Method for producing poly(oxyalkylene) acrylic polymers with high solids content and low viscosity.

Abstract

The present invention provides a method for making an aqueous composition, comprising: polymerizing an aqueous monomer mixture of an aqueous medium and one or more acrylic or vinyl macromonomers containing oxyalkylene side groups in the presence of one or more carboxylic acid group-containing fluids selected from copolymerizable ethylenically unsaturated carboxylic acids, polymeric polycarboxylic acids, and mixtures thereof at a pH of 1 to 5 in the presence of one or more initiators to form an oxyalkylene side group-containing brush polymer, the polymerization being carried out at a solids content in the range of 8 to 60 wt %, and combining one or more aromatic cofactors with the aqueous composition. Additionally, the present invention provides aqueous compositions of oxyalkylene side group-containing brush polymers with two or more phase domains and substantially reduced viscosity to allow for processing with much less energy input or water waste.

Description

[Technical Field]

[0001] The present invention involves polymerizing an aqueous monomer mixture of one or more macromonomers containing oxyalkylene chain groups in the presence of a carboxylic acid group-containing fluid selected from copolymerizable ethylenically unsaturated carboxylic acids, polymeric polycarboxylic acids, or mixtures thereof. Oxyalkylene side chain group-containing brush polymer A method for preparing an aqueous composition comprising forming a compound, wherein polymerization is carried out at a pH of 1 to 5, and Oxyalkylene side chain group-containing brush polymer The present invention relates to aqueous compositions containing one or more aromatic cofactors, such as additive concentrates for use in cement. More specifically, the present invention relates to a method comprising polymerizing an aqueous monomer mixture of one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups in the presence of a carboxylic acid group-containing fluid selected from copolymerizable ethylenically unsaturated carboxylic acids, polymer polycarboxylic acids, or mixtures thereof, wherein the polymerization is carried out at a pH of 1 to 5, or preferably 1 to 4.8. More specifically, the present invention relates to one or more Oxyalkylene side chain group-containing brush polymer The present invention relates to an aqueous composition comprising one or more aromatic cofactors and one or more carboxylic acid group-containing fluids selected from copolymerized ethylenically unsaturated carboxylic acids, polymeric polycarboxylic acids, or mixtures thereof, as part of the oxyalkylene side chain groups containing a brush polymer. The compositions of the present invention find use as thickeners and water-retaining compositions, for example, preferably as aqueous additive concentrates or powder compositions for use in cement-containing compositions.

[0002] Cellulosic materials containing cellulose ethers are well known as viscosity modifying agent (VMA) additives for their thickening and water-retaining properties after the introduction of water. They can be used, for example, in concrete mixtures for cementing well casings used in oil and gas production, and in mortars from dry mixtures such as cement-based tile adhesives (CBTAs). Their water-retaining properties allow for the wet application of mortar to absorbent substrates such as stone, stone structures, concrete, concrete bricks, or clay brick walls, enabling proper setting before the mortar dries. Furthermore, the thickening and water-retaining properties provided by cellulose ethers are dose-dependent, which allows for shear reduction and thus enables highly controllable viscosity of cellulose ether-containing compositions in use. However, cellulose ethers are known to delay the cement hardening reaction, resulting in lower strength properties in cement products. It would be desirable to provide synthetic polymers as a method to increase water retention in cement products without delaying cement hardening.

[0003] Methoxypoly(ethylene glycol) methacrylate (MPEGMA) polymers combined with β-naphthalene sulfonate (BNS) have been proposed as a substitute for cellulose ether containing water-retaining additives for use in cement compositions. However, a significant increase in viscosity occurs during the synthesis of MPEGMA polymers, for example, 1 × 10⁻⁶ with only 10% by weight of solids. 4 This results in high viscosity in water exceeding cP, making commercial production impossible. Dramatically reducing the synthetic solids content to 5% by weight undesirably leads to low reactor yields and high energy demands required to remove any additional water from the composition.

[0004] Baumann et al., U.S. Patent Application Publication No. 2017 / 0240476(A1), discloses an aqueous or powder composition comprising one or more nonionic or substantially nonionic vinyl or acrylic brush polymers having pendant or side-chain polyether groups, one or more aromatic cofactors containing a combination of one or more aromatic groups having one or more phenol groups or at least one sulfuric acid group, and one or more polycarboxylate ether copolymer water-reducing agents. This composition is used in cement. However, unprocessable high viscosity, even with unacceptably low solids content, leads to the production of brush polymers and their compositions.

[0005] The present inventors sought to solve the problem of providing an aqueous polymer composition that, when used as a viscosity modifier in cement admixtures, provides thickening and water-retaining properties for cellulose ether with an acceptable solid content and without an uncontrolled increase in viscosity during composition preparation, as well as a method for preparing such an aqueous composition. [Overview of the Initiative]

[0006] According to the present invention, an aqueous composition for use as a thickening agent and water-retaining composition comprises an aqueous medium, preferably an aqueous medium substantially free of organic solvents; and one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups and polymerization residues of an initiator, in a polymerized or copolymerized form. Oxyalkylene side chain group-containing brush polymer and; With one or more aromatic cofactors; Oxyalkylene side chain group-containing brush polymer The fluid comprises, as part of a copolymerized form of an ethylenically unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid, a polymer polycarboxylic acid, preferably polyacrylic acid or polymethacrylic acid, or more preferably polyacrylic acid, or a mixture thereof, one or more carboxylic acid group-containing fluids selected from these. The composition has a pH of 1 to 5, or preferably 1 to 4.8, and furthermore, the composition is substantially salt-free or does not contain addition salts, except for any one or more initiators or their polymerization by-products. Furthermore, in the aqueous composition according to the present invention, the aqueous medium is water in an amount of at least 90% by weight, preferably at least 98% by weight, or more preferably at least 99% by weight. The aqueous composition of the present invention is Oxyalkylene side chain group-containing brush polymer The polymer may contain up to 1% by weight of the total solids content, one or more initiators such as thermal or redox initiators, or preferably one or more polymerization residues of thermal initiators.

[0007] According to the present invention, the aqueous composition is Total number of moles of carboxylic acid (The total number of moles of carboxylic acid is one or more Oxyalkylene side chain group-containing brush polymer It is defined as the sum of the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce one or more polymer polycarboxylic acids, and if any polymer polycarboxylic acid is not an addition polymer, it is defined as the total number of moles of carboxylic acid groups in the total amount of one or more polymer polycarboxylic acids. The total number of moles of oxyalkylene (the total number of moles of oxyalkylene is one or more Oxyalkylene side chain group-containing brush polymer The molar ratio of the total number of moles of one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups used to produce the macromonomer is determined by multiplying this by the average number of oxyalkylene chain groups in the total amount of acrylic or vinyl macromonomers containing oxyalkylene chain groups, as reported by the macromonomer manufacturer. This is in the range of 0.1:1 to 10:1, or preferably 0.2:1 to 5:1.

[0008] The aqueous composition of the present invention may contain a storage-stable aqueous mixture or additive concentrate having a solid content of 8% by weight or more, preferably 10% by weight or more, preferably up to 60% by weight, more preferably 45% by weight or less, more preferably 12% by weight or more, even more preferably 30% by weight or more, or in the range of 8 to 60% by weight, preferably 10 to 60% by weight, or more preferably 12 to 45% by weight. Furthermore, the aqueous composition may contain a storage-stable dry powder composition, such as for use as an additive. The dry powder composition according to the present invention may further contain hydraulic cement powder.

[0009] Preferably, according to the present invention Oxyalkylene side chain group-containing brush polymer This includes a C1-C4 alkoxypoly(C2-C4 alkylene glycol) (meth)acrylate polymer, or a copolymer in which it is copolymerized with one or more ethylenically unsaturated carboxylic acids, or more preferably, an alkoxypoly(ethylene glycol) (meth)acrylate polymer, or a copolymer in which it is copolymerized with one or more ethylenically unsaturated carboxylic acids, or even more preferably, a methoxypoly(ethylene glycol) (meth)acrylate (MPEGMA) polymer or a copolymer thereof with acrylic acid or methacrylic acid.

[0010] According to another aspect of the present invention, a method for preparing an aqueous composition involves polymerizing an aqueous monomer mixture of an aqueous medium, preferably an aqueous medium substantially free of organic solvents, and one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups, in the presence of one or more carboxylic acid group-containing fluids selected from copolymerizable ethylenically unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid, polymeric polycarboxylic acids, preferably polyacrylic acid or polymethacrylic acid, or more preferably polyacrylic acid, or mixtures thereof. Oxyalkylene side chain group-containing brush polymerIt includes forming. The polymerization can be carried out at a pH of 1 to 5, or preferably 1 to 4.8, in the presence of one or more initiators such as thermal initiators or redox initiators, preferably one or more thermal initiators. The polymerization of the present invention is carried out at a solids content in the range of 8% by weight or more, or preferably 10% by weight or more, or preferably up to 60% by weight, or more preferably 45% by weight or less, or more preferably 12% by weight or more, or even more preferably 30% by weight or more, or preferably 10 to 60% by weight, or more preferably 12 to 45% by weight. The polymerization of the present invention is carried out in the presence of up to 1% by weight, or 0.01 to 0.6% by weight, of one or more initiators based on the total weight of the monomers used to produce one or more Oxyalkylene side chain group-containing brush polymer In addition, in the polymerization of the present invention, the aqueous medium of the aqueous monomer mixture is at least 90% by weight, or preferably at least 98% by weight, or more preferably at least 99% by weight water. The method according to the present invention may further include drying the aqueous brush copolymer composition to form a dry powder, or may further include combining one or more aromatic cofactors with the aqueous composition.

[0011] Furthermore, according to the polymerization of the aqueous monomer mixture of the present invention, The total molar number of carboxylic acids (the total molar number of carboxylic acids is determined as the sum of the total molar number of ethylenically unsaturated carboxylic acid monomers used in the polymerization of one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups and the total molar number of carboxylic acid groups used to produce one or more polymeric polycarboxylic acids. When any polymeric polycarboxylic acid is not an addition polymer, it is the total molar number of carboxylic acid groups in one or more polymeric polycarboxylic acids) of The molar ratio of the total number of moles of oxyalkylene, determined as the total moles of oxyalkylene used to produce one or more brush polymers of an acrylic or vinyl macromonomer containing an oxyalkylene chain group, or the average number of oxyalkylene chain groups in the total amount of acrylic or vinyl macromonomer containing an oxyalkylene chain group reported by the macromonomer manufacturer, multiplied by the total moles of acrylic or vinyl macromonomer, is in the range of 0.1:1 to 10:1, or preferably 0.2:1 to 5:1.

[0012] According to the polymerization of the aqueous monomer mixture of the present invention, Oxyalkylene side chain group-containing brush polymer Based on the total weight of, the total amount of acrylic or vinyl macromonomer containing an oxyalkylene side chain group is Oxyalkylene side chain group-containing brush polymer 20 to 100% by weight, or preferably 30 to 98% by weight, or preferably 97% by weight or less, or more preferably 50% by weight or more, or even more preferably 65% by weight or more, based on the total weight of the monomers used to produce.

[0013] According to the polymerization of the aqueous monomer mixture of the present invention, based on the total weight of one or more Oxyalkylene side chain group-containing brush polymer In addition to one or more carboxylic acid group-containing fluids as solids, the total amount of one or more polymeric polycarboxylic acids is in the range of 2 to 80% by weight, or preferably 2 to 70% by weight, or preferably 50% by weight or less, or more preferably 35% by weight or less, or even more preferably 3% by weight or more. Preferably, when polymerizing the aqueous monomer mixture, it is substantially salt-free or contains no additional salts, excluding any one or more initiators or their polymerization by-products.

[0014] Preferably, in the polymerization of the present invention, the aqueous monomer mixture comprises one or more acrylic or vinyl macromonomers, including C1-C4 alkoxypoly(C2-C4 alkylene glycol) (meth)acrylate polymers, or a mixture thereof with one or more ethylenically unsaturated carboxylic acids; more preferably, it comprises alkoxypoly(ethylene glycol) (meth)acrylate polymers, or a mixture thereof with one or more ethylenically unsaturated carboxylic acids; and even more preferably, it comprises methoxypoly(ethylene glycol) (meth)acrylate (MPEGMA) polymers, or a mixture thereof with acrylic acid or methacrylic acid.

[0015] According to the method of the present invention, after polymerization, the method may further include drying or obtaining each of one or more brush polymers and one or more aromatic cofactors as separate powders, and then mixing them to form a dry powder blend. Alternatively, the method according to the present invention may, after polymerization, add one or more to the aqueous composition. Oxyalkylene side chain group-containing brush polymer The method may include a wet process in which one or more aromatic cofactors, or mixtures thereof, are added in any order to form a stable aqueous composition. Oxyalkylene side chain group-containing brush polymer Alternatively, the method may further involve adding one or more polycarboxylate ether copolymer water-reducing agents to an aqueous composition of a mixture thereof with one or more aromatic cofactors.

[0016] The singular terms “a,” “an,” and “the” include plural referents unless the context makes it clear otherwise. Unless otherwise specified, terms used herein have the same meaning as those commonly understood by those skilled in the art.

[0017] Unless otherwise specified, terms containing parentheses refer, alternatively, to the entire term as if the parentheses were absent, the same term without parentheses, and any combination of each alternative. Thus, the term "(meth)acrylate" alternatively includes methacrylate, acrylate, or mixtures thereof.

[0018] All endpoints covering the same components or properties include the endpoint and can be combined independently. Therefore, for example, the disclosed range of solids content in the range of 8% by weight or more, preferably 10% by weight or more, more preferably 12% by weight or more, preferably up to 60% by weight, or even more preferably 30% by weight or more, or preferably up to 60% by weight, or more preferably 45% by weight or less, or even more preferably 30% by weight or more, or preferably 10-60% by weight, or more preferably 12-45% by weight, or even more preferably 30-45% by weight is equivalent to 8%-60% by weight, or 8-10% by weight, or 8-12% by weight, or 8-30% by weight % means any or all of the solids content in the range of 8 to 45% by weight, preferably 10 to 60% by weight, more preferably 12 to 60% by weight, more preferably 12 to 45% by weight, even more preferably 30 to 45% by weight, preferably 10 to 12% by weight, preferably 10 to 30% by weight, preferably 10 to 45% by weight, more preferably 12 to 45% by weight, more preferably 12 to 30% by weight, even more preferably 30 to 45% by weight, more preferably 30 to 60% by weight, or preferably 45 to 60% by weight.

[0019] Unless otherwise specified, the temperature and pressure conditions are room temperature (23°C) and standard pressure (101.3 kPa), also known as "ambient conditions." In addition, unless otherwise specified, all conditions include 50% relative humidity (RH).

[0020] All cited ranges are comprehensive and combinable. For example, the disclosure of 0.25–0.5% by weight, or preferably 0.35–0.45% by weight, includes all of the following: 0.25–0.5% by weight, or preferably 0.35–0.45% by weight, or 0.25–0.35% by weight, or 0.25–0.45% by weight, or 0.35–0.5% by weight, or 0.45–0.5% by weight.

[0021] As used herein, the terms "acrylic or vinyl" refer to addition polymerizable monomers or addition polymers of α,β-ethylenically unsaturated monomers, such as alkyl and hydroxyalkyl (meth)acrylates, vinyl ethers, ethylenically unsaturated carboxylic acids, alkyl (meth)acrylamides, or monomers containing oxyalkylene chain groups, such as methoxy poly(ethylene glycol)(meth)acrylate (mPEG(M)A) or poly(ethylene glycol)(meth)acrylate (PEG(M)A) and allyl poly(ethylene glycol) (APEG).

[0022] As used herein, the term “aqueous” means that the continuous phase or medium is water and a water-miscible compound in an amount of 0 to 10% by weight based on the weight of the medium. Preferably, “aqueous” means water.

[0023] Where used herein, unless otherwise indicated, the term “average number of oxyalkylene chain groups” refers to the number of oxyalkylene groups in any given acrylic or vinyl macromonomer having oxyalkylene chain groups, as shown in the manufacturer’s literature for a given macromonomer. Since this is an average number, the actual number of oxyalkylene chain groups represents the distribution within each material batch, and the average number of oxyalkylene chain groups in a mixture of two or more such macromonomers depends on the relative amount of each selected macromonomer having oxyalkylene chains to the total amount of macromonomers in the monomer mixture. For example, in a 50:50 (mol / mol) mixture of alkoxy poly(ethylene glycol)(meth)acrylate having 10 ethylene glycol groups per oxyalkylene chain and alkoxy poly(propylene glycol)(meth)acrylate having 6 propylene glycol groups per oxyalkylene chain, the average number of oxyalkylene groups is 8 per side chain.

[0024] As used herein, the term "based on the total weight of monomers" refers to the amount of polymer or a portion thereof compared to the total weight of the addition monomers used to produce a polymer, such as an acrylic monomer.

[0025] As used herein, the terms “dry mixture” or “dry powder” mean a storage-stable powder containing cement, cellulose ether, any other polymer additives, and any fillers and dry additives. The dry mixture is free of water; therefore, it is storage-stable.

[0026] As used herein, the terms “fluid” or “multiple fluids” refer to a composition of a flowing substance, regardless of the state of the substance or phase. Fluids may include suspensions, dispersions, solutions, flowing solids or amorphous materials, aerosols, or gases.

[0027] As used herein, the term “side chain” group refers to a side chain of a polymer, or a group that is covalently bonded to the polymer backbone and is not a terminal group.

[0028] As used herein, unless otherwise indicated, the term “polymer” includes both homopolymers and copolymers derived from two or more different monomers, as well as segmented copolymers and block copolymers.

[0029] As used herein, the term “storage stability” means that, for a given powder additive composition, when left on a shelf at room temperature and standard pressure, the powder does not block after 5 days, or preferably after 10 days, and for a given aqueous additive composition, the liquid composition does not become cloudy, separate, or precipitate.

[0030] As used herein, the term “substantially free of organic solvents” means that the composition contains any one or more organic solvents in less than 0.5% by weight based on the total weight of the composition, preferably no added organic solvents, or more preferably one or more organic solvents in an amount of 1000 ppm or less.

[0031] As used herein, the phrase “total number of moles of carboxylic acid groups” means the number of moles of ethylenically unsaturated carboxylic acid monomers used to produce a given polymer, as determined by aqueous titration of the polymer to KOH to neutralize the composition to pH 7.0, or, if not an addition polymer, the total number of moles of carboxylic acid groups in one or more polymeric polycarboxylic acids.

[0032] When used in this specification, Oxyalkylene side chain group-containing brush polymer The term "weight-average molecular weight" in this context refers to the weight-average value obtained from the weight distribution determined by gel permeation chromatography (GPC) using poly(acrylic acid) standards necessary for analyzing the molecular weight of a given polymer.

[0033] Where used herein, unless otherwise indicated, the term “weight %” means weight percentage based on the denominator shown.

[0034] As used herein, the terms “total solids,” “solid,” or “as a solid” refer to the total amount of any or all of the nonvolatile components or materials present in a given composition, including synthetic polymers, monomers, natural polymers, acids, defoamers, hydraulic cements, fillers, inorganic materials, and additives such as other nonvolatile materials and initiators. Water, ammonia, and volatile solvents are not considered solids.

[0035] According to the present invention, a polymerization method in an aqueous medium involves polymerizing monomers that form a solution in water. However, the polymerization products of the method of the present invention behave in a manner similar to two-phase polymerization, such as stable suspension polymerization or emulsion polymerization, and furthermore, aqueous compositions containing brush copolymers, such as those produced by this method, behave like emulsions or stable suspensions. At a pH below the pKa of the ethylenically unsaturated carboxylic acid in the aqueous monomer mixture or brush polymer composition of the present invention, an associative complex is formed between the protonated carboxylic acid group and the oxyalkylene group of the oxyalkylene side chain of the brush polymer. Therefore, the present invention enables the polymerization of highly water-soluble acrylic or vinyl macromonomers containing oxyalkylene chain groups with an acceptable high solids content while minimizing the use of energy and water in the process. Examples of suitable macromonomers include methoxypoly(ethylene glycol) methacrylate (MPEGMA).

[0036] The present invention enables aqueous monomer mixtures, their polymerization, and substantial viscosity reduction in oxyalkylene side chain groups contained in aqueous brush polymer compositions. For comparison, aqueous compositions of the same monomer mixture or its brush polymer were used, either containing a macromonomer alone or mixed with one or more monomers having less than 1% by weight water solubility in deionized (DI) water at 23°C and 101.3 kPa pressure, such as alkyl (meth)acrylate, styrene, or vinyl ester monomers, such as methyl methacrylate (MMA). Polymerization by the method of the present invention yielded 10% by weight MPEGMA total polymer solids, 10 4 cP over ~10 2 This enabled an in-process viscosity reduction to less than cP. Furthermore, in another example of the method of the present invention, an aqueous monomer mixture containing 15% by weight of methacrylic acid (MAA) based on the total weight of monomers was subjected to 10% by weight of MPEGMA total monomer / polymer solids before, during, and after polymerization. 4 cP over ~10 2This enabled in-process viscosity reduction to below cP. In both of the above examples, 15% by weight of methyl methacrylate (MMA) was used in the comparative MPEGMA aqueous monomer mixture / brush polymer.

[0037] In particular, the present inventors have discovered polymerizable aqueous monomer mixtures of acrylic or vinyl macromonomers containing oxyalkylene chain groups, and aqueous compositions of brush polymers of the same macromonomers in a (co)polymerized form having two or more phase domains, similar to emulsions or suspensions. The aqueous compositions of brush polymers prepared from the aqueous monomer mixtures of the present invention behave similarly to the aqueous monomer mixtures from which they are prepared. The aqueous brush polymer compositions according to the present invention include one or more carboxylic acid group-containing fluids selected from polymer polycarboxylic acids such as polyacrylic acid or poly(methacrylic acid) (pMAA), mixtures thereof, copolymerized ethylenically unsaturated carboxylic acids such as copolymerized methacrylic acid (MAA), or combinations thereof. In addition, the present invention provides a method for preparing an aqueous brush polymer composition, comprising polymerizing one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups in the presence of one or more carboxylic acid group-containing fluids selected from one or more polymer polycarboxylic acids or copolymerizable ethylenically unsaturated carboxylic acids, or combinations thereof.

[0038] One or more acrylic or vinyl materials according to the present invention Oxyalkylene side chain group-containing brush polymer This can be selected from a homopolymer of acrylic or vinyl macromonomers having oxyalkylene chain groups, or a copolymer of one or more macromonomers and one or more ethylenically unsaturated carboxylic acid monomers. The aqueous composition of the present invention may not have a polymer polycarboxylic acid if it contains a brush copolymer containing one or more ethylenically unsaturated carboxylic acids in copolymer form.

[0039] The acrylic or vinyl brush polymer of the present invention may include any such polymer having oxyalkylene side chain groups, preferably poly(ethylene glycol) groups or alkoxypoly(ethylene glycol) groups. The oxyalkylene side chain groups may be poly(alkylene glycol) side chains terminated with, for example, hydroxyl, methyl, ethyl, or any other nonionic group that is uncharged at the pH of the composition. The side chains may be alkylene glycols (EO, PO, BO, etc.) or mixtures thereof. Suitable oxyalkylene side chain groups can be selected from poly(alkylene glycols), e.g., poly(ethylene glycol), poly(propylene glycol), poly(butylene glycol) or two or more copolyethers thereof, alkoxypoly(alkylene glycols), e.g., methoxypoly(alkylene glycol), ethoxypoly(alkylene glycol) and combinations thereof. Preferably, the oxyalkylene side chain groups in the vinyl or acrylic brush polymer of the present invention have 5 to 25, more preferably 7 to 15, ether groups or alkylene glycol groups. More preferably, the ether group is an ethoxy (-CH2CH2O-) or (EO) group.

[0040] The main chain of the vinyl or acrylic brush polymer of the present invention may contain, but is not limited to, repeating units of one or more ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid. The vinyl or acrylic brush polymer of the present invention may also be synthesized using any other unsaturated monomer, such as vinyl-, allyl-, or isoprenyl- groups, in an amount up to 10% by weight of the monomer solids.

[0041] The present invention provides acrylic or vinyl macromonomers containing oxyalkylene chain groups, and acrylic or vinyl Oxyalkylene side chain group-containing brush polymer In this case, one or more macromonomers or Oxyalkylene side chain group-containing brush polymerThe average number of oxyalkylene side chain groups is in the range of 1.5 to 100 ether groups, for example, 2 or more, or 3 or more, or 1.5 to 50 ether groups, preferably 2 to 40, more preferably 3 to 40, more preferably 5 to 25 ether groups, or even more preferably 7 to 15 ether groups. Preferably, the present invention Oxyalkylene side chain group-containing brush polymer The macromonomer used to produce the product has a total of 5 to 25 alkylene glycol or ether units in the oxyalkylene group, for example, 7 or more alkylene glycol or ether units, or up to 15 alkylene glycol or ether units.

[0042] Suitable acrylic or vinyl Oxyalkylene side chain group-containing brush polymer The polymer may be a polymerization product of one or more acrylic or vinyl macromonomers having oxyalkylene chain groups, in an amount of 20-100% by weight, preferably 30-100% by weight, preferably 40-70% by weight, preferably 50% or more by weight, preferably up to 98% by weight, or more preferably 65-100% by weight, for example 65-98% by weight, based on the total weight of monomers used to produce the polymer. Preferably, the remainder of the monomers used to produce the polymer is one or more ethylenically unsaturated carboxylic acids.

[0043] Suitable acrylic or vinyl macromonomers for use in the polymerization or preparation of the brush polymer of the present invention may be any macromonomer having a poly(alkylene glycol) chain with a desired number of ether or alkylene glycol units. Preferably, the acrylic or vinyl macromonomers used to prepare the vinyl or acrylic brush polymer of the present invention are methacrylate monomers having oxyalkylene chain groups such as poly(ethylene glycol)(meth)acrylate, alkoxy poly(alkylene glycol)(meth)acrylate, for example, C1-C4 alkoxy poly(C2-C4 alkylene glycol)(meth)acrylate, hydrophobic C 12 ~C 25It is an alkoxypoly(alkylene glycol)(meth)acrylate or a mixture thereof. More preferably, one or more acrylic or vinyl macromonomers having an oxyalkylene chain group include poly(ethylene glycol)(meth)acrylate, methoxypoly(ethylene glycol)(meth)acrylate or a mixture thereof.

[0044] Suitable acrylic or vinyl macromonomers are poly(ethylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 ethylene glycol units, poly(propylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 propylene glycol units, C 12 ~C 25 alkoxypoly(ethylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 ethylene glycol units, C 12 ~C 25Alkoxy poly(propylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 propylene glycol units, polybutylene glycol(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol units, poly(ethylene glycol)-(polypropylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol repeating units, poly(ethylene glycol)-poly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol units, poly(propylene glycol)-poly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol units, poly(ethylene glycol)-poly(propylene glycol)-poly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol units, methoxypoly (ethylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, preferably 5 to 25, ethylene glycol units, methoxypoly(propylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, preferably 5 to 25, propylene glycol units, methoxypoly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, preferably 5 to 25, total alkylene glycol units, methoxypoly(butylene glycol)mono(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, total alkylene glycol units, methoxypoly(ethylene glycol)-poly(propylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, total alkylene glycol units, methoxypoly(ethylene glycol)-poly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, total alkylene glycol units,Methoxypoly(propylene glycol)-poly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol units, Methoxypoly(ethylene glycol)-poly(propylene glycol)-poly(butylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50 total alkylene glycol units, Ethoxypoly(ethylene glycol)(meth)acrylate or its corresponding (meth)acrylamide having 2 to 50, or preferably 5 to 25, ethylene glycol units, Poly(ethylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 ethylene glycol units, Poly(propylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 propylene glycol units, Poly(ethylene glycol)-poly It may contain (propylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 total alkylene glycol units, poly(ethylene glycol)-poly(butylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 total alkylene glycol units, poly(propylene glycol)-poly(butylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 total alkylene glycol units, methoxypoly(ethylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 ethylene glycol units, methoxypoly(propylene glycol)(meth)allyl ether or monovinyl ether having 2 to 50 propylene glycol units, and the corresponding monoesters, monoamides, diesters and diamides of itaconic acid or maleic acid, or mixtures of any of the aforementioned.

[0045] More specifically, suitable acrylic or vinyl macromonomers having oxyalkylene chain groups are poly(ethylene glycol) 4-40 (Meth)acrylate, for example, poly(ethylene glycol) 4-40 (Meth)acrylate, alkoxypoly(alkylene glycol) 4-40(Meth)acrylates, for example, C1-C4 alkoxy poly(C2-C4 alkylene glycols) 4-40 (Meth)acrylate, C1-C4 alkoxypoly(C2-C4 alkylene glycol) 4-40 (Meth)acrylate alkoxypoly(ethylene glycol) 4-40 (meth)acrylate; or hydrophobic C 12 ~C 25 Alkoxypoly(alkylene glycol) 4-40 It may contain one or more (meth)acrylates. The acrylic or vinyl macromonomer is preferably a C1-C4 alkoxy poly(C2-C4 alkylene glycol). 4-40 (meth)acrylate and poly(ethylene glycol) 1.5-100 (meth)acrylate, more preferably poly(ethylene glycol) 4-40 (Meth)acrylate and C1-C4 alkoxypoly(ethylene glycol) 4-40 (Meth)acrylate, or more preferably methoxypoly(C2-C4 alkylene glycol) 4-40 (meth)acrylate and poly(ethylene glycol) 4-40 Contains (meth)acrylate.

[0046] Examples of suitable acrylic or vinyl brush polymers of the present invention are (co)polymers of an acrylate or acrylamide macromonomer having an oxyalkylene chain group such as poly(ethylene glycol) and one or more ethylenically unsaturated carboxylic acid monomers.

[0047] Oxyalkylene side chain group-containing brush polymerSuitable ethylenically unsaturated carboxylic acids for use in the preparation of the aqueous brush polymer of the present invention containing a carboxylic acid group include, for example, one or more monomers having a carboxylic acid such as methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, citraconic acid, mesaconic acid, 2-methylitaconic acid, cyclohexenedicarboxylic acid, α,β-methyleneglutaric acid, monoalkyl maleic acid, and monoalkyl fumarate, as well as ethylenically unsaturated anhydrides, such as maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, acrylic anhydride, and methacrylic anhydride.

[0048] Furthermore, the aqueous brush polymer composition according to the present invention may contain one or more comonomers in copolymer form that have water solubility of less than 1% by weight in deionized (DI) water at 23°C and a pressure of 101.3 kPa. Preferred comonomers are C1-C 12 The composition may include any alkyl (meth)acrylate, for example, lower alkyl (C1-C8) alkyl (meth)acrylate, such as methyl methacrylate (MMA), ethyl acrylate (EA), and 2-ethylhexyl methacrylate (2-EHA), hydroxyalkyl (meth)acrylate, such as hydroxyethyl methacrylate, arylene, such as styrene, vinyl ester monomers, and mixtures thereof. Such comonomers may include up to 10% by weight of solids, or preferably up to 5% by weight of solids, based on the total weight of monomers used to produce the brush polymer. If the aqueous composition includes one or more polymer polycarboxylic acids as one or more carboxylic acids, the amount of such comonomers may be greater, for example, up to 80% by weight, or for example up to 40% by weight, based on the total weight of monomers used to produce the brush polymer.

[0049] The present invention is aqueous Oxyalkylene side chain group-containing brush polymerThe polymer may be crosslinked, but is preferably not. Crosslinking can be achieved by methods such as including in the aqueous monomer mixture 0.01 to 1% by weight, or preferably up to 0.1% by weight, one or more diethylene unsaturated crosslinking agent monomers, such as (poly)ethylene glycol dimethacrylate or (poly)ethylene glycol diacrylate, (poly)glycol di(meth)acrylate, allyl acrylate or allyl methacrylate, or a combination thereof, in an aqueous monomer mixture based on the total weight of the monomers used to produce the polymer.

[0050] Preferably, one or more of the present invention Oxyalkylene side chain group-containing brush polymer To ensure that the aqueous composition exhibits water retention and not water loss, such polymers contain polymerization products of any salt-containing monomer, such as ethylenically unsaturated carboxylate monomers, in amounts of less than 0.1% by weight, or preferably less than 0.05% by weight, based on the total weight of the monomers used to produce the brush polymer.

[0051] According to the aqueous composition of the present invention, Oxyalkylene side chain group-containing brush polymer It may have a weight-average molecular weight (relative molecular weight, Mw) of 100,000 to 50,000,000 g / mol, preferably 250,000 or more, more preferably 300,000 or more, preferably 20,000,000 or less, or more preferably 10,000,000 or less.

[0052] The polymerization method and aqueous composition according to the present invention may provide one or more polymer polycarboxylic acids, which are any polymers of one or more ethylenically unsaturated carboxylic acids, or, if not addition polymers, may include carboxylic acid-functional polymers such as poly(aspartic acid). The polymer, in copolymer form, includes one or more monomers having carboxylic acids such as methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, citraconic acid, mesaconic acid, 2-methylitaconic acid, cyclohexenedicarboxylic acid, α,β-methyleneglutaric acid, monoalkyl maleic acid, and monoalkyl fumaric acid, and ethylenically unsaturated anhydrides, such as maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, acrylic anhydride, and methacrylic anhydride. Such monomers should be used in an amount that provides 50 to 100% by weight, or preferably 80% by weight or more, of acid copolymerization units based on the weight of all monomers used to produce the polymer. The remainder of the polymer polycarboxylic acid may, in addition to copolymer acid group-containing units, include hydroxyl group-containing copolymer units and, optionally, additional ethylenically unsaturated monomer copolymer units. Therefore, copolymers and copolymer polyacids may contain hydroxyl group-containing ethylenically unsaturated monomers as copolymer units and, optionally, additional ethylenically unsaturated monomers as copolymer units.

[0053] According to the present invention Oxyalkylene side chain group-containing brush polymer In a method for preparing an aqueous composition, polymerization includes conventional aqueous addition polymerization. Polymerization may proceed by a thermal initiator or a redox initiator, or preferably by conventional free radical addition polymerization in the presence of a thermal initiator, such as aqueous emulsion polymerization in the presence of one or more persulfates or peracids. Polymerization may be carried out as shots of an aqueous monomer mixture added together or separately, or by stepwise addition of one or more monomers in an aqueous monomer mixture added together or separately in one or more steps. Polymerization can be carried out in an aqueous medium at a temperature of 40 to 80°C, or more preferably 71°C or lower. Preferably, according to the present invention Oxyalkylene side chain group-containing brush polymerMethods for producing it include conventional free radical addition aqueous polymerization, such as shot polymerization in which the aqueous monomer mixture is added to the reaction vessel all at once.

[0054] Most preferably, the present invention Oxyalkylene side chain group-containing brush polymer Polymerization to form is carried out in an aqueous medium using a thermal initiator at a temperature of 40 to 75°C, or most preferably 71°C or lower. Most preferably, the present invention Oxyalkylene side chain group-containing brush polymer Polymerization to form the polymer is carried out in an aqueous medium using a thermal initiator at a concentration of 0.05% to 1% by weight, or more preferably 0.2% by weight or less, based on the total weight of the monomers (monomer solids) used to produce the polymer.

[0055] One or more Oxyalkylene side chain group-containing brush polymer The aqueous composition has a pH of 5 or less, for example, 1 to 5, or preferably 4.8 or less, or for example, 1 to 4.8.

[0056] One or more Oxyalkylene side chain group-containing brush polymer The aqueous composition contains less than 1% by weight of salt based on the total solids weight of the composition, or preferably does not contain addition salts except as part of the polymerization initiator or its polymerization by-product. If salt is used, it is preferably a monovalent metal salt, such as a sodium salt or an ammonium salt.

[0057] According to the aqueous polymerization method of the present invention, one or more polymer polycarboxylic acids comprise a polymer or copolymer of one or more ethylenically unsaturated carboxylic acids in copolymer form. Suitable ethylenically unsaturated carboxylic acids include, for example, methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, citraconic acid, mesaconic acid, 2-methylitaconic acid, cyclohexenedicarboxylic acid, α,β-methyleneglutaric acid, monoalkyl maleic acid, and monoalkyl fumaric acid, as well as ethylenically unsaturated anhydrides, such as maleic anhydride, itaconic anhydride, citraconic anhydride, mesaconic anhydride, acrylic anhydride, and methacrylic anhydride. Preferably, the ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid. Such monomers should be used in the copolymer or copolymer polyacid in an amount that provides 65 to 100% by weight, preferably 80 to 100% by weight, of acid copolymerization units, based on the weight of the monomers used to produce the polymer polycarboxylic acid. The remainder of one or more polymer polycarboxylic acids (apart from copolymerized acid group-containing units) may contain hydroxyl group-containing ethylenically unsaturated monomers, such as hydroxyethyl methacrylate, and amide group-containing monomers, such as (meth)acrylamide, in copolymerized form. Polymer polycarboxylic acids can be prepared by conventional aqueous addition polymerization in the presence of one or more initiators.

[0058] According to the method and aqueous composition of the present invention, the polymer polycarboxylic acid contains less than 1% by weight of the carboxylate salt based on the total weight of the monomers used to produce the polymer polycarboxylic acid, or preferably does not contain the salt.

[0059] One or more aromatic cofactors of the present invention may be any compound, polymer, or oligomer having one and up to 1,000,000, or up to 100,000, preferably two or more, or more preferably three or more aromatic groups or phenolic groups (e.g., phenolic groups or naphthol groups), wherein if the aromatic cofactor has aromatic groups other than phenolic groups, it further includes at least one sulfuric acid group. Preferably, the aromatic cofactor of the present invention has one or more aromatic groups and at least one sulfuric acid group, or more preferably two or more such combinations. The cofactors may include beta naphthalene sulfonate (BNS) resins, styrene sulfonate (co)polymers, and lignin sulfonates, as well as phenolic resins and tannins. Aromatic cofactors may include, for example, poly(naphthalene sulfonate)formaldehyde condensate resins or polymers, such as β-naphthalene sulfonate formaldehyde condensate polymers or β-naphthalene sulfonate resins (BNS), poly(styrene-co-styrene sulfonate) copolymers, catechol tannins, phenolic resins, such as phenol formaldehyde resins, polyphenols, naphthol, such as 2-naphthol, and mixtures thereof. Preferably, the aromatic cofactor is branched, and more preferably BNS.

[0060] The aromatic cofactor of the present invention has one or more aromatic groups or phenolic groups in 10 to 100%, preferably 30 to 100%, or more preferably 50 to 100% or 60 to 100% of the repeating units of the oligomer or polymer. For example, each of the phenol formaldehyde resin and the naphthalene sulfonate aldehyde resin can be considered a homopolymer or oligomer having phenolic groups or aromatic groups in 100% of its repeating units. Preferably, in an oligomer or polymer having a combination of aromatic and sulfuric acid groups, more than 30% by weight, preferably more than 50% by weight of the aromatic groups are accompanied by sulfuric acid groups, such as poly(styrene-co-styrene sulfonate) copolymer, which is a copolymer product of more than 30 mol% styrene sulfonate based on the total number of moles of vinyl monomer used to produce the copolymer.

[0061] The aromatic cofactor may be linear, as in styrene sulfonate-containing polymers, and preferably branched, as in any condensation resin such as naphthalene sulfonate aldehyde or phenol aldehyde condensate, tannin, or lignin sulfonate. When the cofactor is linear, it preferably has a molecular weight of 600,000 to 10,000,000.

[0062] Suitable examples of aromatic cofactors are commercially available, including MELCRETE® 500 powder (BASF, Ludwigshafen, DE) and its liquid version, MELCRETE® 500L liquid (BASF). Both are BNS polymers or oligomers. MELCRETE® 500 polymer is a condensate of sulfonated naphthalene and formaldehyde.

[0063] The compositions of the present invention can be used in wet (aqueous) or dry powder form. The wet aqueous composition is used with wet cement, and the dry powder is used with dry cement. The aromatic cofactors of the present invention can be used in wet or dry form. Oxyalkylene side chain group-containing brush polymerAdditive compositions can be prepared by combining them wet or dry. Drying to form a dry powder composition can be carried out by spray drying of any polymer or cofactor aqueous composition or both, preferably by heating in a vacuum oven, or by an azeotropic method as described in the prior art before combining with cement powder.

[0064] In the composition of the present invention, Oxyalkylene side chain group-containing brush polymer The brush polymer and one or more aromatic cofactors may be combined such that, at the time of use, the total weight of the brush polymer relative to the total weight of the cement admixture as a solid is in the range of 0.05 to 2% by weight, or preferably 0.1 to 1% by weight.

[0065] The aqueous compositions of the present invention can be used by mixing them with a hydraulic binder or cement and water to produce concrete or cement mixtures, or by drying them and mixing them with dry cement before combining them with water at the time of use. Oxyalkylene side chain group-containing brush polymer Prior to the addition of aromatic cofactors and, if used, any polycarboxylate ether copolymer water-reducing agents, they can be combined with hydraulic cement in any way, provided that they are not added to the wet cement. Preferably, the compositions of the present invention comprise a single aqueous composition to be added to wet concrete or cement.

[0066] If the composition of the present invention further comprises a hydraulic or water-curable inorganic cement, the total amount of one or more brush polymers is in the range of 0.05 to 2% by weight, preferably 0.1 to 1% by weight, or more preferably 0.2 to 0.5% by weight, based on the total cement solid, as a solid. Furthermore, the composition may contain one or more aromatic cofactors in the range of 0.1 to 10% by weight, preferably 0.2 to 5% by weight, or more preferably 0.2 to 2% by weight, based on the total cement solid, as a solid.

[0067] The aqueous composition or dried powder of the present invention may further contain a water-reducing agent such as a cellulose ether, such as HPMC and / or HEMC (hydroxyethyl methyl cellulose), or a polycarboxylate ether. The total amount of any polycarboxylate ether copolymer water-reducing agent in the composition may be in the range of 0.1 to 10% by weight, or preferably 0.2 to 5% by weight, of the total cement solids of the cement admixture.

[0068] The compositions of the present invention may also contain, for example, conventional additives in wet or dry forms such as cement hardening accelerators and retarders, air entrainers or defoamers, shrinkage agents and wetting agents, surfactants, particularly nonionic surfactants, spreading agents, mineral oil dust suppressants, biocides, plasticizers, organosilanes, poly(dimethylpolysiloxanes) (PDMS) and emulsified PDMS, silicone oils and ethoxylated nonionic substances as defoamers; and coupling agents such as epoxysilanes, vinylsilanes and hydrophobic silanes. [Examples]

[0069] The present invention is illustrated by the following examples. Unless otherwise indicated, all parts and percentages are by weight, all temperatures are in °C, and all preparation and test procedures are carried out under ambient conditions of room temperature of 23 °C and pressure (1 atm). The following abbreviations are used in the following examples and in Tables 1, 2 and 3: RDP: Redispersible Polymer Powder, MPEGMA: Methoxypoly(ethylene glycol) methacrylate, MAA: Methacrylic acid, AA: Acrylic acid, MMA: Methyl methacrylate, EO: Ethylene oxide.

[0070] All chemicals other than AA, MMA, and MAA were purchased from Sigma-Aldrich and used without further purification.

[0071] Synthesis Example 1: A poly(acrylic acid) additive with a polymer polycarboxylic acid solid content of 50 wt% was synthesized in a 1 L round-bottom flask. 103.5 g of water was added under a flow of nitrogen gas, and the mixture was stirred at 170 rpm and heated to 73°C. Next, 1.25 g of 0.15 wt% iron(II) sulfate solution and 2.83 g of sodium metabisulfite were added in 5.94 g of water. Then, 40.76 g of sodium metabisulfite dissolved in 63.31 g of water, 150 g of AA rinsed with 3.5 g of water, and 0.57 g of sodium persulfite dissolved in 8.5 g of water were simultaneously added and supplied over 70, 90, and 95 minutes, respectively. The temperature was gradually raised to 75°C, and after the supply of sodium persulfate solution was completed, the temperature was maintained at 75°C for a further 15 minutes. Following this holding period, 0.21 g of sodium persulfate dissolved in 10.0 g of water was added over 10 minutes, and the reactor was then held at 75°C for a further 20 minutes. After cooling to 60°C, 4.8 g of 35 wt% hydrogen peroxide was added over 2 minutes, and the reactor was then held at 60°C for a further 10 minutes. Subsequently, the reactor was cooled to room temperature.

[0072] Synthesis Example 2: Brush polymer composition containing oxyalkylene side chain groups and a separate polymer polycarboxylic acid. The brush polymers of Comparative Example 1 and Examples 1, 2, and 3 of the present invention were synthesized in a 300 mL flat-bottom flask and stirred at 120 rpm using an impeller. 12.8 g of MPEGMA-500 (having an average of 9 EO units and a molecular weight of 500 g), 2.2 g of MMA, and water and a 50 wt% polyacrylic acid solution from Synthesis Example 1 were added to the reactor. The solution was heated to 70°C for 1 hour under nitrogen. Next, a solution of 0.030 g of ammonium persulfate in 1.875 g of water was added and rinsed with an additional 1.875 g of water. The temperature was maintained at 70°C for 2 hours, then an additional solution of 0.030 g of ammonium persulfate in 1.875 g of water was added and rinsed with an additional 1.875 g of water. The temperature was again maintained at 70°C for 2 hours, then cooled to room temperature. The composition and polymer polycarboxylic acid of this synthesis example 2 are shown in Table 1 below.

[0073] Synthesis Example 3: Brush Polymer Composition Containing Oxyalkylene Side Chain Groups and Carboxylic Acid in Copolymer Form The brush polymer of Example 4 of the present invention was synthesized in a 1 L round-bottom flask. 451.1 g of water, 21.3 g of MPEGMA-500, and 3.7 g of MAA were added to the reactor, and each monomer was rinsed with an additional 6.2 g of water. The solution was heated to 70°C for 1 hour under nitrogen. Next, a solution of 0.050 g of ammonium persulfate in 3.124 g of water was added, and the mixture was rinsed with an additional 3.124 g of water. The temperature was maintained at 70°C for 2 hours, and then an additional solution of 0.050 g of ammonium persulfate in 3.124 g of water was added, and the mixture was rinsed with an additional 3.124 g of water. The temperature was again maintained at 70°C for 2 hours, and then cooled to room temperature. The composition prepared by this Synthesis Example 3 is shown in Table 3 below.

[0074] The brush polymer of Example 5 of the present invention was synthesized in a 1 L round-bottom flask. 401.6 g of water, 42.5 g of MPEGMA-500, and 7.5 g of MAA were added to the reactor, and each monomer was rinsed with an additional 12.5 g of water. The solution was heated to 70°C for 1 hour under nitrogen. Next, a solution of 0.100 g of ammonium persulfate in 6.249 g of water was added, and the mixture was rinsed with an additional 6.249 g of water. The temperature was maintained at 70°C for 2 hours, and then an additional solution of 0.100 g of ammonium persulfate in 6.249 g of water was added, and the mixture was rinsed with an additional 6.249 g of water. The temperature was again maintained at 70°C for 2 hours, and then cooled to room temperature. The composition prepared by this Synthesis Example 3 is shown in Table 3 below.

[0075] [Table 1] * -A comparative example is shown.

[0076] Test method: The following test method was used: Solids content: The solids content was measured by weighing the given composition in the indicated amounts and then evaporating the water in a 60°C oven. The solids content for the indicated examples is shown in Tables 2 and 3 below. Solution viscosity: Solution viscosity was measured using a Brookfield viscometer with spindles at frequencies of 10 and 30 rpm, as shown. The solution viscosity results for the examples shown are shown in Tables 2 and 3 below.

[0077] [Table 2] * -A comparative example is shown.

[0078] [Table 3] * -A comparative example is shown.

[0079] As shown in the data listed in Table 2 above, the examples of the present invention prepared in the presence of polyacrylic acid contain 10% by weight of MPEGMA copolymer solids, but yield a much lower viscosity than the comparative examples. This decrease in viscosity is proportional to the amount of poly(acrylic acid) added. It is important to note that all examples and comparative examples have the same MPEGMA copolymer content. However, the total solids increased with the amount of poly(acrylic acid) added. Nevertheless, the measured viscosity decreased with the amount of poly(acrylic acid) added. Finally, Table 3 above lists the viscosities of Examples 4 and 5 of the present invention, which are acrylic. Oxyalkylene side chain group-containing brush polymer , and also contain MAA as a comonomer in copolymer form. The compositions of Examples 4 and 5 showed dramatically reduced viscosity even with the same solid content as Comparative Example 1. Furthermore, although this application relates to the invention described in the claims, it may also encompass the following as other embodiments. [1] An aqueous composition for use as a thickening agent and water retention aid, comprising an aqueous medium; A brush polymer containing one or more oxyalkylene side chain groups, comprising one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups and polymerization residues of an initiator in a polymerized or copolymerized form; With one or more aromatic cofactors; The brush polymer containing the oxyalkylene side chain group comprises one or more carboxylic acid group-containing fluids selected from ethylenically unsaturated carboxylic acids, polymeric polycarboxylic acids, or mixtures thereof in copolymer form as part of the oxyalkylene side chain group-containing brush polymer. The aqueous medium is at least 90% by weight of water. Furthermore, the composition is an aqueous composition having a pH of 1 to 5 and a solid content in the range of 8 to 60% by weight. [2] The aqueous composition according to [1] above, having a pH of 1 to 4.8, and further comprising a composition that is substantially salt-free or does not contain an addition salt, except for any one or more initiators or polymerization by-products thereof. [3] Total number of moles of carboxylic acid (the total number of moles of carboxylic acid is determined by adding the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce the one or more oxyalkylene side-chain group-containing brush polymers and the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce the one or more polymer polycarboxylic acids, and if any polymer polycarboxylic acid is not an addition polymer, the total number of moles of carboxylic acid groups in the one or more polymer polycarboxylic acids) The molar ratio of oxyalkylene to the total number of moles (the total number of moles of oxyalkylene is determined by multiplying the total number of moles of the one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups used to produce the one or more oxyalkylene side-chain group-containing brush polymer by the average number of oxyalkylene chain groups in the total amount of acrylic or vinyl macromonomers containing oxyalkylene chain groups, as reported by the macromonomer manufacturer) is The aqueous composition described in [1] above, wherein the ratio is in the range of 0.1:1 to 10:1. [4] The aqueous composition according to [3] above, wherein the molar ratio of the total number of moles of carboxylic acid to the total number of moles of oxyalkylene is in the range of 0.2:1 to 5:1. [5] The aqueous composition according to [1] above, comprising a storage-stable aqueous mixture or additive concentrate having a solid content in the range of 10 to 40% by weight. [6] A method for preparing an aqueous composition, The process involves polymerizing an aqueous monomer mixture of an aqueous medium and one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups at a pH of 1 to 5 in the presence of one or more initiators, in the presence of one or more carboxylic acid group-containing fluids selected from copolymerizable ethylenically unsaturated carboxylic acids, polymeric polycarboxylic acids, or mixtures thereof, to form an oxyalkylene side-chain group-containing brush polymer. A method wherein the aqueous portion of the aqueous monomer mixture contains at least 90% by weight of water, and the polymerization is carried out with a solid content in the range of 8 to 60% by weight. [7] In the polymerization described above, the aqueous monomer mixture has a pH of 1 to 4.8, Furthermore, the method according to [6] above, wherein the aqueous monomer mixture is substantially salt-free or does not contain an addition salt, with the exception of any one or more initiators. [8] In the polymerization of the aqueous monomer mixture, The total number of moles of carboxylic acid (the total number of moles of carboxylic acid is determined by adding the total number of moles of ethylenically unsaturated carboxylic acid monomers used in the polymerization of one or more macromonomers containing oxyalkylene chain groups and the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce one or more polymer polycarboxylic acids; if any polymer polycarboxylic acid is not an addition polymer, the total number of moles of carboxylic acid groups in the one or more polymer polycarboxylic acids), The molar ratio of the total number of moles of oxyalkylene (determined by multiplying the total number of moles of oxyalkylene side chains in the acrylic or vinyl macromonomer polymer used to produce one or more oxyalkylene side chain group-containing brush polymers by the average number of oxyalkylene side chain groups in the total amount of acrylic or vinyl macromonomers containing oxyalkylene side chain groups, as reported by the macromonomer manufacturer) is, The method described in [6] above, in the range of 0.1:1 to 10:1. [9] The method according to [6], wherein the total amount of the acrylic or vinyl macromonomer containing the oxyalkylene chain group is in the range of 20 to 100% by weight, based on the total weight of the monomers used to produce the oxyalkylene side chain group-containing brush polymer.

[10] The method according to [6] above, wherein the polymerization is carried out with a solid content of 10 to 45% by weight.

[11] The method according to [6], wherein the aqueous monomer mixture comprises C1-C4 alkoxy poly(C2-C4 alkylene glycol) (meth)acrylate as one or more acrylic or vinyl macromonomers.

Claims

1. An aqueous composition for use as a thickening agent and water retention aid, comprising an aqueous medium; A brush polymer containing one or more oxyalkylene side chain groups, comprising one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups and polymerization residues of an initiator in a polymerized or copolymerized form; With one or more aromatic cofactors; The brush polymer containing the oxyalkylene side chain group comprises one or more carboxylic acid group-containing fluids selected from ethylenically unsaturated carboxylic acids, polymer polycarboxylic acids, or mixtures thereof in copolymer form as part of the oxyalkylene side chain group-containing brush polymer. The aqueous medium is at least 90% by weight of water. The composition has a pH of 1 to 5 and a solid content in the range of 8 to 60% by weight. The one or more aromatic cofactors are selected from poly(naphthalene sulfonate)formaldehyde condensate polymer, poly(styrene-co-styrene sulfonate) copolymer, catechol tannin, phenolic resin, polyphenol, naphthol, and mixtures thereof. The oxyalkylene side chain group of the brush polymer is selected from a homopolymer of an acrylic or vinyl macromonomer having an oxyalkylene chain group, or a copolymer of one or more acrylic or vinyl macromonomers and one or more ethylenically unsaturated carboxylic acid monomers. An aqueous composition comprising the oxyalkylene side-chain group-containing brush polymer and one or more aromatic cofactors.

2. The aqueous composition according to claim 1, having a pH of 1 to 4.8, and further comprising a composition that is substantially salt-free or does not contain an addition salt, except for any one or more initiators or polymerization by-products thereof.

3. The total number of moles of carboxylic acid (the total number of moles of carboxylic acid is determined by adding the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce one or more oxyalkylene side-chain group-containing brush polymers and the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce one or more polymer polycarboxylic acids; if any polymer polycarboxylic acid is not an addition polymer, the total number of moles of carboxylic acid groups in the one or more polymer polycarboxylic acids), The molar ratio of oxyalkylene to the total number of moles (the total number of moles of oxyalkylene is determined by multiplying the total number of moles of the one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups used to produce the one or more oxyalkylene side-chain group-containing brush polymer by the average number of oxyalkylene chain groups in the total amount of acrylic or vinyl macromonomers containing oxyalkylene chain groups, as reported by the macromonomer manufacturer) is The aqueous composition according to claim 1, wherein the ratio is in the range of 0.1:1 to 10:

1.

4. The aqueous composition according to claim 3, wherein the molar ratio of the total number of moles of carboxylic acid to the total number of moles of oxyalkylene is in the range of 0.2:1 to 5:

1.

5. The aqueous composition according to claim 1, further comprising a storage-stable aqueous mixture or additive concentrate having a solid content in the range of 10 to 40% by weight.

6. A method for preparing an aqueous composition, The process involves polymerizing an aqueous monomer mixture of an aqueous medium and one or more acrylic or vinyl macromonomers containing oxyalkylene chain groups at a pH of 1 to 5 in the presence of one or more initiators, in the presence of one or more carboxylic acid group-containing fluids selected from copolymerizable ethylenically unsaturated carboxylic acids, polymeric polycarboxylic acids, or mixtures thereof, to form an oxyalkylene side-chain group-containing brush polymer. The aqueous portion of the aqueous monomer mixture contains at least 90% by weight of water, and the polymerization is carried out with a solid content in the range of 8 to 60% by weight, A method wherein the oxyalkylene side chain group of the brush polymer is selected from a homopolymer of an acrylic or vinyl macromonomer having an oxyalkylene chain group, or a copolymer of one or more acrylic or vinyl macromonomers and one or more ethylenically unsaturated carboxylic acid monomers.

7. In the polymerization described above, the aqueous monomer mixture has a pH of 1 to 4.

8. Furthermore, the method according to claim 6, wherein the aqueous monomer mixture is substantially salt-free or does not contain an addition salt, with the exception of any one or more initiators.

8. In the polymerization of the aqueous monomer mixture, The total number of moles of carboxylic acid (the total number of moles of carboxylic acid is determined by adding the total number of moles of ethylenically unsaturated carboxylic acid monomers used in the polymerization of one or more macromonomers containing oxyalkylene chain groups and the total number of moles of ethylenically unsaturated carboxylic acid monomers used to produce one or more polymer polycarboxylic acids; if any polymer polycarboxylic acid is not an addition polymer, the total number of moles of carboxylic acid groups in the one or more polymer polycarboxylic acids), The molar ratio of the total number of moles of oxyalkylene (determined by multiplying the total number of moles of oxyalkylene side chains in the acrylic or vinyl macromonomer polymer used to produce one or more oxyalkylene side chain group-containing brush polymers by the average number of oxyalkylene side chain groups in the total amount of acrylic or vinyl macromonomers containing oxyalkylene side chain groups, as reported by the macromonomer manufacturer) is, The method according to claim 6, wherein the ratio is in the range of 0.1:1 to 10:

1.

9. The method according to claim 6, wherein the total amount of the acrylic or vinyl macromonomer containing the oxyalkylene chain group is in the range of 20 to 100% by weight, based on the total weight of the monomers used to produce the oxyalkylene side chain group-containing brush polymer.

10. The method according to claim 6, wherein the polymerization is carried out with a solid content of 10 to 45% by weight.

11. The aqueous monomer mixture is one or more acrylic or vinyl macromonomers, C １ ~C ４ Alkoxypoly(C) ２ ~C ４ The method according to claim 6, comprising alkylene glycol (meth)acrylate.

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