Polyalkylene oxide addition polymer, polyalkylene oxide addition polymer-containing composition, cement admixture, and hydraulic composition

Abstract

This polyalkylene oxide addition polymer is represented by general formula (I) or (II). (Symbols in the formulae are as defined in the description.)

Description

Polyalkylene oxide addition polymer, polyalkylene oxide addition polymer-containing composition, cement admixture, and hydraulic composition

[0001] The present invention relates to a polyalkylene oxide addition polymer, a polyalkylene oxide addition polymer-containing composition, a cement admixture, and a hydraulic composition.

[0002] Hydraulic compositions (also called concrete compositions), such as cement paste, mortar, and concrete, are used in various fields, including civil engineering and construction. Hydraulic compositions are prepared by mixing a hardening material, such as cement, an aggregate, such as sand, gravel, or stone, water, and, if necessary, additives. Examples of additives include cement admixtures (Patent Documents 1 and 2). Antifoaming agents may also be used as additives.

[0003] JP 2001-220417 A JP 2001-172068 A

[0004] The reason why an antifoaming agent is used in a hydraulic composition is that foaming occurs during kneading. If an antifoaming agent can be omitted or the amount of antifoaming agent used can be reduced, a hydraulic composition using a reduced amount of additives can be realized. To achieve this, it is considered to provide a hydraulic composition in which foaming during kneading is suppressed. However, it cannot be said that sufficient research has been conducted on means for suppressing foaming that are alternatives to using an antifoaming agent. The foaming problem is not limited to hydraulic compositions, but is a common problem in compositions that may generate a gas-liquid interface. In particular, the foaming problem becomes more pronounced in compositions in which the liquid volume fluctuates, since shearing, such as stirring or kneading, is frequently performed.

[0005] Therefore, an object of the present invention is to provide a polyalkylene oxide addition polymer (hereinafter also referred to as "RO addition polymer") that can suppress foaming in a composition that may generate a gas-liquid interface; and a composition, cement admixture, and hydraulic composition that contain the RO addition polymer.

[0006] As a result of investigations aimed at solving the above problems, the inventors have found that an RO addition polymer having a specific structure can solve the above problems and suppress foaming in a composition that may generate a gas-liquid interface, and have completed the present invention.

[0007] That is, the present invention provides the following items [1] to

[15] : [1] A polyalkylene oxide addition polymer represented by the following general formula (I) or (II): (In the above formula, R １ and R ２ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms. ３１ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ may be bonded to each other to form a ring structure. Ａ and R Ｂ each independently represents an alkylene group having 2 to 6 carbon atoms. Ａ O- may be the same or different from each other. Ｂ O- may be the same or different from each other. o and p each independently represent an integer of 0 or 1. m represents an oxyalkylene-R Ａ n represents the number of moles of oxyalkylene-R Ｂ[2] The polyalkylene oxide addition polymer according to the above item [1], wherein o and p are the same number. [3] The polyalkylene oxide addition polymer according to the above item [1] or [2], wherein o and p are 0. [4] In the above general formula (I), R ３１ is a hydrogen atom, and R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ [5] The polyalkylene oxide addition polymer according to any one of the above [1] to [3], wherein R ３２ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ [6] The polyalkylene oxide addition polymer according to any one of [1] to [3], wherein R are each independently a hydrogen atom or a methyl group. ４ , R ５ , R ６ and R ７ [7] The polyalkylene oxide addition polymer according to any one of the above [1] to [5], wherein R is a hydrogen atom. Ａ and R Ｂ are each independently an ethylene group, a propylene group, or a butylene group. [8] The polyalkylene oxide addition polymer according to any one of [1] to [7] above, wherein m and n are each independently within the range of 5 to 100. [9] The polyalkylene oxide addition polymer according to any one of [1] to [8] above, having a weight average molecular weight of 800 to 5000.

[10] The polyalkylene oxide addition polymer according to any one of [1] to [8] above, having a surface tension of 68.0 mN / m in a 0.001% by mass aqueous solution measured at 20°C by the Young-Laplace method in a hanging drop method. ２

[11] The polyalkylene oxide addition polymer according to any one of the above [1] to [9], wherein the surface tension of the polyalkylene oxide addition polymer measured at 20°C by the Young-Laplace method in the hanging drop method using an aqueous solution obtained by diluting the polyalkylene oxide addition polymer with pure water as a sample liquid has a decrease retention rate ΔTs (%) of 50% or more, calculated based on the following formula (1): ΔTs=100×(ΔTs2-ΔTs1) / ΔTs2 (1) (in the above formula (1), ΔTs1 is the difference (mN / m) between the surface tension Ts0 of pure water at 20°C and the surface tension Ts1 of a 0.001% by mass aqueous solution) ２ ), and ΔTs2 is the difference (mN / m) between the surface tension Ts0 of pure water at 20°C and the surface tension Ts2 of a 0.01 mass% aqueous solution. ２ )

[12] Ts1 is 68.0 mN / m ２ or more, and Ts2 is 63.0 mN / m ２

[13] A polyalkylene oxide addition polymer containing composition comprising the polyalkylene oxide addition polymer according to any one of [1] to

[12] above.

[14] A cement admixture comprising the polyalkylene oxide addition polymer according to any one of [1] to

[12] above.

[15] A hydraulic composition comprising the polyalkylene oxide addition polymer or a derivative thereof according to any one of [1] to

[12] above.

[0008] According to the present invention, it is possible to provide a polyalkylene oxide addition polymer (hereinafter also referred to as an "RO addition polymer") that can suppress foaming in a composition that may generate a solid-liquid interface, as well as a composition, a cement admixture, and a hydraulic composition that contain the RO addition polymer.

[0009] The following describes an example of an embodiment of the present invention (hereinafter, sometimes referred to as "this embodiment"). However, the embodiment described below is an example for embodying the technical idea of ​​the present invention, and the present invention is not limited to the following description. Furthermore, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. For matters shown as numerical ranges, when there are several numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred embodiment. In this specification, when a numerical range is described as "XX to YY," it means "XX or more and YY or less."

[0010] [Polyalkylene oxide addition polymer (RO addition polymer)] The RO addition polymer according to the embodiment of the present invention has a specific structure represented by the following general formula (I) or (II): The symbols in formulas (I) and (II) will be described later.

[0011]

[0012] The RO addition polymer according to an embodiment of the present invention has the above-described specific structure, and thereby exhibits the effect of being able to suppress foaming in a composition that may produce a solid-liquid interface.

[0013] Although the detailed mechanism by which the above-described effects are achieved is unclear, the following points are considered. The above-described specific structure has a first hydrophilic moiety corresponding to the first polyalkylene oxide, a second hydrophilic moiety corresponding to the second polyalkylene oxide, and a hydrophobic moiety connecting the first and second hydrophilic moieties. That is, a hydrophobic moiety is present between the first and second hydrophilic moieties. Therefore, the RO addition polymer according to the embodiment of the present invention is less likely to localize at the gas-liquid interface in the composition, thereby contributing to less reduction in the surface tension at the gas-liquid interface. Furthermore, even if the amount of liquid in the composition fluctuates (for example, the amount of water fluctuates in a cement composition), the surface tension is stably maintained at a moderate level, which is thought to suppress foaming due to a decrease in surface tension. On the other hand, in the case of a polymer that does not have the above-mentioned specific structure, for example, a polymer that has a structure in which a single hydrophilic moiety and a single hydrophobic moiety are bonded, such a polymer is more likely to be localized at the gas-liquid interface in the composition than the RO addition polymer according to the embodiment of the present invention, and therefore is thought to be less likely to enjoy the effects based on the above-mentioned mechanism.

[0014] The symbols in the above general formulas (I) and (II) are explained below. １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.

[0015] From the viewpoint of ease of manufacturing, R １ and R ２ is preferably a hydrogen atom, a methyl group, or an acetyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0016] R ３１ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３１ is preferably a hydrogen atom, a methyl group, or an acetoxy group, more preferably a hydrogen atom or an acetoxy group, and even more preferably a hydrogen atom.

[0017] R３２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３２ is preferably a hydrogen atom, a methyl group, or an acetoxy group, more preferably a methyl group or an acetoxy group. ３２ is a methyl group. ３２ When R is a methyl group, the hydrophobicity of the hydrophobic moiety can be increased. ３２ When is a hydrogen atom, the hydrophobicity of the hydrophobic moiety can be prevented from becoming excessively high.

[0018] R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. From the viewpoint of ease of production and polymerizability, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0019] R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ may be bonded to each other to form a ring structure. In addition to the ring structure, any linking group may be included. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１Examples of the ring structure formed by bonding together include a single ring such as a cyclopropane ring, a cyclopentane ring, or a cyclohexane ring; a condensed ring such as a norbornane ring; a tetrahydrofuran ring, a pyrrolidine ring, or a tetrahydrothiophene ring.

[0020] R Ａ and R Ｂ R each independently represents an alkylene group having 2 to 6 carbon atoms. Ａ and R Ｂ Examples of the alkylene group having 2 to 6 carbon atoms represented by include an ethylene group, a propylene group (i.e., —CH(CH ３ ) CH ２ -), trimethylene group (i.e., -CH ２ CH ２ CH ２ -), n-butylene group, isobutylene group, n-pentylene group, isopentylene group, n-hexylene group, cyclohexylene group, and the like.

[0021] From the viewpoint of availability and reactivity, R Ａ and R Ｂ is preferably an ethylene group, a propylene group, or an n-butylene group, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group.

[0022] A plurality of oxyalkylene-R Ａ O- may be the same or different from each other. Ｂ O- may be the same or different.

[0023] o and p are each independently an integer of 0 or 1. m is an oxyalkylene-R Ａ n represents the number of moles of oxyalkylene-R Ｂ represents the number of moles of O— added. The number of moles added usually represents the average number of moles added, and does not have to be an integer.

[0024] From the viewpoint of obtaining a polymer having excellent stability, in formula (I), o and p are preferably the same number, and more preferably o and p are 0. In formula (II), o and p may be the same number or different numbers, and from the viewpoint of obtaining a polymer having excellent stability, o and p are preferably the same number, and in one embodiment, in formula (II), o and p are 0. From the viewpoint of polymerizability, m is preferably 5 to 100, more preferably 10 to 50, even more preferably 10 to 40, and still more preferably 15 to 30.

[0025] In general formula (I), R ３１ represents a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ Preferably, each independently represents a hydrogen atom or a methyl group. ３２ , R ４ , R ５ , R ６ , and R ７ Preferably, each independently represents a hydrogen atom or a methyl group. ３２ represents a methyl group, and R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ each independently represents a hydrogen atom or a methyl group.

[0026] In another embodiment of the present invention, in order to more reliably achieve the intended effects of the present invention, ４ , R ５ , R ６ , and R ７ represents a hydrogen atom, and o and p are preferably 0. In general formula (II), R ４ , R ５, R ６ , and R ７ preferably represents a hydrogen atom, and R ４ , R ５ , R ６ , and R ７ More preferably, represents a hydrogen atom, and o and p are 0.

[0027] <Weight Average Molecular Weight> The weight average molecular weight of the RO addition polymer is preferably 300 to 15,000, more preferably 500 to 10,000, and even more preferably 800 to 5,000, from the viewpoint of achieving the desired effects of the present invention.

[0028] <Surface Tension> From the viewpoint of more reliably achieving the intended effects of the present invention, the RO addition polymer according to the embodiment of the present invention preferably has a surface tension reduction retention rate ΔTs (%) of 50% or more, calculated based on the following formula (1) for the surface tension measured at 20°C by the Young-Laplace method in the pendant drop method using an aqueous solution obtained by diluting the polymer with pure water as a sample liquid: ΔTs=100×(ΔTs2−ΔTs1) / ΔTs2 (1) (In the above formula (1), ΔTs1 is the difference (mN / m) between the surface tension Ts0 of pure water at 20°C and the surface tension Ts1 of a 0.001% by mass aqueous solution). ２ ), and ΔTs2 is the difference (mN / m) between the surface tension Ts0 of pure water at 20°C and the surface tension Ts2 of a 0.01 mass% aqueous solution. ２ The surface tension can be measured in detail by the method described in the Examples section. The surface tension Ts0 of pure water at 20°C is 72.75 mN / m ２ may also be used.

[0029] The reduction rate ΔTs (%) is a measure of how much the surface tension is maintained when the concentration of the sample solution fluctuates. A larger value for the reduction rate ΔTs indicates that the sample (in this embodiment, the RO addition polymer), which is the dispersoid in the sample solution, contributes to maintaining the surface tension of the aqueous solution even when the concentration of the aqueous solution fluctuates. On the other hand, a smaller value for the reduction rate ΔTs indicates that the sample is more likely to cause the surface tension of the aqueous solution to fluctuate when the concentration of the aqueous solution fluctuates; specifically, a larger tendency for the surface tension to decrease significantly as the concentration of the aqueous solution increases.

[0030] Therefore, from the viewpoint of more significantly achieving the intended effects of the present invention, the reduction amount maintenance rate ΔTs (%) is preferably 51% or more, more preferably 53% or more, and even more preferably 55% or more. The upper limit of the reduction amount maintenance rate ΔTs (%) is naturally determined depending on the dispersoid, but may be, for example, 85% or less, 80% or less, or 75% or less.

[0031] The Ts2 is 60.0 mN / m (i.e., in an aqueous solution with a concentration of 0.01% by mass). ２ More than 61.5 mN / m is preferable. ２ More preferably, 63.0 mN / m or more ２ More preferably, it is 60.0 mN / m or more. ２ If the surface tension is equal to or greater than this, it can be said that this is a sufficiently practical surface tension value from the viewpoint of suppressing foaming at such a concentration. Furthermore, the above Ts1 (i.e., in a dilute aqueous solution obtained by diluting an aqueous solution with a concentration of about 0.01% by mass by about 10 times) is 68.0 mN / m ２ More than 68.2 mN / m ２ More preferably, 68.2 mN / m or more ２ More preferably, Ts1 is 68.0 mN / m or more. ２ or more, and Ts2 is 63.0 mN / m ２ As a result, the decrease amount maintenance rate ΔTs (%) can be reliably increased.

[0032] The RO addition polymer may contain impurities. Impurities may include compounds (e.g., polyethylene glycol (PEG)) that can significantly reduce the surface tension even in trace amounts. When the RO addition polymer contains such impurities, the Ts2, Ts1, and ΔTs values ​​for an RO addition polymer containing no impurities or containing only trace amounts of impurities may be estimated by understanding the tendency of the Ts2, Ts1, and ΔTs values ​​to vary depending on the impurity content using a method well known to those skilled in the art. It is preferable to reduce the amount of impurities contained in the RO addition polymer as much as possible by purification or other methods. The amount of impurities contained in the RO addition polymer is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total amount. The PEG content can be determined from the NMR integrated value.

[0033] <Production Method> The RO addition polymer according to an embodiment of the present invention can be produced by a variety of methods, but a representative production method is as follows: The polymer can be synthesized by adding preferably 5 to 100 moles of an alkylene oxide having 2 to 6 carbon atoms to an unsaturated diol having an alkenyl group and having 2 to 12 carbon atoms, such as 2-methylene-1,3-propanediol, in the presence of an alkali catalyst such as potassium hydroxide or sodium hydroxide, or a catalyst such as boron trifluoride or tin tetrachloride.

[0034] [Polyalkylene oxide addition polymer (RO addition polymer)-containing composition] The RO addition polymer composition according to an embodiment of the present invention contains the polyalkylene oxide addition polymer (RO addition polymer) described above. By including the RO addition polymer according to an embodiment of the present invention, such a composition can suppress foaming in a composition that may form a gas-liquid interface. The RO addition polymer composition may contain the RO addition polymer represented by formula (I), the RO addition polymer represented by formula (II), or both the RO addition polymer represented by formula (I) and the RO addition polymer represented by formula (II).

[0035] The RO addition polymer-containing composition preferably contains water or an aqueous dispersion medium. Since the RO addition polymer contains a hydrophilic moiety as described above, it can be well dispersed in water or an aqueous dispersion medium. Because the RO addition polymer has such good dispersibility in water or an aqueous dispersion medium, even a small amount can suppress foaming. From this perspective, the content of the RO addition polymer in the RO addition polymer-containing composition is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.005% by mass or more. The upper limit of the RO addition polymer content in the RO addition polymer-containing composition is not limited as long as the desired effects of the present invention are achieved. The surface tension of the RO addition polymer-containing composition is preferably 60 mN / m ２ From the viewpoint of maintaining the above, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, and in some cases may be 0.1% by mass or less or 0.05% by mass or less.

[0036] The RO addition polymer-containing composition preferably contains a solid component other than the RO addition polymer, preferably a powdery or granular solid component or a liquid oil component. As described above, the RO addition polymer contains a hydrophobic moiety, and therefore tends to exhibit adsorption to solid components and affinity for oil components, thereby enhancing the dispersibility of the solid components or oil components.

[0037] More preferably, the RO addition polymer-containing composition contains solids or liquid oil other than the RO addition polymer and water or an aqueous dispersion medium. This allows the solids or oil adsorbed via the hydrophobic moieties of the RO addition polymer to be well dispersed in water or an aqueous dispersion medium. The content of solids other than the RO addition polymer, preferably powdery or granular solids or liquid oil, in the RO addition polymer-containing composition is not limited as long as they can be mixed with the RO addition polymer (e.g., by stirring or shearing such as kneading). The content of such solids other than the RO addition polymer may be 0.1% by mass or more, 1% by mass or more, or 99% by mass or less, or 90% by mass or less. The total content of the RO addition polymer and solids other than the RO addition polymer in the RO addition polymer-containing composition may be, for example, 0.5 to 80% by mass, 1 to 50% by mass, or 3 to 40% by mass.

[0038] When the RO addition polymer composition according to an embodiment of the present invention contains an RO addition polymer and water, and the content of the polyalkylene oxide addition polymer is in the range of 0.01 parts by mass or more and preferably 0.1 parts by mass or less per 100 parts by mass of water, the surface tension TsA of the composition measured by the Young-Laplace method in the hanging drop method using the composition as a sample liquid is 63 mN / m ２ or more, and the surface tension TsB of the composition measured by the Young-Laplace method in the hanging drop method using a diluted solution obtained by diluting the composition 10 times with pure water as a sample liquid is 68 mN / m ２ By knowing the surface tension when diluted 10 times in this way, it is possible to confirm in advance that even when the liquid amount in the RO addition polymer composition fluctuates, the amount of decrease in surface tension is small and that the desired effects of the present invention can be expected to be achieved.

[0039] <Other Components> The RO addition polymer-containing composition according to the embodiment of the present invention may contain, as necessary, an antifoaming agent, an air-enhancing agent, a cement dispersant, a strengthening improver, a set retarder, a set accelerator, a material separation reducer, a hydraulic powder, a non-hydraulic powder, an aggregate, an alcohol-based solvent such as methyl alcohol or ethyl alcohol, a hydrocarbon-based solvent such as toluene or n-hexane, an ester-based solvent such as ethyl acetate, a ketone-based solvent such as acetone or methyl ethyl ketone, an ether-based solvent such as tetrahydrofuran, etc. However, because the RO addition polymer has the effect of suppressing foaming, the content of the antifoaming agent in the RO addition polymer-containing composition can be kept to a minimum.

[0040] [Cement Admixture] The RO addition polymer and RO addition polymer-containing composition according to the embodiments of the present invention can be suitably used as components of cement admixtures. In one aspect of the present invention, the cement admixture according to the embodiments of the present invention contains the RO addition polymer according to the embodiments of the present invention. Such RO addition polymer may be an RO addition polymer represented by formula (I), an RO addition polymer represented by formula (II), or both an RO addition polymer represented by formula (I) and an RO addition polymer represented by formula (II). In another aspect of the present invention, the cement admixture according to the embodiments of the present invention contains the RO addition polymer-containing composition according to the embodiments of the present invention. Such an RO addition polymer composition may contain an RO addition polymer represented by formula (I), an RO addition polymer represented by formula (II), or both an RO addition polymer represented by formula (I) and an RO addition polymer represented by formula (II). The cement admixture according to the embodiments of the present invention can suppress foaming.

[0041] The cement admixture may contain components other than the RO addition polymer and RO addition polymer-containing composition of the present invention, as long as the effects of the present invention are not impaired. Examples of other components include antifoaming agents, air-enhancing agents, cement dispersants, strengthening improvers, set retarders, set accelerators, material separation reducers, hydraulic powders, non-hydraulic powders, aggregates, water, alcoholic solvents such as methyl alcohol and ethyl alcohol, hydrocarbon solvents such as toluene and n-hexane, ester solvents such as ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as tetrahydrofuran.

[0042] Examples of antifoaming agents include oxyalkylene-based antifoaming agents, silicone-based antifoaming agents, and aliphatic amine-based antifoaming agents. Preferred oxyalkylene-based antifoaming agents are polyoxyalkylene glycol alkyl ethers, preferred silicone-based antifoaming agents are dimethylpolysiloxane, and preferred aliphatic amine-based antifoaming agents are alkyldimethylamines and their salts. One or more types of antifoaming agents may be used in combination. As mentioned above, RO addition polymers have the effect of suppressing foaming, allowing the content of antifoaming agent in the cement admixture to be kept to a minimum.

[0043] Examples of the air-entraining agent include resin soaps, saturated or unsaturated fatty acids, modified rosin acids, alkylaryl sulfonates, and polyoxyalkylene alkyl ether sulfates. Among these, modified rosin acids and alkylaryl sulfonates are preferred. One or more types of air-entraining agents may be used in combination.

[0044] Examples of cement dispersants include polyalkylaryl sulfonates such as naphthalene sulfonic acid formaldehyde condensates, melamine formalin resin sulfonates such as melamine sulfonic acid formaldehyde condensates, lignin sulfonates, polycarboxylic acid dispersants, phosphate dispersants containing phosphate groups, etc. One or more types of cement dispersants may be used in combination.

[0045] Examples of the strength improver include alkanolamines, such as triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, etc. One or more types of strength improvers may be used in combination.

[0046] Examples of the setting retarder include oxycarboxylic acids (salts) such as gluconic acid (salt), citric acid (salt), and tartaric acid (salt), sugars such as glucose, sugar alcohols such as sorbitol, and phosphonic acids such as aminotri(methylenephosphonic acid). One or more setting retarders may be used in combination.

[0047] Examples of the hardening accelerator include soluble calcium salts such as calcium chloride and calcium nitrite, chlorides such as iron chloride and magnesium chloride, formates such as thiosulfates, formic acid and calcium formate, etc. One or more hardening accelerators may be used in combination.

[0048] Examples of the material separation reducing agent include various thickeners such as nonionic cellulose ethers. One or more types of material separation reducing agents may be used in combination.

[0049] Hydraulic powder refers to a powder that hardens when it comes into contact with water. Examples of hydraulic powders include Portland cement, calcium silicate, calcium aluminate, calcium fluoroaluminate, calcium sulfoaluminate, calcium aluminoferrite, calcium phosphate, gypsum hemihydrate, gypsum anhydrite, and self-hardening quicklime powder. One or more hydraulic powders may be used in combination depending on the desired physical properties of concrete.

[0050] Non-hydraulic powder refers to a powder that does not harden by itself even when it comes into contact with water, and also includes powders whose components are eluted in an alkaline or acidic atmosphere, or in a high-pressure steam atmosphere, and react with other eluted components to form a product. Examples of non-hydraulic powders include calcium hydroxide powder, gypsum dihydrate powder, calcium carbonate powder, silica powder, clay powder, granulated blast furnace slag, fly ash, and silica fume. One or more non-hydraulic powders may be used in combination depending on the desired physical properties of concrete.

[0051] Any aggregate may be used as the aggregate, such as fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.). Examples of such aggregates include gravel, crushed stone, granulated slag, and recycled aggregate. Other examples of such aggregates include refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia. One or more types of aggregate may be used in combination depending on the desired physical properties of the concrete.

[0052] The content of the RO addition polymer in the cement admixture can be adjusted appropriately depending on the purpose. From the viewpoint of suppressing foaming, the content of the RO addition polymer in the cement admixture is, for example, 0.00001% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and may be 100% by mass.

[0053] The content of the RO addition polymer-containing composition in the cement admixture can be adjusted appropriately depending on the purpose. From the viewpoint of suppressing foaming, the content of the RO addition polymer-containing composition in the cement admixture is, for example, 0.00001% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and may even be 100% by mass. The solids concentration of the cement admixture may be, for example, 10 to 100% by mass, 20 to 100% by mass, or 30 to 100% by mass.

[0054] [Hydraulic Composition] In one aspect of the present invention, the hydraulic composition according to the present invention contains an RO addition polymer according to the present invention. Such an RO addition polymer may be an RO addition polymer represented by formula (I), an RO addition polymer represented by formula (II), or both an RO addition polymer represented by formula (I) and an RO addition polymer represented by formula (II). In another aspect of the present invention, the hydraulic composition according to the present invention contains an RO addition polymer-containing composition according to the present invention. Such an RO addition polymer composition may contain an RO addition polymer represented by formula (I), an RO addition polymer represented by formula (II), or both an RO addition polymer represented by formula (I) and an RO addition polymer represented by formula (II). Since the hydraulic composition according to the present invention contains an RO addition polymer, foaming can be suppressed, particularly during mixing (shearing, such as stirring or kneading). Since the liquid volume (water content) of a hydraulic composition usually fluctuates, it is preferable to contain an RO addition polymer that is evaluated to have a large value of the loss retention rate ΔTs when made into an aqueous solution.

[0055] Hydraulic compositions refer to cement pastes, mortar compositions, concrete compositions, and the like. The hydraulic compositions according to the present invention may be uncured materials before hardening, partially cured semi-cured materials, or cured materials. During hardening, the RO addition polymer may react with other components to form a reaction product. In this case, the hydraulic composition contains a derivative of the RO addition polymer. The hydraulic composition includes a solidifying agent such as cement, aggregates such as sand, gravel, and stone, water, and the like. If necessary, the hydraulic composition may also include cement admixtures such as antifoaming agents, air-enhancing agents, and cement dispersants, strengthening improvers, hardening retarders, hardening accelerators, material separation reducers, hydraulic powders, non-hydraulic powders, alcohol-based solvents such as methyl alcohol and ethyl alcohol, hydrocarbon-based solvents such as toluene and n-hexane, ester-based solvents such as ethyl acetate, ketone-based solvents such as acetone and methyl ethyl ketone, and ether-based solvents such as tetrahydrofuran. As mentioned above, the RO addition polymer has the effect of suppressing foaming, allowing the content of the antifoaming agent in the hydraulic composition to be minimized.

[0056] The contents of the RO addition polymer and the RO addition polymer-containing composition in the hydraulic composition can be adjusted appropriately depending on the purpose. The content of the RO addition polymer in the hydraulic composition is preferably 0.001 to 10 mass%, more preferably 0.001 to 5 mass%, and even more preferably 0.001 to 3 mass%. The content of the RO addition polymer-containing composition in the hydraulic composition is preferably 0.001 to 20 mass%, more preferably 0.001 to 10 mass%, and even more preferably 0.001 to 5 mass%.

[0057] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0058] [Measurement and Evaluation Methods] Various physical properties were measured or evaluated by the following methods.

[0059] <1. Surface Tension> (1-1. Preparation of Sample Solutions) Two types of aqueous solutions were prepared as sample solutions by diluting the RO addition polymers obtained in the Examples and Comparative Examples described below with pure water. Specifically, 0.40 g of the RO addition polymer sample and 19.61 g of distilled water were first placed in a 50 mL sample bottle and stirred to prepare a concentrated aqueous solution. Subsequently, this concentrated aqueous solution was diluted 200 times and 2,000 times to prepare aqueous solutions. This resulted in two types of sample solutions: an aqueous solution containing 0.01% by mass of the RO addition polymer and an aqueous solution containing 0.001% by mass of the RO addition polymer. The sample solutions were maintained at 20°C. (1-2. Measurement) The surface tensions of the prepared aqueous solutions were measured at 20°C using a Kyowa Interface Science Co., Ltd. fully automated contact angle meter "DMo-701" by the Young-Laplace pendant drop method. The measured surface tension of the 0.001 mass% aqueous solution was defined as Ts1 (mN / m ２ ), the surface tension of a 0.01 mass% aqueous solution is Ts2 (mN / m ２ The results are shown in Table 1.

[0060] (1-3. Calculation of the reduction amount maintenance rate ΔTs) Next, the reduction amount maintenance rate ΔTs (%) was calculated based on the following formula (1): ΔTs=100×(ΔTs2−ΔTs1) / ΔTs2 (1) (In the above formula (1), ΔTs1 is the difference (mN / m) between the surface tension Ts0 of pure water at 20° C. and the surface tension Ts1 of a 0.001% by mass aqueous solution). ２ ), and ΔTs2 is the difference (mN / m) between the surface tension Ts0 of pure water at 20°C and the surface tension Ts2 of a 0.01 mass% aqueous solution. ２ The surface tension Ts0 of pure water at 20°C is 72.75 mN / m ２ The results are shown in Table 1. When the value of the decrease amount maintenance rate ΔTs was 50% or more, it was evaluated as "pass", and when it was less than 50%, it was evaluated as "fail".

[0061] Example 1 2-methylenepropane-1,3-diol was reacted with ethylene oxide by a known method to obtain an ethylene oxide addition polymer (D-1) having a total of 40 moles of ethylene oxide added.

[0062] The number of moles of ethylene oxide added is １ Confirmation by H-NMR revealed that the average number of moles added was 40. Because 2-methylenepropane-1,3-diol is a C2-symmetric molecule, the reactivity of the two alcohol moieties is equivalent, and therefore it was presumed that the same number of ethylene oxides were added to the two ethylene oxide moieties in the ethylene oxide addition polymer (D-1). Therefore, the ethylene oxide addition polymer (D-1) was presumed to be represented by the following formula (molecular weight: 1,848).

[0063]

[0064] The surface tension of the ethylene oxide addition polymer (D-1) was measured, and the reduction retention rate ΔTs was evaluated.

[0065] [Example 2] An ethylene oxide polymer was obtained in the same manner as in Example 1, except that the total number of moles of ethylene oxide added was changed from 40 to 100. This ethylene oxide polymer was designated (D-2). １When confirmed by H-NMR, the average number of moles added was 100. It was presumed that the same number of ethylene oxides were added to the two ethylene oxide moieties, and the ethylene oxide addition polymer (D-2) was presumed to be represented by the following formula (molecular weight: 4,488).

[0066]

[0067] The surface tension of the ethylene oxide addition polymer (D-2) was measured, and the decrease retention rate ΔTs was evaluated.

[0068] Example 3 2-Isopropylidene-1,3-propanediol was reacted with ethylene oxide by a known method to obtain an ethylene oxide addition polymer (D-4) having a total of 50 moles of ethylene oxide added.

[0069] The number of moles of ethylene oxide added is １ When confirmed by H-NMR, the average number of moles added was 50. Since the reactivities of the two alcohol moieties are equivalent, it was presumed that the same number of ethylene oxides were added to the two ethylene oxide moieties in the ethylene oxide addition polymer (D-4). Therefore, the ethylene oxide addition polymer (D-4) was presumed to be represented by the following formula (molecular weight: 2,318).

[0070]

[0071] The surface tension of a compound (D-3) obtained by mixing the ethylene oxide addition polymer (D-4) and the ethylene oxide addition polymer (D-1) in a weight ratio of 1:9 was measured, and the surface tension reduction retention rate ΔTs was evaluated.

[0072] Comparative Example 1 As a comparative compound, an ethylene oxide polymer (E-1) represented by the following formula, in which the number of moles of ethylene oxide added was 50, was prepared. The ethylene oxide polymer (E-1) used was manufactured by Tokyo University Chemical Industry Co., Ltd.

[0073]

[0074] The surface tension of the ethylene oxide addition polymer (E-1) was measured, and the reduction retention rate ΔTs was evaluated.

[0075] Comparative Example 2 An ethylene oxide polymer (E-2) represented by the following formula, in which the number of moles of ethylene oxide added was 80, was prepared as a comparative compound. The ethylene oxide polymer (E-2) used was manufactured by Okusa Corporation.

[0076]

[0077] The surface tension of the ethylene oxide addition polymer (E-2) was measured, and the reduction retention rate ΔTs was evaluated.

[0078] Table 1 shows the measurement results.

[0079]

[0080] It can be seen from Table 1 that the ethylene oxide addition polymers of Examples 1, 2, and 3 had a reduction retention rate ΔTs of 50% or more. Therefore, it was expected that the RO addition polymers of Examples 1, 2, and 3 would be able to suppress foaming of the composition. In fact, when the RO addition polymers of Examples 1, 2, and 3 were used in cement compositions as hydraulic compositions, it was confirmed that foaming during kneading was suppressed compared to the cement compositions containing the ethylene oxide addition polymers of Comparative Examples 1 and 2.

[0081] The RO addition polymer, RO addition polymer-containing composition, and cement admixture of the present invention can be suitably used in compositions capable of forming a gas-liquid interface, such as hydraulic compositions, particularly cement compositions.

Claims

1. A polyalkylene oxide addition polymer represented by the following general formula (I) or (II): (In the above formula, R １ and R ２ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms. ３１ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ may be bonded to each other to form a ring structure. Ａ and R Ｂ each independently represents an alkylene group having 2 to 6 carbon atoms. Ａ O- may be the same or different. Ｂ O- may be the same or different. o and p each independently represent an integer of 0 or 1. m represents an oxyalkylene-R Ａ n represents the number of moles of oxyalkylene-R Ｂ represents the number of moles of O- added.) 2. The polyalkylene oxide addition polymer of claim 1, wherein o and p are the same number.

3. The polyalkylene oxide addition polymer of claim 1, wherein o and p are 0.

4. In the general formula (I), R ３１ is a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ and each independently represents a hydrogen atom or a methyl group.

5. In the general formula (II), R ３２ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ and R １１ and each independently represents a hydrogen atom or a methyl group.

6. R ４ , R ５ , R ６ and R ７ The polyalkylene oxide addition polymer of claim 1 , wherein is a hydrogen atom.

7. R Ａ and R Ｂ 2. The polyalkylene oxide addition polymer of claim 1, wherein each is independently an ethylene group, a propylene group, or a butylene group.

8. The polyalkylene oxide addition polymer of claim 1, wherein m and n are each independently within the range of 5 to 100.

9. The polyalkylene oxide addition polymer of claim 1, having a weight average molecular weight of 800 to 5,000.

10. The surface tension of a 0.001% by weight aqueous solution measured at 20°C using the Young-Laplace method in the hanging drop method is 68.0 mN / m ２ The polyalkylene oxide addition polymer according to claim 1 .

11. The polyalkylene oxide addition polymer according to claim 1, wherein the surface tension of a sample liquid is measured at 20°C by the Young-Laplace method in the hanging drop method, and the reduction retention rate ΔTs (%) calculated based on the following formula (1) is 50% or more: ΔTs=100×(ΔTs2−ΔTs1) / ΔTs2 (1) (in the above formula (1), ΔTs1 is the difference (mN / m) between the surface tension Ts0 of pure water at 20°C and the surface tension Ts1 of a 0.001% by mass aqueous solution). ２ ), and ΔTs2 is the difference (mN / m) between the surface tension Ts0 of pure water at 20° C. and the surface tension Ts2 of a 0.01% by mass aqueous solution. ２ ) 12. Ts1 is 68.0 mN / m ２ or more, and Ts2 is 63.0 mN / m ２ The polyalkylene oxide addition polymer according to claim 11 .

13. A polyalkylene oxide addition polymer-containing composition comprising the polyalkylene oxide addition polymer according to any one of claims 1 to 12.

14. A cement admixture comprising the polyalkylene oxide addition polymer according to any one of claims 1 to 12.

15. A hydraulic composition comprising the polyalkylene oxide addition polymer or its derivative according to any one of claims 1 to 12.

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