokubai Co., Ltd. | Cement additive, its production process and use |
| FR2760004B1 (en) * | 1997-02-25 | 1999-05-14 | Chryso | ADDITIVE FOR AQUEOUS SUSPENSIONS OF MINERAL PARTICLES AND HYDRAULIC BINDER MIXTURES |
| US6166112A (en) * | 1997-03-10 | 2000-12-26 | Nippon Shokubai Co., Ltd. | Cement admixture and cement composition |
| US5854386A (en) * | 1997-08-25 | 1998-12-29 | Arco Chemical Technology, L.P. | Stabilizers for polymer polyols |
| US6294015B1 (en) | 1998-01-22 | 2001-09-25 | Nippon Shokubai Co., Ltd. | Cement admixture and cement composition |
| EP1082276B1 (en) * | 1998-04-29 | 2002-07-24 | Italcementi S.p.A. | Superfluidifying additive for cementitious compositions |
| IT1301974B1 (en) * | 1998-07-31 | 2000-07-20 | Atochem Elf Italia | WATER SOLUBLE ACRYLIC COPOLYMERS |
| US6762269B1 (en) * | 1998-08-13 | 2004-07-13 | National Starch And Chemical Investment Holding Corporation | High temperature viscosity stable thickener |
| CA2339118C (en) | 1998-08-14 | 2010-10-19 | Mbt Holding Ag | Cementitious dry cast mixture |
| DK1044175T3 (en) | 1998-08-14 | 2003-03-17 | Mbt Holding Ag | Cement mixtures with high pozzolan content |
| DE19842859A1 (en) * | 1998-09-18 | 2000-03-23 | Basf Ag | Mixture of polycarboxylate-based liquefier and deaerating agent for cement-based building materials, e.g. concrete, contains butoxylated polyalkylene-polyamine or salts as a deaerating agent |
| DE19843730A1 (en) * | 1998-09-24 | 2000-03-30 | Sueddeutsche Kalkstickstoff | Stabilized, water-soluble polymer powder based on polyoxyalkylene glycol carboxylates and process for their production |
| EP1153071A4 (en) * | 1998-11-24 | 2003-05-02 | Grace W R & Co | Particles attached to first and second polymers having mutual non-covalently associative groups |
| US6310143B1 (en) | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| DE60029666T2 (en) | 1999-03-09 | 2007-08-09 | Nippon Shokubai Co., Ltd. | Additive for cement |
| DE19942301A1 (en) * | 1999-09-04 | 2001-03-08 | Basf Ag | Cement-based composition for use e.g. as repair mortar or tile adhesive, contains an acrylic copolymer with lower alkyl-terminated polyethoxy-acrylate or -methacrylate comonomer units |
| AU2005201589B2 (en) * | 1999-09-04 | 2008-01-10 | Basf Aktiengesellschaft | Cement compositions comprising redispersible polymer powders |
| MY135684A (en) † | 1999-11-29 | 2008-06-30 | Nippon Catalytic Chem Ind | Copolymer for cement admixtures and its production process and use |
| WO2001042161A2 (en) * | 1999-12-10 | 2001-06-14 | Mbt Holding Ag | Water-soluble air-controlling agents for cementitious compositions |
| US8088842B2 (en) | 1999-12-10 | 2012-01-03 | Construction Research & Technology Gmbh | Solubilized defoamers for cementitious compositions |
| AU2005202532B2 (en) * | 1999-12-10 | 2007-07-12 | Construction Research & Technology Gmbh | Water-Soluble Air-Controlling Agents for Cementitious Compositions |
| US6875801B2 (en) | 1999-12-10 | 2005-04-05 | Construction Research & Technology Gmbh | Solubilized defoamers for cementitious compositions |
| WO2001042162A1 (en) * | 1999-12-10 | 2001-06-14 | Mbt Holding Ag | Solubilized defoamers for cementitious compositions |
| US20030187100A1 (en) * | 1999-12-10 | 2003-10-02 | Mbt Holding Ag | Water soluble air controlling agents for cementitious compositions |
| FR2807760A1 (en) * | 2000-04-12 | 2001-10-19 | Atofina | Hydrosoluble thermosensitive copolymer for use as in disposable hygiene products as a component of hydrosoluble films for or as a binder for fibrous components of such products comprising hydrophobic monomer units |
| FR2807759A1 (en) * | 2000-04-12 | 2001-10-19 | Atofina | Hydrosoluble thermosensitive copolymer for use as in disposable hygiene products as a component of hydrosoluble films for or as a binder for fibrous components of such products |
| SG101990A1 (en) | 2000-08-11 | 2004-02-27 | Nippon Catalytic Chem Ind | Cement dispersant and cement composition comprising this |
| SG117450A1 (en) * | 2000-08-11 | 2005-12-29 | Nippon Catalytic Chem Ind | Cement admixture and cement composition |
| FR2814465A1 (en) * | 2000-09-27 | 2002-03-29 | Synthron | Grafted acrylic polymers for use in hydraulic cement compositions as liquefying and-or water reducing agent, optionally comprise alkyl esters of acrylic or methacrylic acids and acid groups esterified with polyethylene glycol monoether |
| US6641754B2 (en) * | 2001-03-15 | 2003-11-04 | Betzdearborn Inc. | Method for controlling scale formation and deposition in aqueous systems |
| US6444747B1 (en) | 2001-03-15 | 2002-09-03 | Betzdearborn Inc. | Water soluble copolymers |
| WO2002088241A1 (en) * | 2001-05-01 | 2002-11-07 | W.R. Grace & Co.-Conn. | Defoamer for water reducer admixture |
| US6803396B2 (en) | 2001-08-16 | 2004-10-12 | Basf Corporation | Stable aqueous polymeric superplasticizer solutions and concrete compositions containing the same |
| US6911494B2 (en) * | 2001-09-28 | 2005-06-28 | Nippon Shokubai Co., Ltd. | Cement admixture and cement composition |
| US6946505B2 (en) | 2001-10-17 | 2005-09-20 | Nippon Shokubai Co., Ltd. | Cement dispersant, its production process, and cement composition using the cement dispersant |
| US7247662B2 (en) | 2001-10-07 | 2007-07-24 | Nippon Shokubai Co., Ltd. | Cement dispersant, its production process, and cement composition using the cement dispersant |
| US20030144384A1 (en) * | 2001-10-09 | 2003-07-31 | Fu Chen | Superplasticizer for concrete and self-leveling compounds |
| US6858074B2 (en) * | 2001-11-05 | 2005-02-22 | Construction Research & Technology Gmbh | High early-strength cementitious composition |
| JP2003300766A (en) * | 2002-02-06 | 2003-10-21 | Nippon Shokubai Co Ltd | Concrete composition, method for producing the same and cement admixture |
| US20030191214A1 (en) * | 2002-04-03 | 2003-10-09 | Mari Masanaga | Admixture composition for hydraulic material |
| DE10224922A1 (en) * | 2002-06-04 | 2003-12-18 | Basf Ag | Process for the preparation of an aqueous copolymer solution |
| AU2002365282A1 (en) * | 2002-11-25 | 2004-06-18 | Die Construction Research & Technology Gmbh | Defoaming agent for cementitious composition |
| MXPA05009164A (en) * | 2003-02-26 | 2005-10-20 | Constr Res & Tech Gmbh | Strength improvement admixture. |
| CN100542989C (en) * | 2003-03-05 | 2009-09-23 | 株式会社日本触媒 | The method of cement additive, cement composition and laying method thereof and production hardening of cement product |
| CA2523686A1 (en) | 2003-03-27 | 2004-10-07 | Construction Research & Technology Gmbh | Liquid coloring suspension |
| JP2006522734A (en) * | 2003-04-08 | 2006-10-05 | 株式会社日本触媒 | Cement admixture and cement composition |
| FR2853646B1 (en) * | 2003-04-11 | 2007-07-06 | Chryso Sas | USE OF DISPERSANTS TO ENHANCE THE MAINTENANCE OF CONCRETE FLUIDITY |
| US20040211342A1 (en) * | 2003-04-25 | 2004-10-28 | Mbt Holding Ag | Rheology stabilizer for cementitious compositions |
| JP3922714B2 (en) * | 2003-10-30 | 2007-05-30 | 竹本油脂株式会社 | Hydraulic cement composition for concrete |
| DE102004008200A1 (en) * | 2004-02-18 | 2005-09-01 | Basf Ag | Use of water-soluble or water-dispersible polymers as additives in mineral building materials |
| US7556684B2 (en) * | 2004-02-26 | 2009-07-07 | Construction Research & Technology Gmbh | Amine containing strength improvement admixture |
| JP5237633B2 (en) | 2004-06-15 | 2013-07-17 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | Freeze-thaw resistant equipment for cementitious compositions |
| US8088218B2 (en) * | 2005-06-14 | 2012-01-03 | United States Gypsum Company | Foamed slurry and building panel made therefrom |
| US20060280899A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Method of making a gypsum slurry with modifiers and dispersants |
| US20060278128A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Effective use of dispersants in wallboard containing foam |
| US7875114B2 (en) * | 2005-06-14 | 2011-01-25 | United States Gypsum Company | Foamed slurry and building panel made therefrom |
| US7544242B2 (en) | 2005-06-14 | 2009-06-09 | United States Gypsum Company | Effective use of dispersants in wallboard containing foam |
| US7572328B2 (en) * | 2005-06-14 | 2009-08-11 | United States Gypsum Company | Fast drying gypsum products |
| US7504165B2 (en) * | 2005-06-14 | 2009-03-17 | United States Gypsum Company | High strength flooring compositions |
| WO2006138289A2 (en) * | 2005-06-14 | 2006-12-28 | United States Gypsum Company | Gypsum products utilizing a two-repeating unit dispersant and a method for making them |
| US20060280898A1 (en) * | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Modifiers for gypsum slurries and method of using them |
| CN101198563A (en) | 2005-06-14 | 2008-06-11 | 建筑研究及技术有限责任公司 | Providing freezing and thawing resistance to cementitious compositions |
| US20060278127A1 (en) | 2005-06-14 | 2006-12-14 | United States Gypsum Company | Gypsum products utilizing a two-repeating unit dispersant and a method for making them |
| WO2007026842A1 (en) * | 2005-08-31 | 2007-03-08 | Nippon Shokubai Co., Ltd. | Polyalkylene glycol |
| US7815731B2 (en) | 2006-06-13 | 2010-10-19 | Sekisui Specialty Chemicals America, Llc | Polyvinyl alcohol fluid loss additive with improved rheological properties |
| DE102007023813A1 (en) | 2007-05-21 | 2008-11-27 | Evonik Röhm Gmbh | Dispersion comprising inorganic particles, water and at least one polymeric additive |
| US8377196B2 (en) | 2007-08-10 | 2013-02-19 | Construction Research & Technology Gmbh | Rheology modifying additive for dry cast cementitious compositions |
| JP4531799B2 (en) * | 2007-10-19 | 2010-08-25 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | Cement additive |
| EP2090599A1 (en) | 2008-02-13 | 2009-08-19 | Construction Research and Technology GmbH | Copolymer with polyether side chains and dicarbonic acid derivative building blocks |
| EP2090596A1 (en) * | 2008-02-13 | 2009-08-19 | Construction Research and Technology GmbH | Copolymer with polyether side chains and hydroxyalkyl and acid building blocks |
| US7973110B2 (en) * | 2008-06-16 | 2011-07-05 | Construction Research & Technology Gmbh | Copolymer synthesis process |
| US8592040B2 (en) | 2008-09-05 | 2013-11-26 | Basf Se | Polymer emulsion coating or binding formulations and methods of making and using same |
| WO2010143630A1 (en) * | 2009-06-09 | 2010-12-16 | 株式会社竹中工務店 | Slurry composition for soil improvement containing blast furnace slag cement and method for preparing soil cement slurry using same |
| KR101106210B1 (en) | 2009-06-23 | 2012-01-20 | 주식회사 실크로드시앤티 | Polymer admixture for ultra-hard contrete |
| US9017520B2 (en) | 2010-03-23 | 2015-04-28 | Basf Se | Paper coating or binding formulations and methods of making and using same |
| US8461245B2 (en) | 2011-02-15 | 2013-06-11 | W.R. Grace & Co.-Conn. | Copolymers for treating construction aggregates |
| US9102848B2 (en) | 2011-02-28 | 2015-08-11 | Basf Se | Environmentally friendly, polymer dispersion-based coating formulations and methods of preparing and using same |
| US9475975B2 (en) * | 2011-02-28 | 2016-10-25 | Kemira Oyj | Defoaming compositions and processes for cementing applications |
| US9034968B2 (en) | 2011-03-31 | 2015-05-19 | W. R. Grace & Co.-Conn. | Cationic polymers for treating construction aggregates |
| US10077392B2 (en) | 2012-09-28 | 2018-09-18 | Kemira Oyj | Defoaming compositions |
| DE102011089535A1 (en) | 2011-12-22 | 2013-06-27 | Evonik Industries Ag | Defoamer compositions for building material mixtures |
| WO2013124003A1 (en) | 2012-02-22 | 2013-08-29 | W R Grace & Co.-Conn | Functionalized polyamines for clay mitigation |
| FR2989082B1 (en) * | 2012-04-05 | 2015-03-13 | Chryso | ADJUVANT FOR HYDRAULIC COMPOSITIONS |
| US20150133584A1 (en) | 2012-05-04 | 2015-05-14 | W R Grace & Co.-Conn. | Method For Treating Clay And Clay-Bearing Aggregates And Compositions Therefor |
| EP2660218A1 (en) * | 2012-05-04 | 2013-11-06 | Construction Research & Technology GmbH | Process for manufacturing a hydraulic bonding agent, corresponding additive and its use. |
| US8845940B2 (en) | 2012-10-25 | 2014-09-30 | Carboncure Technologies Inc. | Carbon dioxide treatment of concrete upstream from product mold |
| AU2014212083A1 (en) | 2013-02-04 | 2015-08-06 | Coldcrete, Inc. | System and method of applying carbon dioxide during the production of concrete |
| US9388072B2 (en) | 2013-06-25 | 2016-07-12 | Carboncure Technologies Inc. | Methods and compositions for concrete production |
| US9376345B2 (en) | 2013-06-25 | 2016-06-28 | Carboncure Technologies Inc. | Methods for delivery of carbon dioxide to a flowable concrete mix |
| US10927042B2 (en) | 2013-06-25 | 2021-02-23 | Carboncure Technologies, Inc. | Methods and compositions for concrete production |
| US9108883B2 (en) | 2013-06-25 | 2015-08-18 | Carboncure Technologies, Inc. | Apparatus for carbonation of a cement mix |
| US20160107939A1 (en) | 2014-04-09 | 2016-04-21 | Carboncure Technologies Inc. | Methods and compositions for concrete production |
| WO2015123769A1 (en) | 2014-02-18 | 2015-08-27 | Carboncure Technologies, Inc. | Carbonation of cement mixes |
| EP3129126A4 (en) | 2014-04-07 | 2018-11-21 | Carboncure Technologies Inc. | Integrated carbon dioxide capture |
| CN104017551B (en) * | 2014-06-17 | 2017-02-15 | 山东聚鑫化工有限公司 | Ionic liquid cement mortar early-strength admixture |
| CN104261719B (en) * | 2014-08-06 | 2016-09-14 | 中交二航武汉港湾新材料有限公司 | A kind of high-performance polycarboxylic acids water reducing agent and preparation method thereof |
| JP6415584B2 (en) * | 2014-09-30 | 2018-10-31 | 株式会社日本触媒 | Method for producing polycarboxylic acid polymer |
| CN107428611B (en) * | 2015-03-31 | 2020-08-18 | 花王株式会社 | Dispersant composition for hydraulic composition |
| CN108349824B (en) | 2015-06-04 | 2021-04-20 | 威瑞飞有限责任公司 | After the materials are mixed, the CMA is added into the concrete |
| EP3353131A1 (en) * | 2015-09-24 | 2018-08-01 | Sika Technology AG | Copolymers having a gradient structure as dispersant for alkalinically activated binding agents |
| CN105271893B (en) * | 2015-10-23 | 2017-10-13 | 上海三瑞高分子材料股份有限公司 | A kind of collapse protection type water reducer and preparation method thereof |
| US10597325B2 (en) | 2015-11-16 | 2020-03-24 | Gcp Applied Technologies Inc. | Postponed onset of quicklime hydration |
| CN105712649B (en) | 2015-12-31 | 2018-06-26 | 江苏苏博特新材料股份有限公司 | A kind of phosphoric acid polycondensates high efficiency water reducing agent and preparation method thereof |
| CA3019860A1 (en) | 2016-04-11 | 2017-10-19 | Carboncure Technologies Inc. | Methods and compositions for treatment of concrete wash water |
| CN110291057B (en) | 2016-12-01 | 2022-08-26 | 亨茨曼国际有限公司 | Functionalized polyacrylic polymer compositions |
| KR102129573B1 (en) | 2016-12-26 | 2020-07-02 | 주식회사 엘지화학 | Cement additive composition comprising polycarboxylic acid-based copolymer |
| WO2018124536A1 (en) * | 2016-12-26 | 2018-07-05 | 주식회사 엘지화학 | Cement additive composition comprising polycarbonate-based copolymer |
| CN106957395A (en) * | 2017-05-11 | 2017-07-18 | 长沙加美乐素化工有限公司 | A kind of synthetic method of new polycarboxylic acid water reducer |
| WO2018232507A1 (en) | 2017-06-20 | 2018-12-27 | Carboncure Technologies Inc. | Methods and compositions for treatment of concrete wash water |
| KR101972571B1 (en) | 2018-05-11 | 2019-04-25 | 주식회사 실크로드시앤티 | Composition for forming concrete in hot weather and concrete formed thereform |
| CA3119769A1 (en) | 2018-11-20 | 2020-05-28 | The Lubrizol Corporation | Graphene production and composition |
| CN113248381B (en) * | 2021-07-02 | 2023-01-06 | 北京金隅节能科技有限公司 | Modified fatty acid, polycarboxylate superplasticizer and preparation method of polycarboxylate superplasticizer |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4029585A (en) * | 1975-07-26 | 1977-06-14 | E. I. Du Pont De Nemours And Company | Aqueous dispersions of perfluoroalkyl esters for treating textiles |
| AU514678B2 (en) * | 1976-11-24 | 1981-02-19 | W.R. Grace & Co. | Hydraulic cement composition |
| DE2961932D1 (en) * | 1978-02-22 | 1982-03-11 | Ici Plc | Cementitious composition, a method to prepare it and shaped article derived therefrom |
| JPS5844711B2 (en) * | 1979-07-04 | 1983-10-05 | 日東電工株式会社 | Water-soluble pressure-sensitive adhesive composition |
| US4471100A (en) * | 1981-01-16 | 1984-09-11 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Copolymer and method for manufacture thereof |
| JPS6060961A (en) * | 1983-09-10 | 1985-04-08 | 日本ゼオン株式会社 | Flowable cement composition |
| NO165879C (en) * | 1984-06-07 | 1991-04-24 | Inst Francais Du Petrole | PROCEDURE FOR PREPARING AN INVERSE, STABLE MICROLATEKS. |
| JPS6270252A (en) * | 1985-09-25 | 1987-03-31 | 株式会社日本触媒 | Slump loss inhibitor for cement mortar concrete |
| US4808641A (en) * | 1986-07-31 | 1989-02-28 | Fujisawa Pharmaceutical Co., Ltd. | Concrete admixture |
| US4997857A (en) * | 1986-09-30 | 1991-03-05 | Arco Chemical Technology, Inc. | Stabilizers for polymer/polyols |
| US4960465A (en) * | 1986-12-09 | 1990-10-02 | W. R. Grace & Co. | Hydraulic cement additives and hydraulic cement compositions containing same |
| US4792360A (en) * | 1987-06-30 | 1988-12-20 | The Dow Chemical Company | Workable cement composition of low water content containing a hydroxyalkyl (meth)acrylate polymer |
| JP2730770B2 (en) * | 1989-04-28 | 1998-03-25 | 株式会社日本触媒 | Cement admixture |
| JPH0341160A (en) * | 1989-07-07 | 1991-02-21 | Kao Corp | Thermoplastic resin composition of excellent liquid repellency |
| EP0448717B1 (en) * | 1989-07-25 | 1995-11-29 | Nippon Shokubai Co., Ltd. | Cement admixture, production thereof, and cement composition |
| DE4135956C2 (en) * | 1990-11-06 | 2001-10-18 | Mbt Holding Ag Zuerich | Additive for cement mixtures and their use |
| US5169894A (en) * | 1990-11-16 | 1992-12-08 | Holland Richard J | Lowering of anionic loading of dispersants on pigment slurries by blending with nonionic polymers |
| US5149576A (en) * | 1990-11-26 | 1992-09-22 | Kimberly-Clark Corporation | Multilayer nonwoven laminiferous structure |
| US5145727A (en) * | 1990-11-26 | 1992-09-08 | Kimberly-Clark Corporation | Multilayer nonwoven composite structure |
| JPH05148454A (en) * | 1991-04-02 | 1993-06-15 | Nitto Kagaku Kk | Protecting and polishing agent for coating film of automobile |
| US5459188A (en) * | 1991-04-11 | 1995-10-17 | Peach State Labs, Inc. | Soil resistant fibers |
| EP0585312A4 (en) * | 1991-04-11 | 1994-09-28 | Peach State Labs Inc | Soil resistant fibers |
| AU664812B2 (en) * | 1992-02-14 | 1995-11-30 | Nof Corporation | Cement admixture composition |
| IT1263969B (en) * | 1993-02-25 | 1996-09-05 | Mario Collepardi | SUPERFLUIDIFYING ADDITIVES WITH HIGH CONSERVATION OF WORKABILITY |
| US5319020A (en) * | 1993-04-21 | 1994-06-07 | National Starch And Chemical Investment Holding Corporation | Redispersible waterborne pressure sensitive adhesive polymer |
-
1994
- 1994-06-08 CH CH01795/94A patent/CH689118A5/en not_active IP Right Cessation
- 1994-06-09 GB GB9411604A patent/GB9411604D0/en active Pending
- 1994-06-09 CA CA002125521A patent/CA2125521A1/en not_active Abandoned
- 1994-06-09 AU AU64657/94A patent/AU678458B2/en not_active Ceased
- 1994-06-10 GB GB9411668A patent/GB2280180B/en not_active Expired - Lifetime
- 1994-06-10 IT IT94RM000369A patent/IT1277296B1/en active IP Right Grant
- 1994-06-10 SG SG1996007659A patent/SG52673A1/en unknown
- 1994-06-10 FR FR9407149A patent/FR2706447B1/en not_active Expired - Lifetime
- 1994-06-10 MY MYPI94001491A patent/MY111223A/en unknown
- 1994-06-10 DE DE4420444A patent/DE4420444B4/en not_active Expired - Lifetime
-
1995
- 1995-12-21 US US08/579,041 patent/US5661206A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5703174A (en) * | 1995-06-21 | 1997-12-30 | W. R. Grace & Co.-Conn. | Air controlling superplasticizers |
| US6139623A (en) * | 1997-01-21 | 2000-10-31 | W. R. Grace & Co.-Conn. | Emulsified comb polymer and defoaming agent composition and method of making same |
Also Published As
| Publication number | Publication date |
|---|---|
| US5661206A (en) | 1997-08-26 |
| DE4420444A1 (en) | 1995-03-30 |
| ITRM940369A0 (en) | 1994-06-10 |
| MY111223A (en) | 1999-09-30 |
| GB2280180A (en) | 1995-01-25 |
| AU6465794A (en) | 1994-12-15 |
| IT1277296B1 (en) | 1997-11-05 |
| GB9411604D0 (en) | 1994-08-03 |
| GB9411668D0 (en) | 1994-08-03 |
| FR2706447A1 (en) | 1994-12-23 |
| CH689118A5 (en) | 1998-10-15 |
| AU678458B2 (en) | 1997-05-29 |
| GB2280180B (en) | 1997-12-24 |
| DE4420444B4 (en) | 2005-10-13 |
| ITRM940369A1 (en) | 1995-12-10 |
| FR2706447B1 (en) | 1997-07-04 |
| SG52673A1 (en) | 1998-09-28 |
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Legal Events
| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |